Fundamentals of Chemical Engineering

FUNDAMENTALS OF CHEMICAL ENGINEERING
COMPILED BY: MUHAMMAD AFTAB AMIN
(COURSE MATERIAL FOR DEPARTMENTAL PROMOTION EXAMINATION (DPE))
Preface.................................................................................................................................................... 4 WHAT IS CHEMICAL ENGINEERING? ........................................................................................ 5 RAW MATERIALS FOR THE CHEMICAL INDUSTRY.............................................................. 9 2.1 2.2. 2.3. 2.4 MINERALS IN THE CHEMICAL INDUSTRY ......................................................... 10 MINING TECHNIQUES .......................................................................................... 14 TECHNIQUES OF PURIFICATION OR REFINING ............................................. 16 EXTRACTION TECHNIQUES FOR SOME MINERALS ......................................... 24
FUNDAMENTALS ............................................................................................................................. 28 3.1. 3.2 3.3. 3.4 3.5 3.6. THE SCOPE OF CHEMICAL ENGINEERING ..................................................... 30 UNITS - THE SI SYSTEM ...................................................................................... 32 THE BASIC RATE EQUATION ............................................................................. 35 DIMENSIONAL ANALYSIS ...................................................................................... 36 HEAT TRANSFER....................................................................................................... 37 FLUID MECHANICS .............................................................................................. 42
MACHINERY ......................................................................................................................... 48 THERMODYNAMICS ...................................................................................................................... 52 4.1 4.2 4.3 4.4 4.5 4.6 4.7 THE THERMODYNAMIC FUNCTIONS................................................................... 53 THE FIRST LAW ......................................................................................................... 54 THE SECOND LAW .................................................................................................... 55 THERMODYNAMIC TEMPERATURE .................................................................... 57 ENTROPY .................................................................................................................... 59 HEAT ENGINES .......................................................................................................... 60 THERMODYNAMICS AND EQUILIBRIUM..................................................................... 64
REACTION ENGINEERING ........................................................................................................... 67 5.1 5.2 5.3 5.4 5.5 5.6 TYPES OF CHEMICAL REACTION ......................................................................... 67 REACTION KINETICS ............................................................................................... 71 CATALYSIS ................................................................................................................. 76 CONTINUOUS REACTION EQUIPMENT ............................................................... 78 REACTOR DESIGN .................................................................................................... 81 SPECIAL CONSIDERATIONS IN REACTOR DESIGN ...................................... 84
UNIT OPERATIONS ......................................................................................................................... 86 6.1 6.2 6.3 MATERIAL AND THERMAL BALANCES .............................................................. 86 MASS TRANSFER ...................................................................................................... 91 ABSORPTION ............................................................................................................. 94
6.4 6.5 6.6 6.7
SOLVENT EXTRACTION .......................................................................................... 96 DISTILLATION ........................................................................................................... 99 CRYSTALLIZATION ................................................................................................ 107 FILTRATION ............................................................................................................ 110
PLANT SERVICES AND PLANT CONTROL ............................................................................. 112 7.1 7.2 7.3 7.4 7.5 7.6 STEAM ENERGY ...................................................................................................... 112 ELECTRICAL ENERGY ........................................................................................... 117 STEAM - WATER SYSTEMS................................................................................... 119 COOLING WATER SYSTEMS................................................................................. 119 OTHER FACTORY SITE SERVICES ................................................................... 121 INSTRUMENTATION AND CONTROL .............................................................. 121
DESIGNING AND BUILDING A CHEMICAL PLANT ............................................................. 129 8.1 8.2 8.3 8.4 DESIGN INFORMATION ......................................................................................... 131 PROJECT PROCEDURE ........................................................................................... 132 PROJECTS INVOLVING A PROCESS UNDER DEVELOPMENT ....................... 133 AMMONIA PLANT DESIGN ................................................................................... 139
THE CHEMICAL ENGINEERING PROFESSION .................................................................... 150 9.1 9.2 THE INSTITUTION OF CHEMICAL ENGINEERS ................................................ 151 THE CHEMICAL ENGINEER IN INDUSTRY ........................................................ 152
REFERENCE:................................................................................................................................... 161 SUGGESTED READING MATERIAL FOR FURTHER READING: ...................................... 161 Sample MCQs: ................................................................................................................................. 162
PREFACE
Chemical industry is one of our major growth and exporting industries. In spite of inflation many of its products have been steadily reduced in price, largely because of the improvements and advances achieved by the industry's technical staff. Chemical engineers find that their training qualifies them for work not only in the chemical industry but also in the whole range of process industries. The process industries are those in which materials are continuously changed from one form into another, and include oil refining, plastics and fibers, food and water, steel, glass, paper, drugs and other chemicals. The operations of many of these industries are increasingly international in nature, involving engineers of both producing companies and the plant construction industry in frequent travel. Chemical engineering is part scientific and part engineering. It is chemical engineers who translate the reactions and processes discovered in the laboratory into thousand tons per day process plants. For this is the scale of operation of many of today's plants- ethylene, ammonia and other fertilizers, oil refining and minerals and metallurgical processing plants. The cornerstone of chemical engineering is its concern with size and processing rates. The chemical engineer must decide the processing steps and equipment needed to prepare the reactants, carry out reaction in one or more stages, and separate the required product from the stream leaving the reactor and purify it. In these processing steps the types of equipment used include distillation columns, absorbers, heaters, driers, crushers, crystallizers, etc. The processes occurring in these units are the unit operations of chemical engineering. The chemical engineer uses his knowledge of the appropriate unit operation to specify the size, shape, internal design and operating temperature and pressure for each item of equipment. In spite of the modern scale of the process industries, the man who enters them today has difficulty in gaining adequate knowledge of these industries at the stage of choosing his course of professional studies. He joins the selected industry as an act of faith without fully realizing what he will find in it. It is one of the objects of this series to help to redress this situation. This book will provide the intending student with a picture of chemical engineering science and its place in the chemical industry; it will also enable him to form a foundation on which to base more detailed study of specific subjects. The contents, then, of the book are twofold. First, there are sections concerning the basic principles of chemical engineering and the tools of the chemical engineer; second, there are sections describing the role of chemical engineers in the industry. Most of the book is descriptive, but chemical engineering is a numerical subject and a few illustrative sections are included to outline the mathematical derivation of certain techniques. These sections could well be jumped over in a first reading of the book and returned to at leisure' (by those who have any). The book, after all, is intended to be readnot studied. When you have read it you will not be a chemical engineer but I hope you will have a better idea of the principles and practice of chemical engineering in industry.
Chapter 1
WHAT IS CHEMICAL ENGINEERING?

Chemical engineering is a relatively new science. The Institution of Chemical Engineers was founded in 1922 and the first undergraduate university department in 1933. There are now 26 universities and colleges with chemical engineering faculties, from which some 600 engineers graduate annually. Unlike most of Britain's other major industries, the chemical industry produces a vast range of products. It is often difficult to remember that the majority of its products would not be regarded as chemicals by the general public at all -for them, chemicals are in the chemist's shop. Pharmaceuticals are important products of the chemical industry, but the plastics, fibers, fertilizers, and detergents industries are giants by comparison. And, on the subject of the general public and its view of the chemical industry, it seems that even many an informed arid educated member of the public would consider that a chemical engineer was some sort of cross between the white-coated man in the chemist's and the overalled mechanic who repairs his car; a few paragraphs on the part played by chemical engineers in industry are therefore in order. The chemical engineer is concerned with the task of taking a chemical reaction that has been established in laboratory experiments and then designing, building, and operating large-scale plant exploiting the reaction. To amplify the part played by the chemical engineer we can look at some of the problems that he must face and the type of information he needs to solve them. The chemical engineer must be aware of the technology involved in all these problems, although some of them are generally tackled by more specialist engineers and scientists. Problem 1: A reaction is known to proceed in the laboratory, but how fast is the reaction, i.e. what length of reaction time is needed in the reaction vessel? This problem -and the more general one of choosing all reaction conditions including temperature, pressure, etc.is usually solved by carrying out laboratory experiments over a range of conditions. The chemical engineer then uses data from these, together with the physical properties of the reactants and other information on the system, to obtain a mathematical equation or set of equations describing the behavior of the process under varying conditions. These equations can be used to calculate the conditions, including reaction time, for which the plant is to be designed. Problem 2: Typically, raw materials available for the reaction will not be in the form required by the reaction; they may have to be dried, heated, purified, or compressed. Likewise, the products of the reaction may include unwanted byproducts or unreacted raw materials. The chemical engineer must design a complete plant including all of the raw material preparation facilities and product treatment sections required. In sizing the equipment for these parts of the plant, the chemical engineer relies on methods described in later chapters of the book. Where no information is available for a specific item of plant equipment, laboratory tests must be carried out to establish the design of that item. Problem 3: How is the plant to be operated? The reaction conditions and those for purification stages, etc., have been chosen, but the designer must ensure that the staff who will operate the plant will be able to maintain the compositions, temperatures, pressures,
etc., at the figures he has selected. The modern approach is to use instruments for these types of control duty. The instrument systems are housed in a centralized control room which enables all process variables to be controlled and adjusted from a single point by one operator. The designer must decide on the control methods required and specify the instruments needed. The detailed instrumentation is carried out by a specialist engineer. Problem 4: Of what materials is the plant to be built? The specification of materials for the plant equipment is the responsibility of the chemical engineer. For this, he uses his knowledge of the nature of the chemicals involved, backed up by laboratory tests in the case of unusual materials or mixtures of chemicals. This problem is, of course, also the realm of the metallurgist and materials engineer. Problem 5: Design of tanks, pumps, compressors and general equipment, buildings, etc. The detailed design now becomes the task of mechanical, civil, electrical, and other specialist engineers; the chemical engineer needs only sufficient knowledge of these spheres to ensure that the requirements of the reaction process are being met. It is not necessary to stress that this list is incomplete; it does indicate the breadth of the field in which the chemical engineer operates. In spite of recognizing the board area of the industry in which the chemical engineer operates, it is still difficult for the student chemist or chemical engineer to 'come to grips' with a chemical plant. One of the difficulties is the similarity many different items of equipment bear to one another. A reaction vessel looks very much like a boiler drum or a storage tank; pumps, compressors, turbines look alike. There is an 'authentic' story of (he chemical engineering graduate who was being conducted round a new plant. After being told the purpose of various reactors, columns, pipes, etc., he enquired, 'And what does that pipe do?" and received the reply, 'Oh! That's a piece of scaffolding!' A further difficulty lies in the scale of the output of modern chemical plant, allied to the fact that often neither products nor raw materials can be seen; there are few men about and it is difficult for the visitor to know whether the plant is running or not. Many modern plants yield a train-load of product a day. A single pump in a plant may deliver more fuel in a minute than a domestic heating system will use in a year. These difficulties of visualization cannot be overcome at once, but this book should help in the process by explaining the complexity and demonstrating its breakdown into constituent basic technologies. The scope of chemical engineering was examined briefly above, but it is wrong to think that only qualified chemical engineers work in this field. Apart from chemical engineers, there are at least four other types of professional staff working in this area. There are, firstly, applied chemists and chemical technologists; courses in their subjects are closely related to chemical engineering, although less comprehensive. While the term 'chemical engineer* is well defined, the term 'chemical technologist' or 'applied chemist' is rather loose and does not immediately define the type of knowledge to be expected precisely. Thirdly, there are physical chemists and, fourthly, chemists who have gained the necessary experience, or training, in the chemical industry to be able to practice chemical engineering. It is generally agreed, however, that a course in chemical engineering provides the best basic training for an interesting career in the chemical industry.
Having seen where chemical engineering fits into the chemical industry, one wish to know where one finds chemical engineers in the organization of a chemical company. This is discussed more fully in the last chapter of the book. At present, it is sufficient to say that chemical engineers can be found in almost any department. Mainly, of course, they work in the technical departments concerned with process development, plant design, and plant operation, but may also work in planning, marketing, and related commercial departments and throughout the management structure of the industry. The chemical industry is far from being the only home for the chemical engineer; chemical engineering is essentially the engineering of processes and the chemical industry is not alone in operating processes. Thus chemical engineers are more and more becoming associated with the power industrygas, of course, but electricity also-with the food industry, and with steel and other metal extraction industries. There is a place for chemical engineers in any industry where materials are put through a series of operations which change their characternot necessarily chemically. Many of the problems in the food industry, for example, lie in carrying out processesheating, freezing, drying, etc.without chemical change.
As indicated earlier, chemical engineering is a branch of science which overlaps with a broad range of other sciences and engineering disciplines. The link with organic, inorganic, and physical chemistry is obvious and, in practice, the majority of chemical engineers initially study chemistry. A point to remember is that chemical engineering, particularly theoretical chemical engineering, has a strong link with mathematics. This is because it is essentially a quantitative science concerned always with methods for determining numerical values. Chapters 3, 4, 6, and 7 have brief sections which exemplify the type of mathematical derivation used in chemical engineering. No student should be disturbed by the mathematics since their standard is similar to that encountered in most scientific or engineering courses. In reading this book it is not essential, or indeed expected, that all its more difficult passages are understood immediately.
A chemical plant is a synthesis of all engineering disciplines-mechanical, civil, electrical, instrumentation, metallurgical, and even electronicand the chemical engineer concerned with design, construction, or plant operation must understand the basic principles of these engineering disciplines. Chemical engineering is the discipline which embraces and coordinates the activities of the chemical industry. For this reason it is probably the most interestingthe key to the decision-making sector of the industry. The object of this preamble has been to show the place of chemical engineering in the industrynow to the layout of the book itself. The next chapter is concerned with the raw materials of the industry. Chemistry textbooks tend to describe the method of preparation of chemicals, while the chemical industry is based on the flow of chemical materials through a processing network which originates with the extraction of raw minerals from the earth. The following chapters, and these represent the major proportion of the book, are an introduction to chemical engineeringboth theoretical and practical. We then review energy, the services required by a chemical plant, and its control. Chapter 8 deals with some of the problems of designing and building a plant which were outlined at the start of this introduction. The book closes with a discussion of the chemical engineering profession.
Chapter 2
RAW MATERIALS FOR THE CHEMICAL INDUSTRY

The raw materials of the chemical industry are energy, air, water, and a wide range of basic minerals which can be extracted from the earth. This chapter provides an introduction to the processing methods used for mineral extraction and purification. Mining is the province of the mining engineer; in dealing with minerals purification processes we enter the area of chemical engineering. We begin to see the sort of continuously operating processes which the chemical engineer designs and some of the equipment which he uses. This chapter, then, covers the starting point for chemical processthe basic materialsand also provides a lead into the subject of chemical engineering.
WATER
The importance of water as a raw material in the chemical industry arises mainly from its relationship to the energy balance of a chemical plant. Most chemical processes result in the liberation or consumption of a significant quantity of energy. If a supply of energy is required by the plant it can be obtained by the combustion of fuels or by use of electricity. Energy considerations are so intimately connected with processes that energy is as important as the raw materials and products themselves. For this reason, Chapter 7 deals with the integration of the energy system with the plant. It is very frequently the need to conserve energy, in order to achieve economy in production that results in the complexity of chemical plants. The most frequently used source of energy or absorbent of energy is steam and steam-water systems represent a significant part of most chemical plants. Natural water, however, is not suitable for use in steam systems, nor as a process raw material, nor, indeed, for many cooling water applications. In a boiler system, natural water would cause hard deposits as occur in kettles and these reduce the boiler efficiency; the salts in natural water are frequently unacceptable to a chemical reaction, while its use in cooling systems will lead to corrosion. The chemical plant must therefore include water treatment systems.
AIR
Air, as well as water, is used as a cooling medium, air being drawn by fans over banks of finned tubes through which passes the process liquid to be cooled the design is like that of a car radiator. Air, however, also plays an increasingly important role as a process raw material. We may divide its uses up into five main ones: 1. as an oxidant; 2. as a stripping agent for removal of unwanted volatile components from a liquid; 3. as a source of nitrogen for the fertilizer industry; 4. as feed to air-separation plants supplying oxygen; and 5. for operation of power tools and plant instruments and valves.
10
The applications of air as a direct oxidant are numerous. In some cases it is used for gas phase reactions over selective, oxidative catalysts; frequently it is used in liquid systems, being bubbled through the liquid or passing upwards through an absorption column in which the liquid flows downward. In the use of air as a 'stripping agent' the process equipment is similar to that for its use in liquid oxidation systems. The air passes through the liquid and transfer of the volatile components from liquid to air takes place. Nitrogen is used by the farmers for their crops to the extent of about 750000 tons per year. The separation of this nitrogen from oxygen occurs in the process for preparation of ammonia synthesis gas. Reaction of liquid or gaseous hydrocarbons with steam, and subsequently with air, yields a gas stream containing nitrogen, hydrogen, and oxides of carbon; when the oxides of carbon are removed, a mixed hydrogen and nitrogen gas stream for ammonia synthesis is produced. One might expect that equipment needed for the use of air in such a process would be simple. In fact, even this section of the plant is of considerable complexity and requires careful chemical engineering. For an ammonia synthesis plant the air up to 50 tons per hour-is first filtered to remove dust particles and then compressed. When air is compressed it becomes hot and compression of hot gases is less efficient. This difficulty is overcome by compression in stages with intermediate cooling of the air. Cooling of the air causes condensation and a gas compressor should not have liquids fed into it. The condensed water must, therefore, be separated from the air before it enters the next compression stage. The development of tonnage oxygen plants has enabled those processes which benefit from the use of oxygen free of nitrogen to obtain oxygen by the liquefaction of air. The nitrogen also finds many industrial uses as do the other gases- argon, helium, krypton, and xenon-which can be recovered from the air. The modern trend with this type of unit is to site individual air separation plants at the places where there is a demand for oxygen in tonnage quantities. In this way, the handling and transportation of large amounts of oxygen are avoided. The design and construction of air separation plants is a specialized field of chemical engineering and has become the accepted province of a few specialist companies. As well as building plants of a packaged nature, these companies often produce and distribute liquefied gases. For the reader wishing to have more information on oxygen, nitrogen, and industrial gases generally, reference is made to the volume in this series of industrial gases.
MINERAL HYDROCARBONS
A most important group of mineral raw materials is that of gaseous and liquid hydrocarbons which, apart from their use as fuels, are also major raw materials for chemical production. Hydrocarbons are of primary importance as raw materials for the organic sector of the industry plastics, fibers, solvents, and the wide range of organic and fine chemicals. Their second major outlet is in the production of ammonia, nitric acid, and nitrogeneous fertilizers.
2.1 MINERALS IN THE CHEMICAL INDUSTRY

Mineral materials are all subject to essentially the same processing stages: 1. They are extracted from the earth by mining techniques.
11
2. 3. 4.
They are ground to a fine powder. They are refined to separate the desired chemical from impurities. They are used to produce metals or chemicals.
Minerals are generally separated into two categories. Those used primarily for their metal values are considered the province of the metallurgical industry, while the mining and treatment of those extracted for their chemical values are generally the responsibility of the chemical industry. In both cases, however, the techniques used are within the scope of chemical engineering. The metallurgical minerals and the metals extracted from them are supplied to the chemical industry in a reasonably pure state for use in the production of chemicals. Because of the close approach of the metals and chemical industry in this area, there are many cases of chemical companies producing metals and vice versa. It should be noted that some minerals find large scale used in the both the chemicals and metal industries. 1. Copper and Iron Pyrites are used both for their metal value and as a source of sulfur for sulfuric acid. The pyrite is produced and purified in the metal industry and usually transported to a chemical works for production of sulfuric acid. The byproduct from the roasting is called calcine and consists of iron and copper oxides. This is sold back to the metals industry for iron or copper manufacture. 2. Bauxite is used as a source of aluminium and of aluminium oxide for the chemical and building industries. The bauxite is extracted and purified by the metals industry and supplied to the chemicals industry. 3. Titanium ores are used as a source of metallic titanium and for titanium dioxide, which is used as a white paint pigment. 4. Salt is used for the manufacture of sodium hydroxide, sodium chemicals, sodium itself, and chlorine. Sodium metal is used primarily for chemical purposes and has very few metallurgical uses; in fact, the whole salt-based, alkali industry, including sodium production, is a part of the chemical industry.
In the rest of this chapter barite discuss we those minerals borates whose dolomite extraction is the responsibility of the chemical industry, while remembering that the technology is
CaSO4 BaSO4 various mixed MgCO3,CaCO3
Sulfuric acid, ammonium sulphate. Paints, barium chemicals (carbonate, sulphide, sulphate, chloride, oxide, hydroxide, peroxide). Enamels, glass, boron chemicals. Building industry, catalysts, magnesium chemicals.
12
feldspars fuller's earth graphite
K, Al, Ca, silicates clay carbon
Na, Glassmaking, pottery, porcelain. Generally in the chemical industry for cleaning and decolorizing. Graphite equipment, lubricants
Table 2.1 OTHER MINERALS OF VALUE TO CHEMICAL INDUSTRY
Note: These minerals are widely distributed as indigenous ores in many countries. The crystalline composition can vary quite largely between deposits. In Table 2.1 some of the other minerals used by the chemical industry are listed. Some minerals are used directly with very little processing, for example sand and limestone for building materials. Even the building industry, however, is using increasing quantities of preformed building materials, whose manufacture is very much a part of the chemical industry. Furthermore, clays and sands, limestone, etc., even when used without chemical processing, must be taken through some mineral treatment stages if good structural properties are to be obtained. Similarly, the diagram shows potassium-containing mineral salts going directly into fertilizers. A potassium chloride mine may cost around $50 million, while the associated surface plant for extracting potassium chloride suitable for use in fertilizers from the raw mineral will add up to another $30 million.
13
Potash minerals
Figure 2.1 MINERALS USED IN THE CHEMICAL INDUSTRY
The chemistry textbook may say, 'Take potassium chloride and treat it with\ but from a chemical engineer's viewpoint the major problem lies in extracting the potassium chloride-the rest is easy!
14
2.2. MINING TECHNIQUES

The first task is the location of suitable deposits of minerals for extraction and the proving of their size and workability. This is the work of the mineralogist and geologist, who use techniques based on their knowledge of rocks, strata, etc. The proving of the size of a deposit is usually carried out by drilling out core samples; these are subsequently examined and analyzed to provide a three-dimensional map of the region from which the cores are taken. The analyses enable decisions to be made on the mining method, the shaft location, and the processes to be used in refining the mineral. There are three methods for recovering the ore from the earth. These are: 1. Surface mining, 2. Underground mining, and 3. Solution mining.
SURFACE MINING
The simplest type of surface mining is dredging, which is typically used for recovering gravels from river beds. A bucket elevator grabs the gravel from the bed and the buckets carry it to a hopper in the hull of the dredger. Here the material is screened and then taken ashore by belt conveyor to pile. The technique used for recovering minerals which lie in seams just below the surface is open-cut mining. The seam may lie at almost any angle to the surface and often seams come to the surface in a hillside. The first action is to remove overburden, etc., to expose a cliff or working face which is vertical, and from which mineral can be extracted with power machinery. In the case of seams parallel to the surface, the working face is exposed by digging down through the seam. Material removed from the face by powerdriven shovels is loaded into wagons or trucks and conveyed to the mineral processing plant. In this country the land is usually restored to its original condition or better once the mineral has been extracted. Minerals frequently extracted by surface mining include clay, limestone, sand, gravel, coal, phosphate rock, bauxite, iron ore, and other metallurgical minerals.
UNDERGROUND MINING
Underground mining itself can be conducted in many different ways, depending chiefly on the nature of the deposit and its orientation relative to the surface. The basic elements of the mine are the shaft down to the deposit, tunneling along the line of the deposit (unless it is very steep), and removal of ore from a face by explosive and/or mechanical means. The ore is transported to the shaft by conveyors, trucks, or wagons and then hoisted to the surface. The chief factor differentiating one mining method from another is the method of treating the space left by the extracted ore, so that dangerous surface subsidence does not take place
15
when mining is over. The simplest method is to leave an empty space; this can be done where rock formations surrounding the ore body removed are strong enough. The alternative procedure to this is only to extract part of the ore perhaps 60-70%leaving the remainder as pillars which support the roof. The 'open' methods above are mining methods in which no artificial roof supports are needed. It is more usual, however, to support the roof. If this is done then some action must be taken when the ore has been removed. The first approach is to refill the space with waste rock and ore. The second is to cave in the roof after ore extraction. There are many variants which have been developed for mines of this type. Mineral is frequently extracted from the face by blasting. Holes are drilled in the face and explosive charges inserted. On detonation, the face falls inwards. After the dust has cleared, mechanical pick-up-and-loading equipment is brought forward. The equipment has long arms which move into the broken ore and feed it on to a conveyor; this loads the trucks or wagons which carry the ore to the shaft. In mining operations, particular attention must be paid to ventilation. Air supply equipment and ducts must be provided to deliver fresh air to the men working at the face, and to vent air by another route out of the mine. Pockets of gas, especially methane, are encountered from time to time and high ventilation rates are used to keep the purity of the air as high as possible. In addition, regular analyses of the atmosphere in the mine are carried out. In all, underground mining is exacting work and requires discipline and rigorous attention to procedures if safe working is to be assured.
SOLUTION MINING
Rock salt sodium chloride-and also potassium chloride may be recovered by a solution technique. A shaft or well is sunk into the salt strata or dome and water is pumped down to dissolve the salt. A saturated brine solution is returned to the surface. The solution is then clarified, heated, and evaporated; as evaporation takes place the solution becomes saturated and then salt is precipitated from the solution as reasonably pure crystals. The rate of production that can be achieved from a salt well is dependent on the rock surface area exposed to water, which in turn increases as salt is extracted. It is not until some years after extraction is started that a well reaches full production. Careful forecasting of future needs is therefore necessary, if a set of wells is to have the right production capacity at the right time.
16
2.3.
TECHNIQUES OF PURIFICATION OR REFINING
The raw product from a mine can contain three types of impurity. 1. Gangueearth, clay, sand, etc.which is recovered together with the major crystalline aggregates of mineral. 2. Similar impurities much more intimately mixed in the crystal mass of the mineral. 3. Co crystalline impurities, which are present as part of the same crystal structure as the chemical product desired. While the first two types of impurity are in principle separable by purely physical methods, the third type of impurity usually requires the use of chemical techniques. In practice, it is not usual to separate co-crystalline impurities at the mine site. The material with its co-crystalline impurities is transported to the chemical plant and any further purification is carried out there as part of the chemical processing. Physical purification techniques involve finding a property of the desired mineral which differs from that of the gangue. A typical example of such a property is the magnetic nature of certain iron ores. This property allows iron ore to be extracted from earthy materials in magnetic separation equipment. Other types of property commonly used are discussed in Section 2.4. The term used for refining of minerals in this way is beneficiation. The first step in beneficiation is to grind the raw material finely. This is because the properties used for separation are those of small particles. The subsequent processes will require that a particular size of particle is used for optimum operation. The first stage of mineral dressing, then, is to break up and classify the lumps recovered in the mining procedure. The process of classification per se often results in some separation of the desired mineral from the gangue. After grinding and classification the mineral is subjected to the chosen separation process. A basic principle throughout chemical engineering is to carry out processes continuously with material flowing at steady rates from one step in the process to the next. This is also the case in minerals processing and the processes and equipment discussed belowall operate on a continuous-flow basis.
CRUSHING AND GRINDING

Crushing is the term applied to the breaking up of large particles of raw mineral, usually in the size range from about 10 mm to about 300 mm. Grinding is the term applied to the process of further breaking down material which is already fairly small. The basic difference in the equipment for the two processes results from the particle size. Large particles require the application of a large force to a relatively small number of particles to crush a ton of material. Grinding small particles requires the application of a much smaller force to a large number of particles. In the case of crushers, the active component of the machine must be able to apply a large force over a rather small surface area which is in contact with the particles. The grinder provides means of applying a small force over a large surface area which comes into contact with the fine particles. An additional difference is that in most crushing machines the particles resulting from first breaking are delivered by the machine,
17
while in a grinder further subdivision of the broken fragments takes place during a protracted period of residence of the material in the machine.
JAW CRUSHER
The jaw crusher consists of two platesone stationary and one moving. The moving plate is made to undergo a reciprocating motion alternately towards and away from the stationary plate. As it approaches the stationary plate the material is squeezed between the plates and broken. Typically, the feed is vertical through the crusher and the plates are positioned to be nearer together at the bottom than the top. The broken particles become smaller as they fall between the plates and are broken, and they finally fall out from the bottom of the plates. A similar type of crusher is the gyratory crusher in which the plates are conical in shape, the moving plate rotating inside the fixed one-usually eccentrically; this rotation brings about the reciprocating crushing motion.
ROLL C RUSHER
There are two types of roll crusher-single- and double-roll machines. In the single-roll type, the particles are crushed between the rotating roll and a fixed breaker plate. The double-roll crusher has two rolls rotating in opposite directions and the particles are 'nipped' between the two rolls. The rolls are not usually smooth but serrated or roughened to improve the grip on the particles to be cracked. The rolls are held by springs which take the fluctuating loads. The use of springs is essential to prevent damage to the bearings of the rolls.
HAMMER CRUSHER
In the hammer crusher, the particles are broken by impact rather than squeezing. A horizontal shaft has a number of bars attached to it so that they pivot as the shaft rotates; the rotation causes the bars to fly round in a circular plane. Particles to be crushed are fed into the path of the rotating hammer bars. The fragments and any particles unbroken in the initial impact are thrown against a breaker plate.
BALL MILLS
The equipment most commonly used for grinding is the ball mill. This consists of a rotating drum containing steel balls which are kept in motion inside the drum by its rotation. The balls break the particles as they are nipped between balls or between the balls and the wall of the drum. Material is fed in continuously at one end of the drum and removed through a grating, which retains the balls, at the other end (Figure 2.2a).
18
FIG. 2.2 (A) SOLIDS TREATMENT EQUIPMENT: Diagrammatic section of a typical ball mill. The rotation of the drum keeps the material and balls in motion. The material flows from left to right through the mill. The larger halls at the left-hand end crush the large material as it enters. The smaller balls with finer material segregate at the right-hand end where the crushed material leaves the mill.
If the feed rate increases, the mill becomes more full and material passes out at a greater rate because a larger area of the exit grating is covered. The mills may be operated wet or dry. In earlier days it was more common to operate wet. This overcame one of the serious problems of operating any crushing equipmentdust. There are other advantages applicable to grinding particular minerals. In wet grinding it is usual to use about 30% waterbelow this the mix is very sticky. With the development of more sophisticated equipment for dust control it has become much more common to carry out dry grinding. After crushing and grinding, the next step is to ensure that the desired size grading of material is taken forward to the refining stage. This is done by a classification process. Classification is frequently incorporated in a circuit with the milling (and crushing) step. The product from the mill is classified and the oversize material is returned to the mill.
SCREENING AND CLASSIFICATION

Screening is a process which can segregate particles only according to size, while classification separates particles into groups or classes identified by other properties as well as size. To this extent, classification can carry out some initial separation of the desired mineral from the gangue. In both cases, the particles which are required for the separation
19
processing step are segregated from the off-size material, which is returned to an earlier stage or passed forward to an alternative processing stream.
SCREENING
The principle used in screening is exactly that of the sieve. The material to be screened is brought into contact with a wire mesh which has holes whose size determines the size of material passing through. The material is divided into two streams. To ensure separation and continuity of operation, two types of motion of the material are necessary. 1. The material must flow across the screen. 2. The individual particles must be maintained in motion so that they are constantly re-presented to the screen surface and given the opportunity to pass through. The wire mesh screen is usually vibrated up and down by mechanical means to ensure that particles are kept in motion relative to the mesh. The vibration mode may also include a horizontal component of motion to move the particles across the mesh surface. Alternatively, the screen may be inclined and the particles made to flow across it under gravity (Figure 2.2b). Screen sizes and capacity vary over a very wide range- typically, a screen 6 m long by 2 m wide sloping at 20 may handle 40 tons of material per hour. If separation into several size ranges is required then a series of screens with decreasing mesh size may be used; the separated product streams are taken from the upper surfaces of the individual meshes. An alternative means of subdivision of a material stream into several size ranges is to use a trommel. This is a rotating drum formed of meshes whose aperture size increases from one section to the next along the drum. The axis of the drum slopes and this ensures that the material passes forward along the drum. The material enters the drum at the end where the aperture is smallest and fractions of increasing particle size are taken in succession as the material passes from section to section. The largest particles pass out at the end of the trommel. It is also possible for trommels to have a set of concentric screens; in this case the mesh with largest aperture is at the inside and all streams leave the drums at the end of the trommel, which is again sloped to give forward motion.
20
FIG. 2.2 (B) SOLIDS TREATMENT EQUIPMENT: Double Deck Sloping Screen. The material is fed on to the top screen and three grades are produced; coarse material comes of the top screen medium size material from the upper surface of the lower screen, and fine material passes through both screens.
Screening has a variety of applications in ore dressing. Crushers and mills usually operate most efficiently on a feed of fairly narrow size range and screening is, therefore, used prior to these operations as well as for separation of the product material of the desired size.
AIR CLASSIFICATION
Air classification is an alternative means of separating particles into sets of different size. It relies on the different effects of air velocity on particles of different sizes. If air is blown across a stream of falling particles, the smallest particles are deflected furthest and if the stream consists of a range of sizes then these are spread out in the direction of the air stream. The particles can then be collected into streams of different sizes. A simple classifier of this type is shown in Figure 2.3(a). There are many other ways in which the principle can be used. For instance, in milling, an air stream through the mill may be used to carry away particles when they become sufficiently fine; the heavier particles cannot be carried by the air and remain to be ground further.
21
Particle
feed
Air and finest particles to cyclone separator
Feed air
(a)
Product particle streams decreasing size
i Overflow
(b)
Feed-
Figure 2.3 EQUIPMENT FOR AIR CLASSIFICATION,
(a) The principle of the classifier: The lighter material is deflected further by the air stream and the finest is carried out in the exit air flow, (b) The cyclone: the feed air stream enters the cylindrical section of the cyclone tangentially which causes the air to flow in the cyclone with a swirling motion. The large heavy particles are separated and fall down the cone wall to pass out at the bottom. Air with fine particles leaves at the top
The particles in the air stream are then separated from the air in a cyclone (Figure 2.3). The gases enter the cyclone tangentially and swirl round inside. The rotation provides centrifugal force which is used toUnderflowthe particles from the air. The particles are forced to the wall separate of the cyclone where they are slowed down by frictional contact with the wall. They drop to the base of the cyclone and fall out through a flap valve. The gases pass out through the central hole at the top. Correct design can allow for particles of a particular size to be carried on with the gas stream. The centrifugal force field acts in a similar way to gravity in the air classifier shown in Figure 2.3(a).
22
In air classification, the different density of materials can also have an effect since, generally, the higher the density the less the particle will be deflected by the air stream. Particles of high density would, therefore, go into the product stream with larger particles of lower-density material. Air classification, however, is not usually used as a means of separating materials of different densities but only for sizing.
WATER CLASSIFICATION
In water classification, the density of the mineral is much closer to that of the classifying fluid and, although the principle of classification is again that of interaction between the fluid and the particle, the results that can be achieved are different. In air classification, density has only a small effect compared with size, whereas in water classification the effect of density differences between particles is more important. We know that if we stir up a powder of different particle sizes in a liquid, the particles will be suspended in the liquid owing to the turbulent motion of the liquid. If stirring is stopped the particles will settle; the large ones will settle first because they have the highest falling velocity through the fluid medium. If we mixed the types of particles- one type having density close to that of the water and one being much heavier than water then even quite fine particles of the heavy material would settle to the bottom before the larger particles of the lighter material started to settle. This is a principle having very wide application in minerals processing. The term classification, however, is usually applied to the separation of large particles from smaller ones, with density having little effect. In a continuously operating classifier, liquid and mineral feed enter the classifier together and mechanical agitation is applied. This keeps the finer particles in suspension while the larger ones settle through the liquid to the bottom. The fine material overflows with the liquid, while the larger settles to the bottom and is raked along the sloping base of the classifier out of the liquid. If the materials are required dry for subsequent operations they must be filtered from the water and dried. A variety of different types of classifier equipment can be used according to the nature of the materials involved. A recent development is the hydro-cyclone. The principle of the hydro-cyclone or hydro-clone is similar to that of the cyclone in Figure 2.3(b), except that there is a bottom exit for fluid as well as one at the top. The top overflow conveys the finer material, while the bottom underflow carries away the larger particles.
SEPARATION
The next stage in mineral processing is separation or concentration, in which the purity of the mineral is improved by separating the impurities from it. The prior crushing, grinding, and classification were necessary to give the fine, evenly sized particles required for the various separation processes. One method of separation, as mentioned in the previous section, is based on the density differences between the mineral and gangue particles and a separating fluid. Separation by this means is called gravity separation; the other common methods are flotation and magnetic separation.
Gravity Separation
23
The simplest way of using gravity separation is to use a liquid whose specific gravity lies between that of the two materials to be separated; the lighter material floats and the heavier sinks. Most minerals and the gangue are heavier than water and suitable high-density liquids are difficult to find. There are methods, however, in which water can be used and separation is still possible. These methods rely on the differences in motion of the lighter and heavier particles when the water itself is in motion. If the water, for example, is made to flow vertically upwards it will tend to carry the lighter particles with it, while heavier ones of the same size will sink. A further development is to make use of the separating effect of the combined liquid-particle mixture. The effect achieved is * one of hindered settling in which the particles in the liquid interfere with each other's motion. Equipment in which hindered settling is exploited is called a jig or a table. Both are names for broad, shallow troughs to which water and ore are fed batch-wise or continuously, and to which it is possible to apply a vibratory motion. In the case of the fig, motion is vertical. The jigging action causes increased liquid motion relative to the solids, and increased particle-to-particle interference; the action results in an equilibrium orientation, in which particles with different properties are stratified in the jig. In jigging, the interaction of the various size, density and shape factors of the particles is complicated. The vertical jigging motion may be applied by pulsing the water or feed flow to the jig-In tabling, the motion is applied directly to the table or trough and is a reciprocating, horizontal motion. The motion is not simple-harmonic but rather with steady acceleration from rest and an abrupt stop. This motion now produces stratification which becomes gradually more defined as the water and ore progress along the table from the feed point to the offtake region. A recent development also has been the use of a fluidized bed of particles as the separating medium. The bed is made up of particles of appropriate density and size which are held in a fluidized condition by air blown upwards through a grid at the base of the bed.
Flotation
One of the most widely used beneficiation techniques is that of froth flotation. The principle of this process is that the mineral particles are not wetted by the liquid and thus remain on the surface of the liquid when the liquidusually water or aqueous solutionis mixed with the raw mineral. The capacity of the quiescent surface of the liquid for holding mineral is not very large. It can be vastly increased by stirring or bubbling the liquid to form a froth, in which the poorly wetted mineral particles are held in the bubble films. The major problem in the use of this technique is that most minerals are relatively easily wetted and do not float. This difficulty is overcome by the use of anti-wetting agents. These agents are used to treat the raw mineral after grinding and they become selectively attached to the mineral particles, which are then held in the surface rather than the bulk liquid. Anti-wetting agents (or surf ace-active agents) are frequently long-chain hydrocarbon molecules with polar radicals at one endfor example, octadecylamine. The amino end of the molecule is polar and is attracted to the mineral salt particle which is a polar material. A loose bond is formed between the salt and the amino end of the organic molecule. The nonpolar hydrocarbon tail of the molecule now repels polar liquids such as water and prevents the mineral particle becoming wetted. Because the agent is only required to form a
24
monomolecular layer on the mineral particle, quite small amounts are required; and this small impurity does not generally interfere with subsequent processing of the mineral. Flotation agents can also show a high degree of specificity for one mineral rather than another. If the right agent is used, flotation can be employed to separate the desired mineral from a crystalline impurity. Froth from the flotation cell overflows and is collected in a tank where the foam breaks either naturally or with the aid of foam-breaking chemicals. The recovered particles can then settle and be separated from the liquid phase prior to filtration and drying or further stages of beneficiation.
Magnetic Separation
Magnetic separation relies on the mineral and the gangue having significantly different magnetic permeabilities. The motion of particles in a magnetic field is influenced by their permeability. If the permeability difference is sufficiently large, a significant segregation of materials into two streams can be achieved. The minerals to which this type of separation is usually applied are those having some degree of ferromagnetism, especially iron-bearing ores. As the material passes through the magnetic field, the ferromagnetic material is attracted to the magnetic pole collecting surface. Various mechanical arrangements are then used to remove the collected material, keep the collecting surface clear, and distribute the materials having different properties to appropriate following stages of processing.
2.4 EXTRACTION TECHNIQUES FOR SOME MINERALS

In this section the processes for extraction and beneficiation of three mineral materials are described to show how the various techniques discussed in the previous section are fitted into a processing scheme. It should be remembered that rarely are two mineral deposits of the same chemical identical and that a processing train suitable for one deposit may require to be considerably modified for processing another deposit. In particular, deposits vary with respect to the nature of the impurities present and different impurities require different separation techniques.
Sulphur
Native sulphur or brimstone occurs in association with other sulphur-containing minerals such as gypsum (CaSO4.2H2O) and anhydrite (CaSO4), and also with calcite or dolomite. The process by which native sulphur is usually extracted is the Frasch process. A hole is drilled down into the deposit and a 150 mm pipe consisting of three concentric pipes is put down into the well, as shown in Figure 2.4. Hot water, which is under pressure so that its temperature is above the melting point of sulphur, goes down the outer annulus and out through holes into the sulphur-bearing rock matrix. The sulphur is melted by the hot water and sinks beneath the water level. The molten sulphur then flows into the central /one of the pipe, and compressed air, which has been brought in down the central pipe, forces the liquid sulphur with the air How to the surface through the middle annulus in a two-phase mixture. At
25
the surface the sulphur is disengaged from the air and allowed to solidify in large vats. Underground, the water replaces the sulphur that has been removed. The sulphur produced in this way is of high purity and may be broken from the solidification vats for transportation. A single well of this type is capable of producing a million tons a year. An increasing proportion of world sulphur requirements is now being met by extracting hydrogen sulphide from 'sour1 natural gas. The H2S is removed by absorption and then stripping of the solvent. Part of the H2S is converted to SO2 which then reacts with the remainder of the H2S in the Clans kiln process. 2H2S + SO2 ______________ 3S + 2H2O
Figure 2.4 SULPHUR WELL The Frasch process
In fact, in Canada at present, natural gas is being extracted, the sulphur recovered, and the gas then returned into the ground as it is not needed.
26
Potassium Chloride
Silvinite is a mixed ore containing separate fine crystals of sodium chloride and potassium chloride. One method by which these may be separated is fractional crystallization. The solubility of the KCl increases quite markedly with solution temperature while that of salt changes little. By making up a hot saturated solution and then cooling, it is possible to separate KCl crystals. It is now more usual to carry out the major separation by flotation. A typical flow-sheet is shown in Figure 2.5. The ore must first be crushed to reduce the particle size to that of the individual KCl and NaCl crystals.
Raw ore (largely potassium and sodium chlorides)
Brine filtrate recycle
Figure 2.5 POTASH BENEFICATION PLANT
To optimize crushing, the ore is screened to three sizes in the first screen which has a coarse mesh with fine mesh below. The 'fines' passing both meshes are already small enough for the next step in the process. The remainder passes through the crushing circuit as shown. Clay and other fine impurities in the ore are next washed off the crystals with brine and separated from them as 'slimes' in the classifiers. The brine -slimes mixture goes to thickening tanks in which the brine is recovered for reuse. The brine containing the crystals is treated with a conditioning agent, which causes the KCl to be floated. Aliphatic amines are used; two stages of flotation are required. In the first stage, the object is to ensure that all KCl is floated and the unfloated impurity can be discarded; some NaCl also floats and the second stage of flotation removes most of this. In the second stage, the objective is to remove all NaCl from the KCl material which is passed forward. A greater fraction of KCl is rejected and so the unfloated material is recycled to the first stage. The KCl product from the second stage is usually 97 98% KCl. It is recovered from the foam in the centrifuge and dried in a drum drier with a counter-current hot air flow. Brine is recovered from all waste streams and recycled; the clay and NaCl waste are dumped. A production rate of a million tons per year may be expected from such an operation.
Phosphate Rock
27
Phosphate rock is a broad term applied to various phosphate-containing minerals. The phosphate is usually combined as tricalcium phosphate Ca3(P04)2. The calcium phosphate is also often associated with calcium fluoride as fluoroapatite [Ca3(P04)2]3.CaF2 , and other common impurities are aluminium and iron phosphates, calcium carbonate, sulphate, and silicate. Deposits are mined by both open-pit and underground mining techniques. The product from the mining operations in Florida is typically one-third each of clay, sand, and phosphate deposits in the form of 'pebble". Pebble is the name given to this type of particulate phosphate deposit mixed with clay and sand; the pebble size may be from 2 to 20 mm. The first stage of beneficiation is to separate the pebble from the clay, sand, and matrix. This is done by a washing operation and screening. The fine material, still containing fine phosphate particles, then goes into a classification stage from which it passes to froth flotation for final separation of the fine phosphate from sand. Use of a fatty acid flotation agent allows the phosphate mineral to be separated. The phosphate minerals recovered from the washing, classification, and flotation stages are, of course, of differing purity as well as differing size grading. Each phosphate mineral producing company therefore markets a range of products and in addition the compositions of minerals from different mines all vary. This variation in composition, size range, etc. presents considerable problems for the designer of the plant consuming phosphate rock. The designer of a phosphoric acid plant must characterize the rock grade or grades which will be used in the plant and design the acid plant accordingly.
28
Chapter 3
FUNDAMENTALS
This chapter begins the chemical engineering section of the book. Let us start with a few thoughts on the contribution made by industry and the value of engineering itself. Industry is concerned with meeting human needs, whether it makes fertilizers to meet food requirements, washing machines to help provide time for leisure pursuits, or golf balls to meet relaxation needs. The consumer tells industry in a very simple way whether his needs are being catered for by his willingness to pay the price the manufacturer asks for his product. In a free society no other indication is necessary. Likewise, industry knows that it is successfully meeting a need if, at the price it can obtain, it is able to sell sufficient of its product to cover costs and preferably expand its production facilities. The major concern of engineers is the minimization of production costs. The success of the engineer in this allows prices to be lowered and sales and production to be expanded which leads to higher standards of living. The cost of production in the factory is made up of several components: 1. Cost of raw materials and power. 2. Cost of man-hours needed. 3. Cost of research and development. 4. Interest or return on capital employed. 5. Depreciation and maintenance costs. 6. Administrative and selling expenses. If the engineer, chemical or otherwise, finds a way to reduce a basic cost of production, several small changes can be expected in due course: 1. Selling price can be reduced, allowing more customers to buy the product. 2. The men working in the factory can be paid higher wages. 3. The expenditure on research and development to find the next improvement can be increased. 4. The interest and dividends paid on capital can be increased so that more capital will become available to build more factories.
These changes occur gradually rather than at once. Over the years, however, progressive improvement in living standards results from developments made by engineers in an industry
29
which operates within the constraints of the monetary, social and legal requirements. The chemical engineer, then, is assisting in progress, improving the standards of his fellow men customers and co-workers- and so justifying his own existence. The success of the individual can only contribute to, and occur within the context of, improved standards for everyone. The cost of the product, together with any reduction which can be made, is thus the essential yardstick with which the engineer must measure his work. The chemical engineer must understand the rudiments of company and project finance and be able to evaluate the financial viability of projects and development work. (For more information on this reference should be made to the volume in this series on social and economic aspects.) The division between engineering and science is frequently a narrow one, and the career choice between the two is a difficult one to make. At the time the choice must be made the student generally has several years of science behind him and 'engineering' is not a term conveying much meaning. Perhaps the simplest way to separate science and engineering is to ask oneself what questions they are seeking to answer. Generally speaking, science is concerned with the question 'why?' and engineering with 'how? Science is probing why a subatomic particle reacts in a given way; engineering asks how this fact can be used to produce power. Engineering is always quantitative: the answers must appear as sizes of buildings, vessels, catalyst pellets, pumps, conveyors, etc. All engineering is concerned with the estimation of the quantitative values which specify the structure and operation of man's material environment. In the engineering of chemical plants, the chemical engineer is concerned with flow rates and physical properties of materials within the plant and with dimensions of equipment used to contain and convey those materials and to alter their physical properties. Once the basic data of a plant are established the details of how vessels are to be constructed, how equipment is to be sited, how foundations are to be built, etc., etc., become the province of specialist engineers. Chemical engineering is particularly concerned with the study of the conditions under which processes, reactions, changes in physical conditions of materials take place, and with the practice of using this information to determine physical design values. That may appear rather abstract but, as an example, consider the question of the fall in pressure as a fluid flows through a pipe. In order to be able to calculate this fall in pressure it is necessary to know a relationship between the pressure drop P and the viscosity of the fluid , its velocity v and density p, and the dimensions of the pipe, length l, diameter d; that is: P = f(, v, p,l,d) (3.1)
30
By study of the theory of fluids flowing in smooth pipes it is possible to derive such a relationship. In practice, the wall of the pipe may be rough, dirty, or rusty and it is necessary to know how to allow for such deviations from the ideal system for which the relationship was derived. Practical experience is a result of experiment and from this methods for allowing for roughness, dirtiness, etc., are worked out. Thus the tools used by a chemical engineer are in part the result of theoretical study of the processes with which he is concerned, and in part empirical factors which the engineer uses to allow for the deviation of the real system, with which he deals, from the ideal system to which his theoretical model applies. This is a recurrent phenomenon of all branches of chemical engineering. It is also interesting to note that there is some tendency to division of chemical engineers into two types-those who enjoy, and are primarily concerned with, the theoretical aspects and those who are primarily practical and work in the empirical area. An objective of chemical engineering research is to extend the area of the subject for which theory is applicable and empiricism is no longer necessary. In fact, one way of looking at the empirical approach is that it is necessary for a particular problem, because that sector is so complex that the theoretical engineers have been unable to develop the appropriate theory. Coming back to A/; in principle there is no reason why the theoretical engineer should not develop a theory which covers entirely all possible pipes, including dirty, rough, rusty ones; then there would be no need for empiricism -it is just that the theory has not yet been developed far enough. The importance of numerical quantities in chemical engineering gives great emphasis to the system of units used by the chemical engineer to express his variables, his flows, pressures, heat fluxes, etc. A common system of units is shortly to be introduced throughout British industry and, it is hoped, on a world-wide basis. In view of this, a section of this chapter is devoted to this system and it is used throughout the book, with the exception that the use of the comma as a decimal marker is not adopted. Another factor, related to the numerical nature of chemical engineering work, is the availability of data on the physical properties of chemicals. The chemical engineer must be aware of the sources of such information. Published literaturebooks, journals, proceedings of conferences is generally the source of the data required as well as methods developed for carrying out design calculations. The chemical engineer soon becomes experienced in using the index and reference systems available to help him in seeking the information he requires.
3.1. THE SCOPE OF CHEMICAL ENGINEERING

Just as chemistry is subdivided into organic, inorganic, and physical chemistry, so chemical engineering may be subdivided into topics. There are two types of topic we might call these 'general' and 'specific'. The 'general' areas provide information which is used throughout a chemical plant, while 'specific' areas are concerned with one type of equipment or step in a plant. General areas in chemical engineering are: Chemistry -knowledge of chemicals and their interactions Physics of solids, gases and liquids: diffusion, kinetic theory, etc. Mechanics of fluid flow, heat flow
31
Thermodynamics Mathematics- calculus, vectors, statistics, economics Principles of engineering mechanical, electrical, civil, control With the brief description of each subject, they are largely self-explanatory. In Chapter 2 we have already met some of the basic processing steps in a plant - size reduction, classifying, etc. If we examine the basic steps in a chemical plant more carefully we will be able to list the 'specific' areas of chemical engineering.
Reactant Preparation
Compression Heating Mixing Crushing Agglomerating Dissolution Classification
Reaction
Catalytic Heterogeneous Homogeneous Non-catalytic - Homogeneous or multi-phase
Product Separation
Absorption Distillation Solvent extraction Crystallization Filtration Evaporation Drying Chemical reaction is normally treated as a separate subject. Topics listed under the other two headings are frequently referred to as 'unit operations' by chemical engineers. (Unit operations listed under reactant preparation may be used for product separation, and vice versa.)
32
These, then, are the subjects making up a course in chemical engineering. In this book particular aspects of some of the subjects will be dealt with using those which are, so far as possible, representative of the whole subject. This chapter is concerned with fundamentals, especially fundamental subjects normally regarded as falling within the scope of a chemical engineering syllabus. The three topics to which this applies are thermodynamics, heat transfer, and fluid flow. The whole of Chapter 4 is devoted to thermodynamics. This chapter continues with discussion of units, the basic rate equation, and dimensional analysis, since these form the foundation for heat transfer and fluid flow with which the chapter ends.
3.2 UNITS - THE SI SYSTEM

Three systems of measurement units have been in common use in this country: Foot, Pound, Second (FPS)
Centimeter, Gram, Second (CGS) Meter, Kilogram, Second (MKS)
The conversion problem between FPS and CGS has been a major difficulty in the dealings of the international engineering companies. The eleventh General Conference of Weights and Measures at an international meeting in 1960 adopted the International System of Units (SI). Most countries using the metric system will adopt the SI. The period of conversion to this system is 1968-72. In fact, SI is MKS with certain adjustments having changes in various conventional uses of symbols. It is possible to base all units on four independent units of mass, length, time and temperature. (The interrelation of the units is shown in Figure 3.1.) SI in fact has six basic units but two of thesethe units of current and luminous intensity - can be derived from the other four.
Basic SI units are Measurement Length Mass Time Current Unit meter kilogram second ampere Symbol m kg s A
33
Thermodynamic temperature Luminous intensity
Kelvin candela
K cd
A change has recently been made in the temperature scale definition Temperatures are now based on the absolute or Kelvin scale in which the triple point of water is defined as 273.16 K, since the triple point can be reproduced with greater accuracy than either boiling point or freezing point. In fact, it is permissible to use for temperature either the thermo-dynamic temperature scale or the International Practical Temperature Scale. The comparison is given below the degree interval is the same in both. Unit Name / Abbreviation Thermodynamic scale Kelvin K Absolute Zero Triple point of water Boiling Point of water 0.00 273.16 373.15 Practical Scale Degree Celsius oC -273.15 0.01 100.0
All other units in SI are derived from the basic six units. A system of units of this sort is called a coherent system; the systems we used previously were, of course, noncoherent-pressure on the FPS system was typically quoted in pounds per square inch. Table 3.1 lists some of the more important derived units used by the engineer. It can be seen that some of the new units of SI have been given names, others not. The names Pascal, Poise and Hertz have not yet been adopted by all countries. There are, in addition, other derived units of electromagnetic and light.
34
{Radiation dosage]
Figure 3.1 . THE RELATIONSHIP BETWEEN BASIC AND DERIVED UNITS: This diagram shows how the basic units of length, time, mass, and temperature enter into many of the derived units used in engineering. The diagram shows that the unit of Current can be derived from the four basic units. In the SI system, however, Current is treated as a basic unit. From 'Standards of Measurement' by Alien V. Astin, Copyright (c) 1968 by Scientific American, Inc.
Frequency Force Pressure Viscosity Density Velocity
Hertz Newton Pascal poise _
Hz N Pa (N/m2) PI _
s-1 kg .m/s2 kg/m.s2 kg/m.s kg/m3 m/s
35
Surface Tension diffusivity work (heat) Power Heat transfer coefficient Enthalpy Specific heat Thermal conductivity Electrical charge Electrical voltage Coulomb Volt joule Watt
N/m
kg/s2 m2/s
J (N.m) W (J/s) W/m2.K J/kg J/kg.K W/mK C V
kg .m2/s2 kg.m2/s3 kg/s3.K m2/s2 m2/s2 K kg.m/s3 .k A.s kg.m2/A.s3
Table 3.1. IMPORTANT DERIVED UNITS IN SI SYSTEMS
For the practicing engineer, the change to the SI system will involve many adjustments changes in standard sizes and threads, and elimination of familiar units.
3.3. THE BASIC RATE EQUATION

Processes proceed. The chemical engineer is concerned with the rate at which they proceed and the influence of conditions within the plant on that rate. Because of this interest in rates, a standard form of rate equation arises in almost every branch of the subject. This standard expression is very simple and takes the form Rate of process = (process rate constant) X (driving force) A very typical example is the equation for the rate of heat transfer from a fluid maintained at temperature T1 through a tube wall to another fluid maintained at temperature T2. The expression is Q = (UA) X (T1-T2) (3.2) Where Q = heat flow (J/s), U = heat transfer coefficient (J/sKm2), T2) = driving force (K). (UA) = process rate constant, A = area of tube wall considered (m2), and (T1-
36
In most of these rate equations, the chemical engineer's problem lies in estimating the rate constant (UA in heat transfer). It is not possible to set up an experiment and determine UA by measurement on each occasion when a heat flow must be calculated. The procedure is therefore to develop methods for calculating the constant, U will obviously depend on many variables such as 1. Thickness and thermal conductivity of the tube wall, and 2. Velocity and physical properties of the two fluids. Equations for calculating U have been built up. These are partly theoretical and partly derived from experimental studies carried out by many workers over a wide range of conditions. The chemical engineer thus uses recognized procedures to determine UA and hence Q. In many of the processes with which chemical engineering deals, the driving force is the simple difference of two values of the same physical property like temperature, pressure, concentration, or electrical potential; the chemical engineer's task then lies with the evaluation of the rate constant only. In chemical reaction, however, the expression which is the driving force is more complex and generally involves the partial pressures or concentrations of all the molecular components taking part in the reaction. Chemical reaction is discussed in detail in Chapter 5. A further concept which the chemical engineer needs to grasp concerning rates is that of continuity. The chemist in his laboratory works in batches; a primary object in all chemical process industry is to achieve continuous operation; raw materials are fed continuously at one end from a bulk store and products leave the plant continuously and are fed to the product storage. The emphasis is on carrying out the necessary processes of mixing, heating, reacting, and purifying during the steady progress of the materials through the plant equipment. Batch processing is now used infrequently.
3.4 DIMENSIONAL ANALYSIS

In chemical engineering it is not unusual to deal with a process or system in which a process variable to be calculated depends on a large number of other variables. In order to calculate the desired variable, an equation is required to express that variable in terms of the variables on which it depends. To look at the problem from another angle, let us suppose that in the laboratory the experimenter has determined a large number of values of the desired variable (say boiling point of a solution) for different sets of values of the other variables (pressure, concentration); he then wishes to do two things. Firstly, he would like to plot graphs of his results using appropriate groupings of the variables and, secondly, he would like to produce an equation or correlation of the variables. This correlation is a simple form of the results which other chemical engineers can use readily. Dimensional analysis enables the groupings and the form of the correlation to be defined. Dimensional analysis is based on a simple principle that, in any equation, the units of the functions on each side must be the same, i.e. a velocity cannot be equated with a force. The dimensions of a quantity are the types of measurement needed, and the way they are used, to define the quantity.
37
Velocity, for example, requires the use of the dimensions of length (or distance) and time in fact length divided by time. The dimensions of a quantity are closely related to its units since the units used to define a quantity are made up from the units used to measure the dimensions of the quantity. The unit of length is the meter, of time the second, and of velocity m/ssimilarly, the dimensions can be expressed (length)/(time). The dimensions of the quantities with which the chemical engineer deals are mass m, length l, time T, temperature t As pointed out in Section 3.2, all units can be derived from these four. However, it is sometimes convenient to use other basic dimensions and this is permissible. The dimension of heat (H) may be used in problems not involving interchange of mechanical and thermal energy. Redundancy in the definition of dimensions must be avoided. This means that it must not be possible to equate one dimension to a function of the other dimensions. For example, having specified the dimensions length and time, one must not specify velocity (ratio of length to time) as a dimension.
3.5 HEAT TRANSFER

The presence of heat energy in a gas, liquid, or solid is recognized by the motion of the atoms or molecules within the substance. There are three basic mechanisms for the movement of heat.
1. Conduction.
In conduction in solids and liquids, heat is transferred from the warmer region of the substance to the cooler by the interaction of individual molecules one with its neighbor, during which the energy of one molecule is shared with the neighbor. In gases, conductive transfer is due to kinetic movement of individual molecules. The kinetic motion allows heat to be conducted in two ways. Firstly, hotter molecules can move into cooler regions and, second, interactions between molecules enable energy to be conducted from hotter to cooler regions.
2. Convection.
Convection heat transfer can occur in fluids which are in motion. Heat moves from the warmer region of the fluid to the cooler by means of bulk motion of the fluid which interchanges small pockets of the fluid. Each time a hot pocket of fluid moves into the colder region, and vice versa, bulk transfer of heat as well as material takes place.
3. Radiation.
Radiative heat transfer occurs by the emission of electromagnetic radiation at infrared wavelengths from one material and its absorption by another material. Solids, liquids, and some gases can exchange heat in this way at the temperatures pertaining in systems, with which a chemical engineer normally deals.
38
While conduction and convection only take place in a continuous system, radiative exchange can occur between bodies well apart.
HEAT TRANSFER C OEFFICIENTS

The problem which frequently confronts us is shown in Figure 3.2(a). Heat is being transferred from a hot fluid flowing inside the tube to cold fluid outside the tube. C is the tube wall and flow is countercurrent. The temperature profile is sketched beside the diagram of the tube and the temperatures are described in more detail shortly. Heat transfer within the regions is as follows:
Region A. When a fluid is flowing within a tube the tube wall causes drag on the fluid and
flow is fastest at the centre of the tube. Within A, convective heat transfer occurs owing to the motion of the fluid.
Region B. In region B, the boundary layer, flow velocity is much slower and insufficient for
convection. Heat transfer is conductive in this region. conduction.
Region C. This is the solid material of the tube wall through which heat passes by Regions D, E. These regions for the outer fluid correspond to B and A respectively, for the
fluid inside the tube. From the temperature diagram, it will be seen that most of the temperature difference is in the two conductive transfer zones. This is because conduction in these zones provides a slow rate of heat transfer. (For the moment we are neglecting radiationit is usually not significant below about 500 C.) Heat transfer problems of this type are solved by using heat transfer coefficients. To demonstrate such a coefficient we can consider heat flow through the tube wall by conduction. The heat flow rate Q is given by Q = conductivity X area X temperature gradient = k.A.T where T= temperature difference across the tube wall, = thickness of tube wall, k thermal conductivity of wall material. Thus, for that tube Q = A. T. k/ =h.A. T (This formula is only strictly true for heat flow through a flat plate but is a good approximation for thin-wall tubes.) h is the heat transfer coefficient for that tube wall and is the heat flowing per unit time per unit area per unit temperature difference. It was seen earlier that heat transfer rates in the liquid zones are also limited by conduction through a liquid layer and a similar equation can be written for flow of heat from the bulk fluid to the inner tube wall and from outer tube wall to outer fluid. For transfer of heat, an expression can be written Q = h.A. T (3.4)
39
where Q - heat flow rate (J/s) A = area for heat flow (m2)
h = heat transfer coefficient (J/s K m2 )
T = difference in temperatures (K) between which heat transfer is being considered. The temperature graph in Figure 3.2(a) shows that the temperature of the fluid in the tube is not uniform, but the fluid does have a mean temperature or 'cup temperature'; this is the uniform temperature which the whole liquid volume would attain if heat transfer from the liquid were suddenly stopped. It is this mean temperature (T1 in the graph) which is used in the heat transfer equation to calculate T.
Figure 3.2 Heat transfer through the wall:
TYPES OF HEAT EXCHANGER The discussion here has been concerned with tubes because the majority of heat exchangers are made up from a large number of tubes, which provide the surface area needed for transfer of heat between two process fluids. The same heat transfer relationship is used for the whole set of tubes as for the single tube. One of the process fluids flows through the tubes and the other flows outside the tubes, the tubes being surrounded by a shell which contains the outer fluid. This is called a 'shell-and-tube' heat exchanger (see Figure 3.4) and the fluid in the tubes is called the tube-side fluid, that outside the shell-side fluid. It is usual to put baffles in the shell which make the shell-side fluid flow back and forth across the tubes as it goes from end of the shell to the other.
40
Figure 3.4. SHELL AND TUBE HEAT EXCHANGER. This exchanger is made up of U-shaped cupro-nickel tubes in a bundle and an outer shell (not shown) which fits closely over the bundle. The tubes are continuous from the upper section of the tube plate to the distant end, where they bend, and then come back to the lower section of the tube plate. The cover over the tube plate has a lower entry hole, an upper exit and a central horizontal partition to ensure that liquid passes through the tubes. The baffles can be seen in the bundle and these cause cross-flows in the shell side giving higher velocity and improved rate of heat transfer. The exchanger has a mixture of cocurrent, counter-current and cross-flow. A typical use for this exchanger would be as a cooler.
This cross-flow factor speeds up the flow over the tubes and increases the shell-side heat transfer coefficient. Allowance is made for this, by standard techniques, in calculating the coefficient. A few further common forms of exchanger used for cooling duties should be recognized by the reader. 1. Serpentine coolers. The fluid to be cooled passes through a set of horizontal zigzag tubes; the set of tubes lies in a vertical plane. The cooling water is distributed over the length of the top tube section, runs round it, and then drops off on to the next tube section and so on. 2. Air coolers. Heat transfer coefficients for air and gases are much smaller than for liquids, and large surface area is therefore necessary. It is commonly achieved in air coolers, where air is used to cool a gas or liquid, by putting fins on to the outside of the tubes. This can give up to ten times the surface area. The fluid to be cooled passes through the tubes and the cooling air is drawn through a bank of closely packed, finned tubes by a fan placed in the space above the tubes. 3. Solid coolers.
41
Solids are frequently cooled by air. This must be done by keeping the solids continuously in motion in the air. A standard method is to use a rotating drum which has plates protruding a short way from the inner surface of the drum. These repeatedly lift the solid particles up and then drop them through the air. A slope of the drum or angling of the lifters causes the solids to move along the drum counter-current to the air flow. Inventiveness is still vital to chemical engineering and a recent invention is a new type of solids coolerthe waterfall cooler. The solids fall downwards through up-flowing air in a series of cascades. The effect is similar to the drum, but the equipment is cheaper in cost and requires less power. Calculation of Heat Transfer Coefficients Heat transfer is a process in which the following factors are involved: Liquid velocity Liquid density Liquid viscosity Liquid specific heat Liquid thermal conductivity Tube diameter Tube length v p u Cp k d l
The importance of most of these is obvious, of others perhaps not so obvious. Velocity is important because as velocity increases so also does the rate of interchange of liquid 'pockets' causing convection transfer; p and Cp measure the heat-carrying capacity of a pocket, and the viscosity affects the "mobility' of the liquid and rate of movement of the 'pockets'. It is possible to use dimensional analysis to derive a useful relationship between the variables: hd / k (pvd / u)a X (uCp / k)b X (l / d)c The left-hand side includes only the coefficient // which we wish to determine and k and d which are physical properties of the system. Firstly, what is the significance of l/d in this relationship? Its appearance is indicative of the fact that the flow pattern of the liquid in a tube changes along the length of the tube. In fact, the liquid must be 20-40 diameters along the tube before a constant flow pattern is established-more about this in the next section of this chapter. In heat transfer design problems, this "entry region' effect is usually ignored and only the first two terms of the righthand side are used in practical correlations. The three dimensionless groups are given the names of their originators. hd / k = Nusselt number = (Nu) pvd / u = Reynolds number = (Re)
42
uCp / k = Prandtl number = (Pr) Thus (Nu) (Re)a x (Pr)b
By further dimensional analysis, other dimensionless groups can be derived, but these can be expressed in terms of the three above. Peclet number - (Pe) = (Re) .(Pr) Stanton number - (St) = (Nu)/(Re).(Pr) The relationship of (Nu) with (Re), (Pr) is used by experimenters to correlate their results and establish equations for common use by chemical engineers in design work. Experiments on tubes with fully established, turbulent flow have led to this equation: (Nu) = 0.023 (Re)0.8 (Pr)0.4 (3.18)
Results for flow outside tubes allow similar correlations to be made, so that the two transfer coefficients can be determined and used with the fouling factors and the tube wall coefficient to evaluate U.
3.6.
FLUID MECHANICS
Fluid mechanics is concerned with the behavior of gases and liquids in motion and we will start by listing the parameters involved:
1. Fluid density.
Density is defined as for a solid as the mass per unit volume.
2. Fluid velocity.
The property of fluidity allows different parts of a continuous fluid to have different velocities. There is a velocity in each region of the fluid. Also, for any containing pipe or duct in which a fluid is flowing, there is the mean fluid velocity obtained by dividing the volumetric flow through the pipe or duct by its cross-sectional area.
3. Fluid pressure.
Each point in the flowing fluid has a pressure; because the fluid is flowing, the pressure-sensing device used for measurement will indicate a different value depending on whether it is placed perpendicular to the flow or parallel to it. By the pressure in the fluid we mean the pressure that would be detected if the sensing device were able to be moved with the fluid at the point of measurement.
4. Viscosity.
43
Viscosity is a well-recognized phenomenon. It is seen in the tendency of a fluid to resist change of shape; treacle and oils are highly viscous, water and organic solvents are of low viscosity. The 'perfect' fluid has no viscosity. Viscosity is not apparent in a stationary fluid; it is noticed only when the fluid is in motion. When treacle is spread over toast, the knife adheres to the top of the fluid while the bottom of the fluid adheres to the toast and it is necessary to apply a force to the knife in the direction of spreadinga shear force. The effect that is created by this force is to maintain layers of the fluid in motion over one another and, while the knife moves at a constant speed, the layers beneath all move at different velocities; a 'velocity gradient' is created and the greater the force the greater is the velocity difference between one layer and the next. The velocity gradient is proportional to the shear force applied per unit area, i.e.
F dv / dy
or
F = u (dv / dy)
The viscosity is the shear force per unit area required to achieve unit velocity gradient in the fluid. Most fluids obey this equation, and these are called Newtonian fluids, while those that do not are non-Newtonian. (Frequently, non-Newtonian fluids are those containing long-chain molecules which interfere with each other or are fluids containing suspended solids.) A 'theoretical' fluid having zero viscosity is said to be inviscid. In a stationary fluid the only property which varies throughout the fluid is the pressure; pressure increases with depth owing to the increasing weight of fluid above. The pressure p at a depth h below the surface due to the weight of liquid of density p is P=pgh (3.19)
Because of this linear relationship between pressure p and head of liquid h, it is common to measure pressure as the equivalent 'head' of liquid. Two kinds of fluid flow are distinguishable-laminar flow and turbulent flow. Laminar flow is characteristic of low-density, viscous, slowly moving fluids; transition of the flow of any fluid to turbulent flow takes place at higher velocity. Laminar flow is also called streamline flow because it is characterized by the fact that all particles of fluid arriving at a given point in the system will follow the same path or streamline through the rest of the flow system. The lines of flow through the system can all be plotted and flow remains along these lines. In turbulent flow, the reverse is true; while the average motion remains in the direction df flow, individual particles of fluid dart hither and thither in random motion.
EQUATIONS OF MOTION
In studying the equations of motion of fluids, we shall consider fluids under conditions where they have constant density, i.e. where they are 'incompressible'. Fluids will deviate from these equations when their velocities begin to approach the velocity of sound.
The Continuity Equation

Because the fluid is continuous and incompressible, the mass flow through any cross-section of the flow is constant, i.e.
44
pva = constant where v = mean fluid velocity through cross-section of area a.
The Acceleration Equation

This equation is exactly the same as in mechanics, i.e. Force = mass X acceleration In dealing with fluids it is more convenient to use the alternative form Force = rate of change of momentum or F = m x v where m is the mass flow per unit time and v is the change in mean velocity between the two points in the flow path which are being considered.
The Energy Equation

The energy equation due to Bernoulli states that, in streamline flow of an in viscid fluid, the total energy of the fluid is constant throughout the flow system. Consider the flow system shown in Figure 3.5(a). Liquid level in the reservoir is h1 above the datum and liquid at the top of the reservoir has potential energy h1g per unit mass.
45
(b)
Figure 3.5. FLUID FLOW SYSTEMS: (a) Constant-energy flow, (b) Flow of water through nozzle at end of flexible hose
At point (2) there is no significant flow but the potential energy of the liquid is less by (h1 h2)g. This energy has been converted to 'pressure energy'; if a hole were made in the tank at this point the energy of the stream released would be derived from this pressure energy. In fact, the energy comes from the loss of potential energy of the system as the liquid level falls. The fluid issuing from the hole behaves as though it has Total energy = pressure energy + potential energy Equation (3.19) shows that p2 = (h1 h2)pg Thus, the potential energy change between (1) and (2) (h1 h2)g is replaced by pressure energy p2/p. Total energy per unit mass at (2) = h2g + p2/p. At point (3), the potential energy is h3g and the pressure energy is p3/p. In addition, the flowing liquid has kinetic energy per unit mass v2/2. Total energy per unit mass at (3) = h3g + p3/p + v2/2. Bernoulli's theorem then equates the energies at (1), (2), (3), i.e. h1g = h2g + p2/p = h3g + p3/p + v32 /2 (3.20)
An example of the use of the energy, momentum and continuity equations is in the calculation of the force necessary to hold a fire hose-see Figure 3.5(b). It is assumed that the pipe is flexible and provides no restraining force.
Continuity Equation
pv1A1 = pv2A2 = m where m is the mass flow rate (kg/s).
46
Energy Equation
V22 / 2 =p1 / p +v12 / 2 = p0 / p where p0 is the pressure in the supply reservoir feeding the hose. All pressures are measured above atmospheric pressure.
Momentum Equation
p1A1 - F = m(v2 v1)
REAL FLOW PATTERNS

We have seen earlier that viscous flow is streamline and have mentioned that velocities can vary throughout a flowing fluid. In practice, the viscosity of a fluid causes the layer in contact with the material containing the flowing fluid to adhere to the material. Thus at the wall the velocity is zero. The effect of viscosity is that successive layers slide over each other at increasing velocity, giving rise to a velocity profile. The laminar flow profile in a pipe is as shown in Figure 3.6(a).
The shape of this profile is a parabola and the mean velocity is half the velocity at the centre. The pipe wall is having a 'dragging' effect on the fluid near it and prevents it going at the mean stream velocity. The pipe wall applies a drag force against which the fluid must expend energy. Returning to Bernoulli's theory (Eq. (3.20)) it will be seen that, in a straight level pipe, loss of energy can result only in a reduction in pressure pipe drag or friction causes pressure drop in the fluid. If f is the frictional force per unit pipe surface area, then for a pipe of length Z, and diameter 6/ the pressure drop is given by p = 4FL / d (3.21)
As the velocity in the pipe increases, it reaches a critical value above which the How starts to become turbulent. Turbulence starts at the centre of the pipe and the transverse random motion causes velocities in the central region to be equalized. As the velocity increases more, the turbulent core extends out towards the tube wall, leaving a diminishing laminar layer at the wall (see Figure 3.6(Z))). This type of flow is often referred to as 'plug' flow, because most of the fluid now has a constant velocity and the average velocity approximates
47
closely to the maximum. We are still concerned with laminar flow at the wall and Eq. (3.21) still applies. In the case of flow where frictional effects are important, Bernoulli's theory can still be applied, provided that allowance is made for frictional losses. It may also be applied to turbulent flow in a pipe if the pipe is considered as a whole and provided that a constant containing surface is presented to the fluid. A sudden change in the containing surface results in break-up of the streamlines in the laminar flow or, in the case of turbulent flow, breakaway of the laminar layer. This breakaway causes eddies and vortices in which pressure energy is lost although flow returns to streamline further downstream. An example is a sharp expansion of pipe diameter.
FLOW MEASUREMENT
Most methods concerned with flow measurement are based on the principle of using a device which can detect a pressure drop, from which the fluid flow may be determined. Four measuring devices are now described briefly.
1. The orifice plate.

This is by far the most common means of measuring flow. A plate is placed inside the pipe; it has a central hole with diameter about two-thirds of the pipe diameter. This accelerates the fluid and causes a pressure drop; tappings on either side of the plate are taken to a manometer which indicates the pressure difference. This p is used to calculate the flow rate using standard constants applicable to the plate in use.
2. The venturi meter.

A venturi is a pipe which contracts smoothly to a reduced-diameter throat and then expands smoothly back to the original diameter. Because the changes are smooth, no energy is lost by turbulence. Bernoulli shows that pressure is less in the throat where velocity is higher. The pressure difference between the throat and main pipe again give a measure of flow rate.
3. The rotameter.
The rotameter consists of a conically shaped float in a tapered, transparent tube through which the fluid whose rate is to be measured flows upward. As the flow rate increases, it lifts the rotating float higher up the tapered tube. The tube is graduated in units of flow rate of the fluid for which the meter is designed.
4. The Pitot tube.

The Pitot tube is a tube pointed directly into the direction of flow. The pressure measured by the tube is compared with the static pressure in the fluid and this difference measures the velocity head of the fluid; it is therefore an indication of fluid velocity. All aircraft rely on this method for measurement of airspeed; the Pitot tube projects well into the
48
air stream which is undisturbed by the presence of the aircraft. A tapping in the side of the tube detects static pressure. A few words now about instrumentation. The chemical plant operator does not want to be told a p; he wants the instrument to inform him of the flow rate either on the plant or in the control room. Commonly, this is done in the following way. The two pressure tapings are connected by short pipes to either side of an instrument called a "DP cell', which converts the pressure difference (DP) into mechanical movement. The DP cell acts in much the same way as the aneroid barometer or the altimeter in an aeroplane. By simply adjusting lever lengths, etc., in the mechanical side of the cell, the movement can be made to deflect a needle on the indicator over the desired distance for the flow rate to be measured. The scale on the indicator is marked in appropriate flow units. The DP cell works on a principle similar to that of the aneroid barometer; it contains a small metal diaphragm and the two pressures are fed to either side. A change in the pressure difference causes movement of the diaphragm, and this movement is transmitted mechanically to the needle. In the case where indication in the control room is required, the movement of the mechanism is converted to a signal -either air pressure or electrical. This is carried by pipes or wires as appropriate to the rear of the control panel, where it is converted back to a mechanical movement which moves the needle on the indicator in the panel. In principle, it would be possible to take the pressure tapping pipes to the control room, but this is frequently inconvenient; the process fluid is in these lines and it may be subject to freezing, vaporizing etc., so that it is rarely practicable to take these pipes to the panel. Instrumentation and the transmission of information between the plant and control room are discussed more fully in Chapter 7.
MACHINERY
The machinery of fluid flow is concerned with the interchange of mechanical and fluid energy. The objective is to be able to create fluid How and pressure by carrying out mechanical work and, conversely, to be able to obtain mechanical work from fluids under pressure or at high velocity. Let us consider first the creation of work from fluids. The principle of the steam engine was to use high-pressure steam in a cylinder to drive a piston, whose motion was transferred to the rotating shaft through a crank. This reciprocating type of machine has now been replaced in most applications by the turbine. There are two turbine types, based on the Watermill' principle and the 'windmill' principle, respectively. The 'watermill' is more scientifically defined as an impulse turbine. The fluid flow is tangential to the disc of rotation of the turbine and momentum is transferred from liquid to turbine blades. In a modern impulse turbine, the blade design is an improvement on the watermill, the object being to design the blades so that they absorb the maximum proportion of the momentum of the fluid stream. The stream is aimed as a jet at the blades. The impulse turbine converts velocity energy into work. The windmill has its disc of rotation perpendicular to the wind direction and it is the flow of the air over the blades which cause rotation. When this principle is used in a gas or steam turbine a large number of small blades is set around the periphery of the turbine disc see Figure 3.8. In the same way that the wing of an aeroplane is shaped to give 'lift' as air flows
49
past it, so a force is created on the turbine blade in the direction of rotation as the gas or steam flows past it. This type of turbine is called a reaction turbine. To make full use of the fluid energy the reaction turbine usually consists of a set of turbine discs on the same shaft, each disc having its blades individually shaped and set to achieve maximum recovery of energy from the fluid stream. In between the turbine discs, sets of stationary blades are placed which adjust the direction of fluid flow after the fluid has passed each turbine disc. These stationary sets of blades are fixed to the turbine casing. The reaction turbine converts pressure energy into work as the fluid passes through it. There are a number of different pieces of equipment in which mechanical work is converted into fluid energy. The basic objective in all of them is to create fluid pressure. In some cases this is simply to overcome the pressure losses in a pipe due to friction; in others it is to lift a liquid from one level to another or to compress a gas. All pieces of equipment of this sort for liquids are called pumps. In the case of gases there are two names:
Compressors are used when the object is to attain higher gas pressure, and Fans are used to obtain
gas flow.
Pumps
As in the case of the steam engine, the first types of pump were of the positive displacement type in which direct force on a piston in a cylinder pushed liquid into the higher-pressure side through a valve. When the cylinder was empty, the outlet valve closed and the inlet valve opened to allow filling from the low-pressure side as the piston returned to the start of the stroke. This type is still used when very high pressure is required. The modern pump, however, achieves pressure by centrifugal force. The fluid enters the rotating disc of the pump at the centre and is then made to rotate with the impeller by the impeller blades as it flows towards the periphery of the impeller. At the periphery, the fluid has high velocity and is constrained by the pump casing to a rotational direction; pressure is therefore created at the periphery of the impeller by the centrifugal force. If the pump is simply filled up and the motor started, the impeller will freewheel, but a fluid rotation will be created in the casing and operating pressure will be set up in the delivery chamber. If a supply of fluid in a tank feeds the pump, it will be possible to allow liquid to pass out of the pump and a certain flow rate will be established. This will depend on the pressure against which the pump is made to work. '1 his pressure is referred to as the delivery head, and is measured as the difference in levels between the 'suction' and delivery sides of the pump.
50
Figure 3.8. TURBINE COMPRESSOR SET FOR NITRIC ACID PLANT. This picture shows the set with the covers removed. The turbine rotor with bladed discs is at the near end. The discs increase in size towards the rear of the picture and that is the direction of steam flow. The compressor discs at the far end are of the centrifugal type and can be seen to have spaces between the flat discs; this is the space through which the air flows. The final disc beyond the compressor is the gas expansion turbine
The relationship between the delivery head and the fluid rate delivered by the pump is called the 'pump characteristic'. In the description above we have assumed that the pump characteristic would show head decreasing as flow rate increases (Curve A in Figure 3.9). This is not always the case, and many pumps are designed to have maximum head at some flow rate. If the pump we considered above had been of this sort, then, as soon as the head against which the pump is to deliver was reduced to that given by the characteristic for zero flow, the flow rate would go from zero up to that value at which the head is again the same - flow rate X in Figure 3.9. In designing pumping systems, particular attention has to be paid to the provision of 'suction head'.
51
This means that adequate head of liquid, hs, must be provided on the feed side of the pump. As liquid passes into the pump its velocity increases and, as Bernoulli's theorem tells us, pressure decreases. If adequate suction head is not provided, it is quite possible for pressure at some point on the impeller to decrease to the extent that evaporation of the liquid occurs. This result in a phenomenon called 'cavitation'a localized vibration which causes rapid damage to the impeller.
Compressors
Compressors also may be of the reciprocating or rotary type, but there is a continuing tendency for the latter type to replace the former in more and more applications. The reasons are lower cost, higher efficiency of operation, greater continuity of operation, and lower maintenance costs for the rotary type. Rotary compressors again may be divided into two types. The centrifugal one is similar in principle to the pump, pressure being created in the outer casing. The axial-flow compressor is the opposite of the turbine described above; the gas passes through a series of rotating, bladed discs interspaced with sets of static blades. The discs are of decreasing area along the flow path and pressure increases. The compression of a gas results in an increase in temperature, but more energy is required to compress a hot gas than a cold one. Interstage coolers are therefore provided to reduce the temperature of the gas after each stage of compression.
Fans
Fans, or blowers, as they may be called, are used to create a flow of gas where no significant compression is required. Axial fans, like aeroplane propellers, may be used for large-quantity flow when there is small resistance. Centrifugal fans like centrifugal pumps can be used to blow gases along pipes or ducts. There are also other types of fans and blowers used for specific duties.
52
Chapter 4
THERMODYNAMICS
Thermodynamics is the science of physical and chemical change. Since the chemical engineer's business is the engineering of such changes, thermodynamics is the basis of much of his work. He is concerned with the application of thermodynamics to both chemical and thermal energy changes. Historically, the principles were first applied to problems involving thermal energy. The discussion in the first sections is therefore related to such problems and only towards the end of the chapter is the theory of chemical thermodynamics discussed. Thermodynamics is a subject built up entirely logically from a few simple premises. These premises arise from our everyday experience of heat and the part played by heat in those changes which either liberate or employ ithence its significance in chemical processes. The principles of thermodynamics, as will be seen later, can be rigorously applied to all chemical processes. The use of thermodynamics enables answers to be obtained to the following questions: 1. Under what conditions of temperature, pressure, composition, etc., will the change take place? 2. To what extent will the change proceed under specified conditions? 3. When the change occurs what changes in energy take place and what forms of energy are involved? Thermodynamics does not provide any information about the speed with which a change will occur. In thermodynamics it is necessary to refer frequently to 'that which is changing', i.e. the section of matter which is to undergo change. The matter for example, may be simply a gas which is expanding, or the gas expanding in its containing vessel, or the gas expanding in the vessel driving a piston, etc.. For ease of continual reference to such 'matter' which is changing, it is referred to as a 'body' or a 'system'. Theory of thermodynamics is built up from consideration of ideal bodies and systems, while real systems are studied by approximating them to appropriate ideal systems. A system or body, then, is some defined matter which is able to undergo change. To begin with, the only bodies we shall consider are those of a single chemical component, since it is simpler to discuss the basic laws of thermodynamics without the complication of chemical change. In Section 4.8 the discussion is broadened to include multi-component chemical systems and the term 'chemical potential' is introduced. There are many forms of energy-thermal, mechanical, electrical, nuclear, chemical and all are interchangeable using various types of device. The extent to which any pair may be interchanged under any specified set of conditions is limited. The concepts of thermodynamics are the four laws of thermodynamics. The first and second laws are the two premises or principles which are the cornerstones of thermodynamics. The
53
zeroth and third laws are postulates which must be made in rigorous development of thermodynamics. The laws, then, are in outline as follows.
Zeroth Law
This is concerned with the fact that when two bodies are put in contact they reach the same temperature. The law is usually stated as follows. Two systems, which are each in thermal equilibrium with a third system, are also in thermal equilibrium with each other.' The statement in this form allows 'temperature' to be defined later as a thermodynamic concept.
First Law
The first law is concerned with the interchangeability of different forms of energy and the fact that energy in one form can only be obtained at the expense of another form of energy. The law may be stated as follows: 'In an isolated system the total energy must remain constant, although it may be changed from one form to another.' A corollary of this, which is sometimes used as an alternative statement of the law, is that the total energy change required to alter the state of a body from stated to state B is independent of the series of states through which the body passes in changing from state A to B. (This is most important in chemical processes, since it means that reaction of material A into product B may go by various steps, but the net energy change will always be the same.)
Second Law
This law is concerned with the limitations on interchangeability of heat energy with other forms of energy. It is not possible simply to take heat from a source and convert it into mechanical energy. We do not need to examine the reasons yet, but they are related to the fact that thermal transfers are irreversible. Heat cannot be persuaded to flow from a cold body to a hot one. The second law has been stated in several ways: 1. Clausius It is impossible to construct a device that, operating continuously round a cycle, will produce no other effect than the transfer of heat from a colder to a hotter body. 2. Kelvin It is impossible to construct a device that, operating continuously round a cycle, will produce no effect other than the extraction of heal from a reservoir and the performance of an equivalent amount of work. 3. All processes which occur without external interference are irreversible.
Third Law
This is concerned with establishing the zero reference state of a function called entropy, which is defined as a result of the second law. The third law states that the entropy of a crystalline substance in pure state is zero at the absolute zero of temperature.
4.1 THE THERMODYNAMIC FUNCTIONS
54
Two types of property of a system must be recognized:
1. Extensive functions: these are properties or variables which get larger as the size
of the system increases, e.g. mass, volume, and energy.
2. Intensive functions: these do not change as the size of the system changes; e.g.
pressure, density, and energy per unit mass. These common variables are all involved in thermodynamics, but the laws enable additional properties to be defined the thermodynamic functions, which arc internal energy, temperature, and entropy. These will be defined as they arise. Temperature is a property we all recognize. A number of properties of materials, which are dependent on temperature, are used to measure it; thermodynamics provides a rigorous definition of temperature, and a means of measurement for all conditions. Temperature is a thermodynamic function, which is recognized qualitatively as a result of our experience of thermal equilibrium stated in the zeroth law, that 'If two bodies arc both in thermal equilibrium with a third body then they are in thermal equilibrium with each other.' We recognize thermal equilibrium by equivalence of temperature, but the zeroth law is expressed without reference to temperature, since a quantitative definition of temperature is to be made later on the basis of the second law. The question may be raised as to how 'thermal equilibrium' is determined without temperature measurement. The answer is that thermal equilibrium is said to be reached when all observable properties of the two bodies are constant. I laving achieved such a situation both between A and (.' and between bodies B and C, we can put bodies A and B in contact and find that there is no change in any of their properties pressure, composition, density, color, etc. This is our basic concept of thermodynamics the recognition of changes which take place when 'hot' and 'cold' bodies are put in contact and the understanding of tlie phenomenon of 'thermal equilibrium' in terms of such changes.
4.2 THE FIRST LAW

Work is defined quantitatively as the product of force and the distance the point of application of the force moves. Energy is expended by a system which docs work, and the quantity of energy in a system defines the amount of work of which it is capable. The fact that work could be derived from systems in which energy was stored in a variety of ways led to the recognition of different forms of energy and the convertibility of energy. It also led men such as Joule to investigate the quantity of energy in one form which could be obtained from another form. The realization that, whenever energy was converted from one form to others, the amount of energy obtained in the new forms was equal to the energy lost in the initial form resulted in the acceptance of the 'principle of energy conservation'. This principle, together with the interchangeability of energy, provides the first law. If, then, energy is indestructible, the total energy of an isolated body must be a property of the body. Furthermore, interactions between bodies must produce calculable changes of the energy of each body, while the energy of the two bodies taken together remains constant. The total energy of a body is made up of various parts; firstly, there are those which depend on what is happening to it in relation to its external environment -i.e. its kinetic and potential
55
energy; second, there are those parts which are dependent only on the internal state of the body. The internal state of the body depends on temperature, pressure, and composition so far as we arc concerned in studies of thermal mechanical and thermal chemical changes. That energy of the system which is only dependent on internal state is called internal energy symbol U. Suppose that a system is allowed to undergo a change in which nothing else can occur except that an amount of work w is done by the system on a body external to the system. W = U1 U2 Where U1, and U2 are the initial and final internal energies of the body. An example of this would be the slow expansion of a gas in a perfectly insulated cylinder lifting a frictionless piston. No heat is lost from the system (the gas in the cylinder) and work is done in lifting the piston. U1 and U2 will be different and the states of the gas in conditions 1 and 2, as defined by temperature and pressure, will also be different. If it were now possible to do work w on the gas it would recover its initial internal energy U1 and the state of the gas, temperature and pressure, would return to the original values. Whenever the system is in its initial state, its internal energy is U1. The internal energy of the body could have been changed by heating it. If an amount of heat q is transferred to the body then U increases and U2 - U1 = q It is conventional in thermodynamics to regard work done by the body under study as positive and heat given to it as positive. Thus, if the body undergoes a change in which it does work w and receives heat q, then U2 - U1 = q - w or for a differential change dU = dq dw (4.1)
We shall need to use this equation and the fact that internal energy is a function of the state of the body when we come to the definition of the absolute temperature scale in Section 4.4.
4.3 THE SECOND LAW

The second law, like the first, is a statement of actual experience. While the first law defines the energy transfers involved in a change within a system, the second law is concerned with the definition of what changes or transfers of energy are possible. Two types of energy transfer were studied by Kelvin and Clausius.
1. Kelvin
56
Joule had shown that work could be converted into an equivalent amount of thermal energy. Kelvin concerned himself with the possibility of the reverse process and asked himself, 'How do we go about removing heat from a hot body and converting it into an equivalent amount of work?' In considering the problem he was led to think of bodies repeatedly going through cycles. The idea would be to take a body in state 1 and put it into contact with the hot body; during this contact it would receive thermal energy and go to state 2. It would then be removed from contact with the body and be allowed to deliver up work during which its state returned to state 1. Such a device working on a cycle of this sort could not be found.
2. Clausius.
He examined the question of heat exchange. When a hot body is placed in contact with a cold body, heat is transferred from the hot body to the cold one. Clausius tried to devise a cyclic method for removing heat from a cold body and transferring it to a hot one. He also was unsuccessful. These two processes are possible only if some additional body is brought into the system and its state is changed during the process. The processes of transfer of work into heat and transfer of heat from a hot to a cold body are said to be irreversible', the processes in the opposite direction can only be carried out if an additional body is involved and that body is in a different state at the end of the process. Those of us who have not had experience of attempting to devise cyclic methods to convert heat into work or to transfer heat from a cold to a hot body must accept the Clausius and Kelvin statements of the second law as accurate. We can all recognize that some processes occur naturally or spontaneously, i.e. without any outside interference; the transfer of heat from a hot to a cold body is such a natural process. What processes, then, are not 'natural'? Those processes which require only an infinitesimal change in the conditions under which they are occurring to make them proceed in the opposite direction, i.e. they are reversible processes. As an analogy, consider a perfect cube and a perfect sphere standing stationary on a perfectly flat table. The cube is perfectly balanced on an edge. Tilt the table slightly for a moment and then return it to the level. The cube drops onto one side and stopsthe sphere starts to roll very slowly. Now repeat tilting in the reverse direction and the sphere stops. Sphere rolling -reversible process: cube falling-irreversible or natural process. Note that the cube goes from an unstable to a stable state while the movement of the sphere is through a series of stable or equilibrium conditions. Although this is not a perfect analogy of a reversible process, it is a fact that processes which are reversible are those which pass through a continuous series of equilibrium conditions. To summarize, Kelvin and Clausius proved to their own satisfaction that there are certain processes which can only be reversed by introducing another body which is in a different state at the end of the process. We have seen from our own experience that natural or spontaneous processes are not easily reversed, while processes which can be reversed reversible processes-are those which pass through a series of equilibrium conditions. We conclude that Clausius and Kelvin were trying to reverse natural processes and this accounts for their lack of success.
57
Natural (irreversible) processes we know take place readilywhat about reversible processes? As an example of a reversible process, consider saturated steam at a temperature fractionally higher than the temperature of a" large body. Heat will slowly be transferred from the steam to the body and steam will condense. Note that, because of the very small T, heat transfer and condensation will be very slow. Throughout the condensation process, the system is essentially at an equilibrium condition. A very small reduction in pressure of the steam will cause the process to be reversed and water on the surface to evaporate. This example demonstrates the two properties of reversible processesthey proceed very slowly and the system is very close to equilibrium. In fact, if we want to know whether a process will proceed or not we must ask ourselves whether it is a spontaneous process. There are, then, processes which will proceed and those which will not. When such a behavioral difference as this is noted it is usually possible to find some physical property which accounts for the difference. To take a rudimentary example if one observed people picking up a book and starting to read and one noticed that some put on spectacles before reading and others did not, one could examine various properties of the peopletheir age, weight, sex, height- and one would find that age was the important factor. Conversely, if one excluded 'age' from the study and found there was no variable which could be correlated with one's observations one might be led to postulate the variable 'age'. Sue! s rather the case with regard to changes in thermodynamics which are, or are not, observed to occur. The variable postulated is entropy symbol S. In Section 4.5, the variable entropy will be examined in more detail and we shall see the physical significance of it and how it determines whether or not processes will occur. The second law, then, recognizes the existence of irreversible processes. Irreversible (natural or spontaneous) processes take place at a finite rate; reversible processes occur under equilibrium conditions at an infinitesimal rate. The variable entropy is the property which determines the category into which a process will fall.
4.4 THERMODYNAMIC TEMPERATURE

We have shown that the second law imposes limits on the interchange-ability of heat with other forms of energy, and we can now show how the thermodynamic temperature scale is based on this law. Consider two bodies undergoing identical reversible cycles (Carnot cycles) as shown in Figure 4.1. Step I. Isothermal expansion, the body (A) receiving heat Q2 reversibly from a large supply of heat at temperature T2. Step 2. Adiabatic expansion. Step 3. Isothermal compression, the body (A) delivering heat Q1 reversibly to a large heat sink at temperature t1. Step 4. Adiabatic compression.
58
Body (A)
Figure 4.1. CARNOT CYCLES. Body (a]
Both bodies arc passing through cycles o] changing pressure, volume and temperature, as shown by the graphs
An adiabatic change is defined as one during which heat is allowed neither to enter nor to leave the body undergoing change. The temperatures t1 and t2 are measured on some recognized scale, e.g. in C on a mercury thermometer. In going round this cycle the body (A) does an amount of work W such that Q2 Q1 = W by the first law. The body (a) performs precisely the same cycle with the same heat supply and sink but the cycle is in the reverse direction and the heat changes, q2 and q1, are also in the reverse direction (i.e., the body receives heat from the cold sink and delivers it to the hot source). When the number of cycles N and n performed by (A) and (a), respectively, are such that NQ2 = nq2 Then the cold sink is unchanged. Since (A) and (a) have been undergoing cycles, they are unchanged and the hot sink must also be unchanged if it were not, the second law would be broken by that fact that heat was taken from the hot source and converted into work with no change to any other body. Therefore NQ1 = nq1 Hence, Q2 / Q1 = q2 / q1 The only variables of state of the system which have been specified are t1 and t2 Thus q2 / q1 = f(t1 , t2)
Considering (A) alone for a moment, in each cycle a certain fraction of the heat withdrawn from the hot source is converted to worka fraction W/ Q2 and this fraction also is a function only of the two temperatures. Temperature c, is entirely independent of t2 and it is difficult to see why t1should be dependent on t1, . In fact, it can be shown rigorously
59
that
q2 / q1 = f(t2) / f(t1)
Remember that t2 and t1, were measured on a common temperature scale. If we now define T = f(t), T is the thermodynamic temperature scale defined such that the value T of a body is proportional to the quantity of heat q which it can receive from, or deliver to, another body when it undergoes reversible isothermal volume change in thermal contact. For all bodies T= 0 under the same conditions at -273.16 "Celsius, and q2 / q1 = T2 / T1 (4.2)
It is possible to define the efficiency of the cycle through which the body goes- the Carnot cycle in terms of T. The efficiency of the cycle for conversion of heat into work is W / q2 = (q 2 q1) / q2 = (T2 T1) / T2 (4.3)
The absolute scale of temperature has been defined in terms of heat absorbed or released by bodies undergoing reversible Carnot cycles.
4.5 ENTROPY
In Section 4.3, it was stated that entropy, S, is the variable which determines whether or not the process from a state A of a body to a state B is spontaneous or not. We shall define entropy, then show that it is a function only of state, and finally see why it is that entropy is the variable which defines for us the nature of the process. We consider initially only differences in 5, not the absolute values of entropy. For a small, reversible process in which heat dq is absorbed by a body at a temperature T, the entropy increase of the body is given by dS = dq / T (4.4)
Since this was a reversible process the body or system delivering the heat dq will show exactly the same entropy decrease. Referring to the Carnot cycle earlier, the body (a) underwent a cycle in which it delivered heat q{ and lost entropy q1/Tl and then received heat q2 and gained entropy q2/T2 to return to its initial state. Rearranging Eq. (4.2) thus q1/Tl = q2/T2 and the entropy of the body (a) is unchanged after the cycle. By considering any cycle of the body (a) in the P V diagram to be made up of an equivalent set of Carnot cycles, it can be shown that quite generally for any reversible cycle dq / T = 0 Thus, only by changing the state of the body can its entropy be changed: entropy is therefore said to be a function of state.
60
Let us now reword our defining statement for entropy. The entropy change of a body between two states is defined by those states only; if the transition between those states is made reversibly and isothermally, then the entropy change is the ratio of the heat absorbed to the absolute temperature. If the state of !he body changes in other ways then its entropy still changes by the same amount but the change cannot be calculated as q / T. Now we can return to the use of entropy as a criterion for irreversibility. The second law enables it to be proved that, under adiabatic conditions (i.e. q = 0), the entropy of a body remains constant when it undergoes a reversible change but increases as a result of any natural change, in an isothermal change, the entropy increase of a body is equal to the ratio of heat absorbed to absolute temperature for a reversible change, but is greater for a natural change. The above conditions are expressed below: Adiabatic change Isothermal change dV 0 dS dq / T (4.5)
Where the equals sign applies to reversible processes, and the greater than sign applies to natural processes.
4.6 HEAT ENGINES

The basic functions of thermodynamics are T, U, and S, but for systems in which heat exchanges with gases are involved a further function, enthalpy, is defined. Enthalpy H is a composite function, not a new one. H = U + PV (4.7)
Enthalpy is a function of particular use to the chemical engineer in designing heat engines. Enthalpy is alternatively referred to as heat content, since (dH / dT) constant pressure =Cp where Cp is the specific heat at constant pressure. For the purpose of tabulating or quoting values of enthalpy an arbitrary zero may be selected such that H = 0 at T= T0. Then, integrating Eq. (4.8) between limits T0 and T, HT = Cp x dT (4.9) (4.8)
25 "Celsius is frequently selected as the arbitrary zero and enthalpies are quoted with H= 0 at To = 25C. (Enthalpy data are sometimes referred to other datum temperatures.)
61
The advantage of H to the chemical engineer lies in its use in particular types of system where enthalpy is conserved. These systems are the steady-flow systems in which, for example, steam is made to drive a turbine. The steam raised elsewhere in the plant passes into the turbine, where it is reduced in both pressure and temperature in order to drive the turbine and do the work needed to drive a pump, compressor, etc., as shown in Figure 4.2. This is not, of course, a cyclic system; steam is simply fed to the turbine under one set of conditions and leaves under different conditions. In this example, we know the feed and exit pressures of the steam and the feed temperature and we wish to determine the flow rate and the exit temperature needed to provide sufficient power to drive the pump. We might at first think that there is a fluid flow system involving energy changes and that we should apply Bernoulli's energy equation to the problem. Bernoulli, however, is concerned with the pressure, kinetic energy, and potential energy changes resulting from steady flow. In the case of the turbine, the energy given up to the shaft as work is drawn from internal and pressure energy and is so much greater than the kinetic and potential energy aspects of the flow that these are negligible. We will also neglect at the moment any heat losses from the steam as it passes through the turbine. The energy balance on the steam is Enthalpy of steam at point (1 ) = work done per unit weight of steam + Enthalpy of steam at point (2) Consider first the case that the turbine operates reversibly. Since the process is called adiabatic, no gain in entropy will occur. In solving this type of problem, it is remembered that H and S are both functions of state. Tables are therefore available in which H and S' are quoted for values of T, P. In practice, two charts are used; these arc temperature-entropy and enthalpy, entropy charts, as shown in Figure 4.3. We know that if the process could be carried out reversibly it would be isentropic (no entropy change) and also that, in a real process occurring at a finite rate, entropy must increase. The H, S' diagram shows us that if entropy increases the enthalpy change is less i.e., less work is delivered to the shaft. How do we know what the entropy increase will be? The answer lies in the experience of the turbine designer. He knows that in practice, when he designs a turbine in a certain way, a given gain of entropy will occur. This is quoted by the designer as the isentropic efficiency ('isentropic' means constant entropy) Suppose that the turbine we intend to use has an isentropic efficiency of 80%: the change in enthalpy will be 80% of that at constant entropy. We can therefore select the point in the H -S diagram which satisfies this criterion. This allows us to use the T - S diagram to determine T2. Knowing the work per mole of steam delivered to the turbine, (H1 H2), we can calculate the steam How rate required to achieve the given shaft horsepower. Let us look at a few practical points arising from the example above. Given steam at a certain temperature and pressure, the maximum useful work can be obtained from it if 1. The pressure at the exit of the turbine is as low as possible, and
62
2. The turbine is designed to operate as nearly as possible to isentropic or reversible conditions.
Figure 4.3. THERMODYNAMIC CHARTS FOR WATER STEAM. These charts are used for calculations on heat engines using steam. On both charts constant pressure lines are plotted. In the T-S chart, the pressure lines are horizontal in the two-phase region between the initial boiling line on the left and the saturated steam line on the right. Only a section of the full H--S chart is shown; the complete diagram (also called a Mollier chart) would show the initial boiling line also, (a) T-S diagram, (b) a section of the H-S diagram
Failure to operate isentropically does not result in loss of energy from the steam. It simply means that the work obtained from a given pressure change is not as high as it could be, and that the steam leaves the turbine at a temperature higher than it would if isentropic conditions existed. In practice, the 'usefulness' of the steam is reduced by isentropic inefficiency because its pressure is lower than it would have been if the turbine worked isentropically. With lower pressure it is not so 'useful' for further jobs of work involving expansion, hut its heat content is still available for heating duties. In a chemical plant the steam system of multiple heaters, coolers, turbine drives, boilers, etc., is interconnected and it is nut usually necessary to consider together the turbine and the
63
boiler. In other applications e.g. small electrical generating sets - the turbine and the boiler form an integral unit in which the steam passes round a cycle. An elementary cycle is the Rankine cycle- see Figure 4.4.
The output of work per unit weight of water circulated is dependent on the ratio of T1 / T2, where T1 is the peak absolute temperature of the steam and T2 is the temperature of the coldest part of the cycle. This accounts for the use of the condenser. By condensing the steam leaving the turbine, the turbine exhaust temperature and pressure are made as low as possible, allowing the maximum energy to be extracted from each kilogram of steam. Finally in this section, let us return to the turbine driver pump system and look briefly at overall efficiency, starting from the liquid being pumped. The objective of the equipment is to take liquid at pressure Pin and deliver it at pressure Pout. At each point where inefficiency occurs in the system, energy is lost. Let us consider these points and their evaluation.
1. Losses in the pump ducts and pipes. The liquid flowing through the pump will lose
some head and therefore energy due to friction losses in the ducts and due to changes in flow direction. 2. Pump impeller. The pump impeller will no! deliver to the water the pressure rise calculated theoretically. 3. Mechanical losses due to the friction in bearings etc., occur in the pump. Sealing water for pump seals also causes some energy loss. 4. Shaft losses. Air friction on the shaft, etc. 5. Turbine mechanical losses similar to those for the pump 6. Turbine heat losses to the atmosphere. 7. Turbine isentropic inefficiency.
64
All the losses or inefficiencies except (7) increase the amount of energy which must be taken from the steam to achieve the pumping duty. The allowances made for these losses are all calculated empirically or theoretically by the designer of the unit.
4.7
THERMODYNAMICS AND EQUILIBRIUM
In chemical engineering the processes with which we deal are often earned out continuously under steady-flow conditions. The treatment of these systems, however, is based on knowledge of how the process behaves under batch conditions. It was pointed out earlier that thermodynamics is not concerned with the rules of processes what it tells us is the extent to which a process will lake place under a given set of conditions. By 'batch conditions' we mean that we take the 'materials' for the process and isolate them together. We then see what happens. Under such conditions all processes move towards an equilibrium condition. Example: Put saturated steam with a piece of cold metal. Steam will condense until the metal, water, and steam temperatures are equal. Note that exactly the same end-condition could have been reached by putting hot metal with water provided correct conditions of temperature and pressure were chosen and heat transfer in or out of the system was prevented. Since both processes took place, the final condition must have higher entropy than either initial condition. The equilibrium condition is one of maximum entropy (i.e. dS = 0, or, if we differentiate with respect to w, the weight fraction of steam, dS / dvv = 0, for the equilibrium condition). Similarly for the isomerisation reaction, A = B, if a - weight fraction of A, then at equilibrium dS /da = 0. To the reader following the previous section carefully there may now appear to be a conflict between the statement here that reaction stops when the condition of zero entropy change is reached and earlier discussion of the Carnot cycle, etc., in which we supposed processes to take place reversibly under conditions of zero entropy change. In fact, there is no conflict. Two points make this clear. 1. It is repeated that, in studying the Carnot cycle, it is merely a theoretical assumption that so many cycles are made. The steps in the cycle of the body are imposed externally by the transfer of heat, removal of work, etc. 2. Similarly, we could theoretically postulate the isomerisation reaction to proceed under isentropic, reversible conditions. When the system is at equilibrium we must feed A into the system and remove B, both at the same rate and infinitely slowly. There is no inconsistency, then, in the statement that the equilibrium condition is determined by the situation where S = maximum and dS = 0. This condition is used to calculate equilibrium compositions. In studying chemical reactions, this is not a simple criterion to use and a further variable a function of previous variables U, T, S, P, F-is introduced. This is Gibbs free energy, or 'free energy', defined by the equation
65
G=U + PV-TS
(4.10)
G, like H and U, is an extensive variable and is a function of the state of a body only. It is primarily applied to systems which undergo changes at constant temperature and pressure, when dG=dU + dPV-TdS As we saw previously, dU = dq- dw and for an isothermal process with only pressure -volume work dU= TdS-PdV If, however, other types of work are possible and 'other work' done by the system amounts to dw' when the process is carried out reversibly, then dw = dw' +PdV and hence dU = TdS-PdV-dw Therefore dG = dw Thus the change in free energy between two states of a system is equal to the amount of non-PF work obtainable from the system when the change is carried out reversibly at constant temperature and pressure. It will be remembered that when the process is irreversible dq < TdS and that dw is reduced (see Eq. (4.6)). Thus, dG represents the maximum non-PV work that can be obtained for a change between the two states at constant pressure and temperature, For an infinitesimal change at constant pressure and temperature, therefore, dG dw' or, if in addition dw' is zero, i.e. no work other than PV work is done, then dG<0
In all spontaneous processes under such conditions, G decreases, while at the reversible or equilibrium condition G has reached a minimum value and dG = 0. Conditions of'constant temperature and pressure with no non-PV work' are commonly those of chemical reaction, and this criterion of equilibrium is therefore of great importance. Let us look a little further at dG when pressure and temperature are allowed to change. Then, differentiating Eq. (4.10)
66
but and
dG = dU=TdS-PdV dG=VdP-SdT
dU
PdV
VdP-TdS-SdT
(4.11)
This equation, in common with the whole of this chapter so far, still applies only to a body composed of a single chemical species. Suppose it is applied to two chemicals contained together which we know will react with each other. Then, if we use Eq. (4.11) as it stands, no change in dG occurs in spite of the spontaneous reaction process. This problem can be circumvented if, for multi-component systems, additional terms are included which depend on the number of moles of each component present. We rewrite (4.11) dG=VdP-SdT + ui x dni (4.12)
where the values of u1 are called the 'chemical potentials' of the k components involved in the reaction and dni are the changes in the mole numbers of the components present when the infinitesimal step in the reaction occurs, ui, then, may be looked upon as the change in free energy of the system which occurs per mole of the ith component when a small change is made in the number of moles of that component presentthe temperature, pressure, and number of moles of all other components being held constant. (The chemical potential is analogous to specific heat, which defines how the heat content of the system changes for unit change in temperature.) We now see that the condition of equilibrium for a chemical process at constant temperature, pressure, and when no non-PV work is done in a k-component system is ui x dni = 0 (4.13)
If we had a method for determining the value of p. for each component, we could calculate the values of the left-hand side in any situation, since the changes dni are related to one another by the stoichiometry of the reaction. To summarize again, It can be shown that a derived variable of state free energy, G can be used as the criterion for equilibrium. The introduction of chemical potential enables account to be taken of chemical equilibrium in a multi-component system.
67
C HAPTER 5
REACTION ENGINEERING
The work of designing a reactor for a specified chemical process falls into two basic categories. The first category is concerned with the reaction itself and the second with the equipment in which the reaction is carried out. Reaction rates and degree of conversion of all processes are affected by the conditions of temperature, pressure, and composition under which they are carried out. It is necessary to choose those conditions which 'optimize" the design. The criterion for such 'optimization' is not a process condition such as maximum degree of conversion or minimum reactor volume. The optimum design must satisfy two requirements firstly it must be safe, secondly it must be the most economic in terms of cost. It is not within the scope of this book to discuss the details of methods by which the minimum cost design is chosen, nor even whether capital cost or operating cost is to be considered. It can be seen, however, that in choosing the thermodynamic conditions for the reaction, it may be necessary at that stage to consider the possible reactor designs in considerable detail. This is not to suggest that, in designing every reactor, the chemical engineer carries out a full cost optimization he does not. He can frequently base his choice of conditions largely on his experience of the cost of such systems. Furthermore, it is often the case that the optimum is very flat, i.e. costs change very little over a wide range of thermodynamic conditions; in such a case, the effort needed to optimize within that relatively flat region is not justified by the cost saving achieved in reaching the precise optimum. The second basic category of work comes when the thermodynamic conditions of the reaction have been chosen and the reactor design must be specified. The shape of the reactor must be fixed, together with fluid entry- and exit-points and any ancillary equipment such as stirrers, heaters, coolers, pumps or fans for passing reactants through the vessel, etc. Much of this work may be necessary in fixing the thermodynamic conditions if they are to be optimized accurately. In this chapter we want to see how chemical reaction is transferred from the test-tube scale to that of the reactor integrated into its position in the chemical plant. We shall be discussing the types of reaction met in chemical industry and the methods used by the chemical engineer to exploit these in large-scale production.
5.1 TYPES OF CHEMICAL REACTION

The simplest way of categorizing reactions is according to the phases involved in the reaction. Table 5.1 lists the types of reaction according to the phases involved arid indicates the frequency with which they are used, together with some common examples. The last column indicates whether they are normally carried out batch wise or continuously. The ability to operate a reaction continuously usually results in very large
Table 5.1. TYPES OF REACTION
68
Phases
Homo- or Batch or Frequency of Heterogeneo Continuous use us homo homo hetero hetero hetero hetero C C/B C/B C C C/B medium frequent rare frequent very frequent medium
Examples
gas liquid solid gas liquid gas solid liquid -solid
hydrocarbon cracking esterification reactions cement manufacture ammoniation of nitric acid many catalyzed gas reactions ammonia, methanol, synthesis dissolution reactions e.g. reaction of nitric acid with rock phosphate fermentation reactions
gas liquid solid hetero
C/B
rare
two-phase liquid
hetero
rare
hydrolysis of a number of nonmetallic halides and oxyhalides
reductions in both capital and operating costs. The reasons for this are 1. The equipment is utilized continuously for production in a continuous process, whereas time is taken for filling, emptying, cleaning, etc., in batch processes. 2. Batch processes always require considerable intermediate storages between stages which are not necessary in continuous processes. 3. Energy wastage in batch processes is usually high, owing to heating and cooling between stages. 4. A continuous process can more readily be made to operate under automatic control and therefore the plant manning is reduced.
69
For these reasons, hatch operation is usually avoided. A few exceptions are: 1. Processes such as polymerization which may require high pressure. 2. Fermentation reactions, where problems of control or bacterial and enzyme activity arise in continuous operation, 3. High-value, low-volume products where the points mentioned above have little effect on product cost arid improved control under manual operation may give marginally higher yields. 4. Processes having particularly long reaction times where it is most simple to leave the reactants in a single tank. We can now discuss briefly each of the types of reaction in Table 5.1 and the type of equipment in which they are typically carried out.
Homogeneous Gas or Liquid Phase Reactions

This type of reaction is carried out in an empty vessel through which the gas or liquid is passed. The volume of the vessel is adjusted in relation to the volumetric flow rate in order to allow the reactants to remain there for the length of time needed-the residence time. We shall come later to the question of residence time distribution; this may be important and the use of fluid mechanics to achieve the right internal configuration of the reactor may be necessary.
Solid-Phase Reactions
In any reaction, it is necessary to bring the molecules of one reactant into contact with molecules of the other. Because of the relative immobility of solid molecules, this is difficult in their case and solid reactions are generally slow. Solids must be heated to a high temperature to react with each other and must be finely ground and well mixed. Even in the examples given, the true reaction probably does not take place solid-to-solid, but as a result of reaction between either liquid melt or gas formed from one solid and the other solid.
Gas Liquid Reactions

In all heterogeneous reactions, molecules must cross the interface between the two phases in order to allow reaction to take place. To achieve a high rate of reaction it is usually necessary to have a large interfacial surface area. One simple way of achieving this is to divide the gas stream into small bubbles which flow through the liquid held in a tank. A wide range of other contacting devices is available and all of them achieve high interface surface areas. Commonly, these reactions are carried out in absorption towers, referred to in more detail in the next chapter.
Gas Solid Reactions
70
The most common reactions of this type are heterogeneous, gas-phase, catalytic reactions. A solid material acts as a catalyst to two or more gases, the reaction rate being greatly increased by the presence of the catalyst in contact with them. Many of these types of catalyst have such a large effect on the rate of reaction that, in their presence, the reaction can take place at reasonably high rates under thermodynamic conditions where no reaction would be detectable without the catalyst. The reaction takes place at the gas-solid interface, i.e. on the surface of the catalyst. It is therefore essential to provide a large surface area and to ensure access of the gases to this surface. The catalyst is therefore used in the form of pieceslumps, granules or pellets which are filled into the reactor. The catalyst pieces are highly porous and have a large internal surface area. Gases pass through a bed of the pieces and reactants diffuse through the pores in the pieces to the internal surface and products diffuse out to rejoin the main flow stream. The catalyst particles are supported on a grid in the reactor and the gases pass into the reactor at the bottom through the grid into the bed of catalyst, through the bed, and out at the top-flow can, of course, be in the reverse direction.
Liquid-Solid Reactions
There is a vast range of liquid-solid reactionsthose in which dissolution or precipitation or both take place. Again, the interfacial area is of importance, since the reaction usually occurs at the surface of the solid. The design of reactors for these processes is difficult to undertake on theoretical grounds alone, and it is usual to base design on experience in the laboratory or previous full-scale plant. Crystallization is a process which is particularly difficult to control. It is usually desirable to obtain well-shaped crystals of even size to ease the problems of subsequent separation of the solid from the solution. Relatively minor changes in solution conditions can give rise to undesirable changes in crystal form and size.
Three-Phase Reactions
Three-phase reactions are not common. Essentially, the same criteria apply as to both gasliquid and liquidsolid reactions. The form of the equipment used to provide interface area between gas and liquid is severely limited by the fact that many types of equipment would become blocked by the solid phase. Types of equipment are limited to those containing no packing, such as bubblers, or very open packing through which the liquid passes.
Liquid Liquid Reactions

It is possible to carry out reactions between two liquids which are immiscible with each other- the product forming a solution in one of the reactants. This would provide a twophase system and equipment suitable for solvent extraction (see Section 6.4) would be suitable for this sort of reaction. In addition, another type of reaction is where a solid is produced as a result of this reaction between two immiscible liquid phases. This latter type of reaction is another kind of three-phase process, in which again the problem of solid blocking the equipment used to contact the two liquid phases must be circumvented.
71
We have categorized reactions above according to the form or phase of the reactants; also of importance to the chemical engineer is the thermodynamic nature of the reaction and the course of the reaction-whether one or more products are formed, etc. These aspects we shall discuss together with rates of reaction in the next section.
5.2 REACTION KINETICS

All chemical reactions proceed to an equilibrium condition under any set thermodynamic conditions. This can be shown in the case of perfect gases from the previous chapter, Eq. (4.18). It will always be possible to find ratios of the product and reactant partial pressures which satisfy the equation. Sometimes, the degree of conversion at the equilibrium condition is very, very close to 100% but there will always be at least a few unreacted molecules or atoms. Thermodynamic treatment of the reaction allows the equilibrium degree of conversion to be determined for each set of thermodynamic conditions for the reaction. Equations (4.19) and (4.20) show that the variation of Kp with temperature depends on H the heat of reaction. If H is negative-the exothermic reaction which liberates heatthen the degree of conversion at equilibrium decreases as temperature increases; in the case of the endothermic reaction (H positive), equilibrium conversion rises as temperature is raised. This is a typical example of 'nature's law of cussedness'-Le Chatelier's principle. To achieve high conversion in an exothermic reaction, heat must be removed to keep temperature from increasing as heat is liberated during the course of reaction: in the endothermic reaction, heat must be supplied to prevent temperature falling. Reaction equilibrium is important but it is not sufficient information. The point is that all reactions become progressively slower as reactants are used up and equilibrium is approached; equilibrium is only reached after infinite time, although some reactions do get very close very quickly. What we must know is how fast a reaction isor, in other words, how long it takes to achieve a given degree of conversion. There is no way to obtain this information other than experimentation. It might be said that experimentation is sufficient and that, once conversion under one set of conditions has been measured, it is the end of the story. But remember that our object as designers is to choose the best design; this implies the ability to design and compare reactors for a wide range of conditions. Mere we come to the point of reaction kinetics. Experimentation is expensive and difficult and rate measurement for each condition we wish to consider is out of the question. We therefore use a theory of chemical reaction-reaction kineticswhich enables us to calculate reactor design for a wide range of operating conditions, given the results of experiments under a few sets of conditions. Reaction kinetics is based on two primary principles: 1. That reaction rates depend on the concentrations of reactants and products present. 2. That variations of reaction rate with temperature follow the Arrhenius Law (Eq. (5.4)).
Rate Equations
Rate equations were discussed in an earlier chapter. The simplest form of reaction rate equation is the first-order equation. It is termed "first-order' because the rate of
72
reaction (mole/s) is proportional to the first power of the concentration a: of a single component. rate = kx mole/s
k is a constant which varies only with temperature. Suppose the reaction is isomerisation A - B. Then this equation can be rewritten; the reaction results in decrease in the concentration of A denoted by x thus dx / dt = -kx or x = Ce-kt
where C is the integration constant. If the value of x at time 0 =xo then This equation is basically a decay equation. Individual reactant molecules suddenly reach a condition under which they may isomerise. The frequency with which they reach this condition depends on their concentration.
Second-order rate equations also arise. For example, the rate of our perfect gas reaction
A + B 2C would be given by rate = kab
where a, b are the concentrations of A and B, respectively; in the case of gases, the effective concentrations of reactants are their partial pressures rate=k1papb (5.1)
If the initial partial pressures of A and B are pa and pb then we can express pa at any instant in terms of pa as follows: Pb = Pb - (Pa - Pa) This applies since any reduction in the partial pressure of B due to reaction is balanced by an equivalent decrease in that of A. Expressing rate in terms of the rate of change of partial pressure of A we have dPa / dt = - k1pa [Pa - (Pa - Pb) ] This equation also may be integrated to give a relationship between pa and t. If we think of what is happening on the molecule or atom scale in this reaction, it is clear that reaction between A and B will occur only when a molecule of A comes in close proximity with one of B. As we shall see later, not all such approaches result in reaction, but the rate of reaction is dependent on the frequency of such approaches. This frequency in turn is proportional to the product of partial pressures or concentrations.
73
First- and second-order rate equations are the most common. Third-order reactions resulting from the interaction of three molecules are possible but do not frequently arise. Other non-integer orders of reaction do occur in rate equations-particularly when catalytic processes are considered. We obtained a rate equation for the reaction of A and B, but Eq. (5.1) would not give zero rate until either A or B was completely consumed. In practice, we know that the reaction reaches equilibrium and this is because, as a concentration of C builds up, it becomes possible for molecules of C to react together to form A and B. This is also a second-order reaction with rate = k2 / Pc 2 (5.2)
The net, forward rate of reaction may therefore be expressed rate = k1papb-k2p2c (5.3)
At equilibrium the net forward reaction ratio is reduced to zero, i.e. or k1papb = k2p2c p2c / papb = k1 / k2 = kp The equilibrium constant which is the ratio of the rate constants defines the ratios of partial pressures at which equilibrium is reached. Like k1 ,k2 and kp varies only with temperature. Processes which go very nearly to completion have large values of kp, and also a large negative value of G (see Eq. (4.19)). For these reactions the rate of the reverse reaction is negligible; the term for the reverse reaction can be eliminated from the rate expression.
Temperature Effects
Reaction does not take place every time A and B molecules approach. Whether reaction takes place depends on the energy states of the two molecules; if the combined energy is sufficient, reaction will occur. The gas consists of molecules having a range of energy levels and, as the temperature of the gas mixture rises, the fraction of interactions in which there is sufficient energy will also rise; reaction rate increases with temperature. The kinetic theory of gases shows that collision energy varies with temperature such that the number having energy greater than E is proportional to e-E/RT. Considering then the reaction on a molar scale, we obtain the equation k = k e-E/RT (5.4)
E is referred to as the activation energy, since it represents the energy level which the reactants must exceed before they will react. Equation (5 .4) is the Arrhenius equation. If the value of the rate constant, ko, has been determined by experiment at an absolute
74
temperature T0, then the value of the constant at some other temperature can be calculated from the expression k = ko e-E/RT(1/T T0) (5.5)
For simple non-catalytic reactions, then, we now have a basis for expressing their forward and reverse rates in terms of rate equations and the variation of the forward and reverse rate constants can be related to temperature. It will be clear that the variation of the value of kp with temperature is also determined, since it remains the ratio of k1 and k2. Figure 5.l(a} shows how the reaction rates vary with composition for a simple first -order isomerization. A <=> B given k 1 = k2
Although the rate equation theory, as well as that of the Arrhenius equation, has been based on perfect gases in this section, it is generally applicable to any reaction in a single phase.
Time
75
Figure 5.1. Reaction composition profiles: (a) isomerisation, A = B starting from A, (b) consecutive reaction system
Consecutive and Branched Reactions

It is helpful to think of a single reaction in developing the basic theory of reaction kinetics. It is, however, much more usual to meet reactions having a rather complex series of stages, whose analytical treatment is more difficult. A typical example is the reaction of steam with liquid hydrocarbons in the modern process for making ammonia synthesis gas. Take, for example, a schematic view of the reaction of heptanea component of the hydrocarbons used. Here 'cracking' is simply breakdown of heptane molecules into the shorter hydrocarbon molecules. Before considering the problems of dealing with this reaction, we will look at the more simple cases, lake a simple consecutive reaction: A+BCD+E Both of these steps are reactions which go nearly to completion and reaction rates in the reverse direction may be neglected. The first reaction is second-order and the second is firstorder. It is quite practicable to write rate expressions for these reactions and integrate the resulting expressions to obtain the concentration of A, B, C, D, and E as a function of time. The first stage proceeds as though the second did not exist. Concentrations follow the curves sketched in Figure 5.1. The shape of the curves depends on the relative values of the rate constants for the two reaction steps. A similar reaction scheme, which can be treated by writing reaction rate equations and integration, is the reaction involving a by-product, e.g. A+BC and D The reader will find that this and other reaction sequences which involve simple first- and second-order reactions may be treated analytically. As stated earlier, the use of such kinetic reaction schemes is in simulating experimental results so that the rate equations can be used for calculation of behavior under other conditions. The procedure is 1. Experimental work. 2. Deduction of reaction scheme. 3. Derivation of rate equations for this scheme. 4. Fitting results of calculations made with these rate equations to the experimental data in order to determine reaction rate constants. The procedure in the case of the hydrocarbon reactions mentioned above is much the same, but now reaction equilibria must be included. The experimental data are studied to derive a
76
form for the reaction scheme. Experiments may be undertaken to study individual steps separately. The ultimate set of rate equations becomes complicated, and analytical integration is no longer possible. Here the computer comes into its own. Integration of the rate equations is carried out numerically. The reaction rate equations are normally written dCa / dt = f (Ca, Cb, Ci, ..) dCb / dt = f (Ca, Cb, Ct, ..) where Ca, Cb, Ct, . are the concentrations of the reactants. For a small change of time bt each equation may be rewritten in the form Ca = f (Ca, Cb, Ci, ..) t A similar equation, relating the change of temperature of the reaction, 57", to the specific heat of the components, the heat of reaction, and the concentration change can also be written T = F (H, Cpa, Cpb, .) Ca The computer can now be programmed to carry out the calculation of these changes in composition and temperature if the time interval 5t and thermodynamic data are fed into it. Further, it can be made to repeat the calculations for successive steps t as long as we wish. This procedure is called stepwise numerical integration. Because the computer calculates very quickly, a very small time interval t can be used in the calculation and accurate numerical integration can be achieved. The calculation is repeated with different values of the rate constants, activation energies, etc., until these variables are fitted to the experimental results.
5.3 CATALYSIS
Catalyst systems divide broadly into two types.
Type I. Those in which the catalyst molecules become involved in the chemical
reactions. After the reaction the catalyst molecule has the same chemical formula but does not contain the identical atoms which it had before the reaction. This would be demonstrated by a radioactive tracer experiment. If a radio isotope of one of the atomic species of which the catalyst was made up was injected into the reaction, then at the end of the reaction some of the catalyst molecules would be found to be active.
Type II. Those in which the presence of the catalyst causes the rate of reaction to be
increased but the catalyst molecules are chemically unaltered by the reaction. The majority of gas reaction catalysts conform to this type. The modus operandi of the two systems is different. In the former the reaction
77
X + Y----->Z Is replaced by steps of the type X + C --> XC XC + Y --> Z + C step1 step 2
If steps 1 and 2 are both faster than the basic reaction X + Y ---> Z, then the catalyst molecules C accelerate the reaction. It should be noted that the kinetics of the reaction are totally changed by the introduction of C. Studies of the X, Y system alone will give no help in deducing the kinetics of the X, Y, C reaction system. In the second type of reaction the affect of the catalyst is rather different. The reaction takes place on the surface of the catalyst, which provides sites where molecules of one reactant can be adsorbed in an active state. Here they await the arrival of a molecule of the second reactant upon which a product molecule is formed. The reaction becomes possible at very much lower temperaturethe ammonia reaction can be made to take place down to 350 C in the presence of a catalyst, while 800 C is needed with no catalyst. Again, kinetics are markedly altered and also activation energy is reduced.
Type I Reaction Kinetics

Derivation of reaction kinetics for this type of catalytic process presents the chemical engineer with problems similar to those described in Section 5.2. The reaction involved in such a catalytic process can be broken down into a series of sequential reactions, with branches for byproduct formation. A process currently in use for production of vinyl acetate from acetic acid and ethylene is an example. This reaction 1/2HO2 + C2H4 + CH3COOH ----> CH2 - CHOOCCH3 + H20 is catalyzed by palladium salts together with cupric chloride and lithium acetate and chloride. In the reaction system as many as thirty identifiable molecular and ionic species may be involved in a complex sequence of process equilibria and reactions. The cupriccuprous re-oxidation system is commonly used in organic chemical industry. It is employed, as in the vinyl acetate process, to re-oxidize an ion which has been reduced from its high valency state to its lower state in the process. In the reaction between ethylene and acetic acid, the palladous ion Pd++ is reduced to metallic palladium; this in turn is oxidized back to Pd++ by the copper redox reactions Pd + 2 Cu++ ----> Pd++ + 2Cu+ 2Cu+ + 2H+ +1/2 O2 ----> 2Cu++ + 1/2 H2O
The derivation of a complete set of equations for such a complex reaction system is usually unnecessary. This is because one step in the process can be shown to be slow relative to the other steps, and this one therefore controls the rate of the reaction. The rate of the overall process is controlled by the rate of this slow step and the kinetics of this step are the kinetics of the process. Careful and detailed study by experiment is still needed to ascertain this fact and to demonstrate its validity over a wide range of possible operating conditions.
78
Type II Reaction Kinetics

There is a vast number of reactions of Type II and formation of sets of kinetic equations to represent this type of reaction is a major problem which faces chemical engineers today. These reactions take place on the active surface within a porous catalyst mass. We can first set down the steps which take place in a bed of such a catalyst with gases flowing through it. 1. Reactant gas molecules flow through the pore structure of the catalyst pellet to reach all the internal surface of the pellet. The internal surface area may be about 1040 m2/g. 2. The reactant molecules are adsorbed on the surface. 3. Reactant molecules react at the surface to form product molecules. In some cases a series of reaction steps and byproduct steps occur at the surface. 4. Product molecules are desorbed. 5. Product molecules diffuse back through the pore structure to rejoin the main flow. Any one of these steps may be the one which determines the rate of reaction more often it is a combination of more than one step. The ammonia reaction has been undertaken by the Haber process since the beginning of the century, but the kinetics of this simple process are still not completely understood. The famous Temkin rate expression based on steps (2), (3), and (4) was derived in 1 939, and is still in use today for ammonia plant design. The test of a satisfactory equation is that the rate constants do not vary with partial pressures of reactants. The Temkin equation cannot be made to satisfy this requirement. With the size of catalyst particle typically used in this process, the reaction is just in the region where steps (1) and (4) have an influence on reaction rate. No satisfactory procedure has yet been developed to deal with diffusion limitation. Diffusion modifies both the form of the kinetic equation and the activation energy. The reason is this: diffusion is a first -order process with a rather small rate of increase with temperature. The kinetics of a simple second-order reaction are reduced by diffusion limitation to the order 3/2. The apparent activation energy is halved. Here, then, is a field of challenge to the chemical engineer a field where theory will go so far and the rest is empirical. Catalytic processes outweigh others in significance and in interest for the chemical engineer. Definition and improvement of catalysts and quantitative methods for studying their behavior must be developed.
5.4 CONTINUOUS REACTION EQUIPMENT

So far we have thought of reaction rates in terms of time only. This is perfectly satisfactory in the case of well-stirred, batch reactions. For continuous reaction processes, material is flowing through the reactor and reaction time is represented by the residence time of the
79
reactants in the reactor. In this section we shall look at the more important flow reactor types and the affect of flow on reactor performance. Let us start with the constant-volume stirred- tank reactor (CVSTR). This is a simple vessel of fixed volume. Reactants flow in and products flow out at an equal volumetric rate. Inside, the contents are thoroughly mixed. Firstly, we should look at the flow pattern and consider a small element of fluid entering the reactor. The most simple theoretical assumption that can be made about the CVSTR is that mixing inside it is perfect; under perfect mixing conditions, as soon as the small element of fluid has entered the reactor, that fluid is completely uniformly mixed throughout the fluid already present in the reactor. The result of this is that there is at once a small concentration of the fluid which has just entered in the fluid leaving the reactor. Other parts of the element stay in the reactor for longer periods of time before leaving. There is said to exist a distribution of residence times. In Figure 5.2 the volumetric flow rate is v; suppose that for an instant of time a trace material say a dye is introduced into the input stream at time t = 0. This is immediately mixed evenly throughout the volume V. Suppose M molecules of dye are introduced and c = concentration in the reactor at any time t. Then Co = M / V The distribution of residence times can be defined by the fraction of the dye initially introduced which remains in the vessel after time t. The number of molecules of dye leaving the system between time t and t + dt is given by vc dt and this results in a decrease in concentration. Thus -Vdc = vcdt
E A ^t0) 0 E
Figure 5.2. Constant-volume stirred-tank reactor
Suppose we now consider the first-order reaction for which the concentration of reactant is given by the equation
80
X = Xo e-kt All material enters the reactor at time t = 0 with concentration Xo . The material becomes perfectly mixed and leaves the reactor at different times after the moment of its introduction. The fraction of material df which leaves at time t will have concentration X = Xo e-kt For the whole residence time distribution, the mean concentration in the product stream is calculated by integration and further distributing gives: X = Xo / (1 + Vk/v) There is, however, a simpler way to obtain this result. In the reactor the concentration is x. The rate of reaction is therefore Vkx. Reactant flows in at rate vxo and leaves at rate vx: V (Xo X) = v kX How does this conversion compare with the conversion at the same residence time under batch conditions? The mean residence time is V/v. The conversion in a batch reactor after time V/v is given by (1 + Vk / v) as the first term in the expansion of eVk/v and note that therefore the CVSTR gives a higher value of x, and lower conversion, than is achieved in the batch reactor after time equal to the mean residence time in the CVSTR. In designing a reactor, then, we should attempt to make the system approach batch conditions if maximum conversion is desired. The material in the batch reactor all has the same residence time and Figure 5.2 shows how the residence time distribution would have to appear in a flow reactor system which gave conversion equivalent to the batch reactor. This is called a plug flow system. This term is used because one way to obtain this residence time distribution is in a tube under a turbulent flow regime; the velocity profile in the tube is like that shown in Figure 3.6 plugshaped. A tubular reactor with plug flow is one way of achieving maximum conversion in a flow reactor. A second way of achieving this is to use a series of CVSTRs. The more that are used in series, the more nearly the system approximates to plug flow. In practice, no reactor will give perfect plug flow. The packed catalyst bed reactor gives a good approach to plug flow if care is taken to get even packing of catalyst and good initial distribution of the gas over the whole catalyst cross-sectional area. To summarize, the common flow reactor types are: 1. CVSTR: approximates to perfect mixing. 2. Series of CVSTRs: approximates to plug flow (conversion as for batch). 3. Plug flow tubular reactor: approximates to plug flow (conversion as per batch).
81
4. Laminar flow tubular reactor (residence time distribution is amendable to calculation as in case of CVSTR). 5. Packed bed catalytic reactor: approximates to plug flow (batch).
5.5 REACTOR DESIGN

The discussion so far has concerned the development and use of reaction kinetics for the purpose of describing the reaction and calculating reaction rate. We now come to the use of the kinetic equation in design, and to the other practical aspects of the design of a reactor. The reactor for a catalytic gas-phase reaction is one which presents many design problems and the main discussion in this section centers around it. Exemplifying this type is the ammonia reactor. The designer of the reactor must be given the following information: 1. Feed gas flow rate, . Feed gas composition, 3. Feed gas temperature, 4. Reactor operating pressure, 5. Ammonia production rate or concentration of ammonia in gas leaving the reactor. The designer needs information also on the performance of the catalyst he is going to use. This information is obtained experimentally by carrying out laboratory tests in the case of new catalyst, or by tests on full-scale plant in the case of a well established catalyst. To use the Temkin equation described in Section 5.3 for calculations on a steady-flow reactor the time, A, must be related to residence time of the gas in the catalyst bed. The complexity of the Temkin equation is such that the stepwise integration method described in Section 5.2 must be used. The rate constant must be related to the volume of catalyst. The residence time in an element of the catalyst is given by Volume of catalyst-free space / volumetric gas flow rate through catalyst The gas flow rate must be corrected for temperature, pressure, and degree of conversion and the total free space in the catalyst, including internal pore volume, should be used. In the case of a well-established catalyst already in use, catalyst performance data are obtained from full-scale plant tests by using a calculation method based on the Temkin equation to fit values of catalyst activity and activation energy to the test data. These values are then used in design. One problem with ammonia catalyst is that activity decreases with time and the designer must have information on the effect of catalyst age or activity. The further data needed by the designer are specific heats and heats of reaction for the system. He is then equipped to make a mathematical model of the catalyst bed and carry out the stepwise integration of the composition and temperature equations. The ammonia synthesis
82
reaction is exothermic, and as gases pass through the catalyst they become hotter at higher temperatures the equilibrium conversion is lower and therefore close to actual conversion. The gas composition and temperature for a bed of catalyst are shown diagrammatically by the broken lines in Figure 5.3; the upper composition curve shows the equilibrium composition corresponding to the reaction temperature.
Equilibrium %NH3 at actual catalyst temperature indicated in lower curves
30
10 -
540 520 500
480
460 Entry
440
Exit
Distance through catalyst Figure 5.3. Composition, temperature and equilibrium composition in ammonia catalyst: single bed-broken line; three beds solid line
It can be seen that, in the latter part of the catalyst, equilibrium and actual composition are very close to each other and reaction has to all intents and purposes ceased. A much higher conversion can be obtained with the same gas flow rate through the catalyst and same catalyst volume, if the bed is broken up into sections, in between which the gas is cooled. This is shown in the unbroken lines in Figure 5.3. At the end of the reactor, equilibrium is still not reached and reaction is proceeding. The reduction in temperature between beds can be done in a number of ways. For the ammonia reaction, the most popular is to introduce cold gas from outside the reactor and allow this to mix with the reaction gas before it goes into the next bed. In designing the set of catalyst beds, optimum design- i.e., minimum volumecan be achieved by correct choice of the inlet temperature
83
and size of each bed. The designer makes repeated use of his model to optimize the design. Ultimately he succeeds in specifying the number of beds, volume and inlet temperature of each, final bed exit temperature, and the quantity of cold gas needed for cooling between beds. Thus far it has not been necessary to consider the shape of beds, only their volume. The ammonia reaction temperature is in the range 400-500 C but gas is fed to the reactor at, say, 40 C. Since the reaction is exothermic, the final temperature is higher than the inlet temperature and a heat exchanger can be designed so that the heat from the product gas is used to warm up the feed gas. This exchanger is situated in the same pressure shell as the catalyst beds. Design of the heat exchanger requires the diameter of the shell to be specified. The larger the diameter, the lower will be the gas velocities and the larger the heat transfer surface required, but the lower will be the pressure drop in the heat exchanger and, more particularly, the catalyst. In addition, the larger shell calls for thicker walls. At this stage, then, economic factors must be considered. Once the diameter is chosen, the heat exchanger is designed by the methods described in Chapter 3, with fouling factors based on experience of reactors previously operated. The dimensions of the vessel and the sizes of catalyst beds and heat exchanger have now been specified and the design becomes the province of the mechanical engineer. He must design the pressure shell, the catalyst containers, the heat exchanger tube plates, all internal pipe-work, etc. In this mechanical design attention must be paid to a number of mechanical and operating factors: 1. How is the catalyst to be put into, and removed from, the vessel? 2. How quickly can the vessel and internals be heated up and cooled down? 3. How quickly can pressure be reduced on shut-down? 4. What provision must be made for repairing the internal equipment after lengthy service? 5. What information must the plant operating staff be given to ensure that the reactor is operated safely and within the design limits? The reader may have wondered how the reactor is started up; the feed gas has to be heated by the product gas and there will be no temperature difference between the two gases unless reaction is occurring. The answer is that an electrical element heater is installed in the reactor. A small feed gas rate is passed through the heat exchanger and to the heater, then through the catalyst and back through the heat exchanger. At first only the catalyst warms up, but subsequently heat begins to be fed back to the incoming gas by the exchanger and the whole reactor slowly comes up to reaction temperature. Once the top of the catalyst reaches the catalyst initiation temperature, reaction starts and feeds heat into the catalyst and the rest of the reactor much more quickly.
84
Figure 5.4. AMMONIA REACTOR IN TRANSIT. The containing shell for an ammonia reactor designed to operate at 300 atm pressure is a massive welded vessel This one for a 500 tons per day plant weighed 140 tons. Within the shell are the sections containing catalyst, the heat exchanger and heater. The 150 mm thick closing plate at the near end (the top of the reactor) is held in place by 20 nuts on studs. This is typical of the scale of equipment to be installed in modern ammonia plants.
Finally, the catalyst itself is made in the form of lumps of iron oxide about 5-10 mm in size. It is the reduction of this to iron which gives the catalyst its porous structure with a large, active surface area of about 20-30 m2/g. The reduction is carried out under carefully controlled conditions using the synthesis gas, when the plant is first put on-line.
5.6 SPECIAL CONSIDERATIONS IN REACTOR DESIGN

In the ammonia reactor, heat is removed during the course of reaction with the object of increasing the degree of conversion. In many organic oxidation reactions for which heterogeneous catalysis is used, there are other considerations which necessitate careful control of temperature. A catalyst, which is designed to give high activity for a particular oxidation reaction to the exclusion of other possible reactions, is often sensitive to temperature and the maximum catalyst temperature must be strictly limited. Second, the range of temperature over which the catalyst is selective for the desired reaction may be quite small. A typical reaction of this type is the oxidation of butene, butane, and butadiene to maleic anhydride. A mixed stream containing the reactant hydrocarbons is frequently a product of alkene production by hydrocarbon cracking. The catalyst used is capable of producing a wide range of byproducts as well as carbon dioxide and steamthe ultimate oxidation products of hydrocarbons. Ail the reactions are exothermic and when the reactants come into contact with the catalyst, temperature rises rapidly as they pass through the bed. The temperature rise can be controlled by immersing tubes containing the catalyst in a bath of a liquid, which is circulated to remove heat. Other factors affecting the temperature profile of the gases as they flow through the catalyst packed tubes are the flow rate; the concentration of hydrocarbons in the feed gases; the pressure; and the rate of heat transfer inside the tube, which in turn depends on catalyst particle size.
85
Given laboratory data on the reaction, it is again possible to construct a mathematical model of the reaction system which allows the effects of factors such as these to be evaluated. If the model shows that a particular set of conditions is needed to obtain maximum yield, then these can be tried out in the laboratory. A second factor which is frequently of importance in reaction systems is mass transfer absorption and/or desorption. There are very many reaction systems in which one of the reactants is first transferred from the gas phase into the liquid where reaction occursfor example, neutralization of phosphoric acid by ammonia gas and the vinyl acetate reaction mentioned earlier. In designing reactors for this type of reaction it is important to be able to consider the interphase mass transfer and the reaction separately. Since the steps of mass transfer and reaction are consecutive, either one could be many times slower than the other or it is the slower step which will determine the overall reaction rate. We shall see in the next chapter how interphase transfer rates are calculated. At the moment, we shall only note that, if the mass transfer is limiting reaction rate, then it is important to design the reactor to have a large interface area between the two phases and thus get high mass transfer rate. If the limitation lies in the reaction itself, then adequate reaction time must be allowed and reaction conditions must be optimized. A type of reactor which is of considerable importance is the fluidized-bed reactor. A fluidized bed is a bed of particles, in which the particles are kept in motion by the upward flow of a liquid or gas through the bed. The particles move about in random motion. Fine solid material can be fed into the bed and immediately become thoroughly mixed with the bed; an overflow stream of solid particles can be taken from the bed. So far as solid flow through the bed is concerned, the bed behaves like a CVSTR. For the gas stream, the turbulent motion of the solid particles causes the residence time distribution to be far from plug flow. This type of reactor is particularly useful for reactions where the solid as well as the gas must flow through the reactor. Examples of its use are in: 1. Catalytic cracking of hydrocarbons, where carbon forms on the catalyst which must be removed from the reactor for the carbon to be burnt off. 2. The roasting of pyrites to obtain SO2 containing gases. 3. Decomposition of uranyl nitrate to form uranium dioxide. In the two latter applications a further advantage of fluidized beds is utilized. If heating or cooling tubes are placed in the bed, high rates of heat transfer can be obtained. This is because the normal convective heat transfer process is augmented by the heat transferred through the laminar layer at the tube wall by the motion of the particles.
86
Chapter 6
UNIT OPERATIONS
In Chapter 3, the list of unit operations included the main processes involved in the preparation of raw materials prior to reaction and the treatment of reaction products. This chapter does not deal with all of these processes, but covers mainly the type of process used for purifying the reaction products. The unit operations of this type are listed in Table 6.1. Except for the case of the last two unit operations-filtration and dryinga common principle is involved. Initially there is a single phase present containing two or more components and it is desired to separate one of the components from this phase. This is achieved by transferring one of the components into another phase and then separating the two phases. In drying and filtration the two phases already exist and separation only is required. Some of the operations listed result directly in separation, whereas others are only steps in a sequence which ultimately results in separation of the desired product. Other separation processes of less importance in chemical engineering are:
Sublimation of a volatile solid from a two-solid mixture. Sublimation occurs in a

number of processes, roasting pyrites ores for example, but the author is not aware of any examples of its being used deliberately as a unit operation.
Adsorption of a gas component from a gas mixture, or a liquid component from

a solution, onto a solid. Liquids are frequently cleared of traces of dissolved impurities by adsorption of these on a solid, e.g. fuller's earth or carbon.
Diffusion through membranes for gas separation is used for separating the heavier isotope of uranium from the lighter. The diffusing species is UF6. Ion exchange is most frequently used in water softening.
There are two topics which are of general application to all unit operations and Sections 6.1 and 6.2 deal with these. A unit operation is carried out in a piece of equipment with a number of process streams of different compositions flowing into it and out of it at different temperatures. It is necessary, therefore, to be able to calculate stream compositions, flow rates, and temperatures such that the laws of conservation of mass and energy are obeyed. Such calculations are called material and thermal balances and are the subject of Section 6.1. A further common feature of unit operations is that of mass transfer, by which the chemical engineer means transfer of matter from one phase to another across the interface between the two phases. The general principles for dealing with mass transfer quantitatively are examined in Section 6.2.
6.1 MATERIAL AND THERMAL BALANCES
87
The application of the principles of conservation of energy and matter, both to the chemical changes described in Chapter 5 and to unit operations, enables the flow rates and compositions of the process streams leaving a unit to be related to the flows and compositions of the streams entering it. By the use of these principles for each unit in a plant, the overall flowsheet for the plant can be calculated. This flowsheet specifies not only the process units but also the temperature, pressure, composition, and flow rate of each process stream in the plant. It is only after such a flowsheet has been prepared that the individual items of equipment can be designed in detail. In a plant operating continuously under steady conditions, the material which goes into a particular unit each second must equal what comes out\ a material balance can be made in which the material fed into the unit is equated to the material which leaves. If a chemical reaction takes place within the unit, then this balance can be carried out for each atomic species; the number of atoms of each element entering the unit per second is equal to the number of atoms of that element leaving the unit per second. If the process within the unit is only physical and does not include chemical reaction then the material balance is done on molecules: the number of molecules of each compound entering the unit per second is equal to the number of molecules of that compound leaving the unit per second. The unit operations are of this latter type, since they involve materials moving from one phase to another without chemical changes. The conservation of energy within a unit leads to an energy balance calculation, in which all forms of energy entering are equated to energy leaving. In most cases, there is no mechanical work resulting from the reaction and only a thermal balance is needed. The heat entering the system per second, in the form of enthalpy of the feed streams plus heat transfer into the unit, is equated to heat leaving the unit per second. In most chemical plant units, the material and thermal balance calculations are simple and straightforward; for example, a reactor having a single feed and product stream, with reaction going to completion, is easily dealt with. Some of the units which the engineer must design are more complicated and for these standard methods for carrying out the calculations are learnt; the basis is still the two principles of matter and energy conservation. To amplify these statements, we can look at a few examples of how such balances are applied in some specific situations which the chemical engineer meets in designing plants. The material balance on the reaction, in which there is only a single feed stream and a product stream is simple but when a third stream is present the material balance is slightly more difficult. We can take the case of combustion of a fuelmethane and see how the material balance is worked out. The three streams are methane, air, and combustion products. The methane burns to form carbon dioxide and water vapor. CH4 + 2O2 ------> CO2 + 2H2O The air contains 21 mole % oxygen and the remaining 79% consists of nitrogen and inert gases which do not change; if a stoichiometric quantity of oxygen is used, the material balance is very simple. In practice, it is usual to ensure complete combustion by using a small excess of air over the stoichiometric quantity. We shall assume that it is desired to operate so that there is 3 mole %02 in the combustion gases. We can write down (Table 6.2)
88
the feed streams and product streams using algebraic symbols for quantities we do not know. We are now going to write balance equations for each atomic species by equating the rate of flow of each species into the burner to the rate of flow out. It can be seen in the table that the air has not been separated out into each speciesnitrogen, argon, krypton, etc.; since these are all unchanged, they can be treated as a single component. If they had been separated, the concentration of each would be listed in stream 2 and a symbol for each included in stream 3. There would be one unknown symbol and one equation for each enabling the concentration of each to be calculated in the product stream. In this example, we are concerned only with their amount in total. The balance equations are C balance H balance O balance I + 0 = F3c3 4 + 0 = 2F3w3 0 + 0.42F2 = F3 (2c3 + w3 + 0.06) 0 + 0.79F2 = F3n3
(N2 + 1) balance
A final equation for the product stream mole fractions is n3 + c3 + w3 + 0.03 = 1 Solution of these simultaneous equations enables the flow rates of the air and product streams and the composition of the product stream to be calculated. Now, as a simple example of a heat balance we can consider the case of a steam desuperheater. Superheated steam is steam at a temperature above its condensation temperature; when it is required to produce from this, steam at a temperature near condensation then a desuperheater is used. In this the appropriate amount of water is added. The evaporation of this water into the steam cools it to the lower temperature. In our example we will assume that the superheated steam is at a specified pressure and temperature 7\ and that we wish to cool it to a lower temperature T2. The problem is to calculate the flow rate of water F3 at specified temperature T3 which must be used. The initial steam flow rate is Fl and the final rate F2. In solving this type of problem steam tables are used. The steam tables list the properties of water arid steam over a wide range of temperature- pressure conditions. We look up the enthalpy of steam h1, h2 at Tl and T2, and enthalpy of water h3 at T3 . There are two balance equations: Material balance Thermal balance F1 + F3 = F2 F1h1 + F3h3=F2h2
In these equations, only F2 and F3 are unknown and they can therefore be calculated by solving the simultaneous equations. Many problems of the sort, which involve the mixing of two streams having different enthalpy and composition, can be conveniently solved graphically using the lever rule'. A graph or chart is used, in which enthalpy is plotted against composition for a range of
89
temperatures. The chart for sulphuric acid is shown in Figure 6.1. If a certain quantity of acid of one concentration is mixed with a quantity of different concentration at a different temperature the conditions of the mixture are found as follows:
0 20 Composition (wt. % H2S04)
40
60
80
Figure 6.1 Enthalpy composition diagram for sulphuric acid water svstcm
1. The two points representing the two acids are plotted on the chart A and B a line is drawn to join them. 2. The point X is then marked such that BX / AX = quantity of acid / quantity of acid B 3. X represents the conditions of the mixture. 4. The quantity of acid of composition X - quantity of A + quantity of B.
and
This chart of course demonstrates the well-known fact that if pure H2S04 is mixed with pure water the mixture gets hot. By drawing a straight line between water at 0 C and H2SO4 at 0 C it can be seen that a 50-50 mixture will be at about 1 20 C. Graphs of this type can be extended into the vapor region of the enthalpy composition chart and are then used for calculations of the two-phase systems involved in distillation and absorption. The final material and thermal balance case to be discussed in this section is that of an exothermic gas reaction, which is limited by equilibrium. Consider the conversion of SO2 with air to SO3. If SO2 is mixed with air in the presence of catalyst above the 'activation
90
temperature' of the catalyst, the reaction will take place. The reaction is exothermic and, if no heat is removed, the heat evolved from the reaction is used to raise the temperature of the gas mixture. If sufficient residence time is allowed in the catalyst then reaction will continue until the gases reach equilibrium conversion, if 1 00% conversion were achieved, the calculation of composition would be very similar to the first case of methane combustion. In practice, the gas does not reach 100% conversion. In a problem of this type, we will assume that the initial mole fractions of SO2 and air in the gas are specified and also the starting temperature, T1 . What information in addition to the reaction equation is needed so that the equilibrium composition and temperature can be calculated? 1. The equilibrium constant. 2. The specific heat of the gas involved. 3. The heat of reaction. All of these variables are dependent on temperature. As we have seen in Chapters 4 and 5, none of the variables is a simple linear function of temperature and it will not be possible to derive any simple equation which gives the solution. Rather, it will be necessary to solve the problem by trial and error. This is still not a difficult problem if a logical and careful approach is adopted. The reaction equation is 2S02 +02 2S03 As in the methane combustion example, the nitrogen and inert gases present in the air are unaffected by the reaction. The procedure for calculation will be as follows: 1. Guess a final gas temperature, T2. 2. Calculate the equilibrium gas composition at that temperature. 3. Use the heat of reaction at temperature T1 to calculate the heat made available as a result of the reaction reaching that degree of conversion at temperature T1. 4. Using specific heats together with the product gas composition, calculate the temperature rise and hence a value of T2 given by the heat balance. 5. Compare the new T2-value with the guessed temperature. 6. Then revise the guess, and repeat until agreement is reached between (1) and (5). To perform step (2), a general material balance equation is needed. Let the initial mole fractions of SO2, O2, and (N2 + inerts) be S1 , O1, and n1, respectively, and assume that we start with 1 kg mole of gas. Then, when a fraction x of the S02 has been converted to SO3, the moles present are
91
SO2 =s1(l-x) O2 = 01 XS1 SO3 = xsj (N2 + inerts) = n1 total moles = s1 (1 - x} + o1 - XS1+ xs1 + ni = S1 + O1 + n1 - XS1 = 1 - XS1 The reaction is taking place at atmospheric pressure and mole fractions may be used in the equation for Kp. Each time a value of temperature is guessed we look up the value of Kp and then solve this equation (trial and error) to find x. It is now possible to calculate the heat released by carrying out the reaction to the degree x at the temperature T1. A further trial-and-error calculation is made to determine the temperature to which this quantity of heat will raise the product gas. The specific heat data for each gas are used in the temperature range being considereda mean value can usually be taken for each. This final step gives the temperature (T'2) to be compared with the guessed value. The calculations can be shown diagrammatically, as in Figure 6.2. Like the ammonia catalyst calculation in Chapter 5, this is typical of the type of calculation now carried out by computer. The algebra is simple and the arithmetic is simple but long-winded. In the earlier days of computers this would only have been programmed for complete calculation if it was to be repeated many times. Nowadays, with modern computer languages, it is almost as quick to write the computer program as to solve the problem and an experienced programmer would probably make use of a computer for just a single calculation. He would need to check out the first iteration of each step by calculation but subsequently the computer would do the work.
6.2 MASS TRANSFER

The common feature of most of the unit operations is that of mass transfer', by which we mean the transfer of material from one phase to another. Just as heat can be transferred from one body to anothertube metal to liquidthrough the interface between them, so a material can be transferred from one phase to another through the phase interface. The rate of transfer of heat depends on temperature difference; mass transfer rates depend on concentration differences between the two phases. A common example of mass transfer is the absorption of ammonia into water from an ammonia-air mixture. Perhaps even more common is the absorption of oxygen from air by the bloodstream, but in this case there is a membrane separating the two phases. Material flow can, of course, take place in a single phase if a concentration gradient exists. This is simply the process of diffusion. If two different gases in a single vessel are separated by a partition, then, when the partition is removed, they will diffuse into each other under the influence of the concentration gradient until even distribution is obtained throughout. The rate of diffusion of component 1 in component 2 is given by
92
R=-AD12-dc1 / dx
(6.1)
where R = the rate of flow in the direction x, A = cross-sectional area, D12 - diffusion coefficient for component 1 molecules diffusing through component 2, and c1 concentration of component 1. The same molecular diffusion process would take place if the partition separated water containing dissolved acetic acid from acid-free water with, now, D12 being the diffusivity of acetic acid in water and C1 the concentration of acetic acid. In studying heat transfer, we found that the rate of flow of heat in a liquid could be increased above the rate due to conduction if the liquid was in motion and convection occurred. Convection is the transfer of heat due to the turbulent motion of the fluid, which transports "pockets of fluid' from regions of high temperature to regions of low temperature and vice versa. This mechanism can also convey "pockets of fluid' from regions of high concentration to regions of low and vice versa. The convection effect therefore augments mass transfer flow rates due to molecular diffusion. Thus, in the acetic acid and water example, if the water and the solution were both in motion at the same speed in the same direction when the partition was removed, the rate of flow of acetic acid into the pure water would be higher. While the molecular diffusivity is a constant depending only on the two materials concerned (at a given temperature and pressure), the contribution to mass transfer of the convective effect varies with the conditions of velocity, etc., under which the fluid is flowing; this is analogous to the heat transfer coefficient.
Final composition as given by X Final temperature = 7~2 END
93
Figure 6.2. Diagram of calculation method for material and thermal balance on SO2 oxidation reaction.
In unit operations we are not concerned with the cases of mass transfer mentioned above, in which there is only a single phase; a much more effective method than mass transfer for making the acetic acid concentration the same in the original solution and pure water would be to give them a good stir. In unit operations we are concerned with the transfer of mass from one phase to another, but this transfer is still related to concentration gradients in the two phases. Suppose that in the acetic acid and water example the liquid on the other side of the partition had been not pure water, but another liquid which is immiscible with water-say benzene. Acetic acid will also dissolve in benzene. On the removal of the partition acetic acid would still pass into the benzene. It would stop when the concentrations in each phase were related by the partition coefficient, Y, such that Cb / Cw =concentration of acetic acid in benzene / concentration of acetic acid in water Across the interface between the phases, there is a large concentration difference and yet no mass transfer is taking place. Equilibrium is established between the two phases with different concentrations in them. In thermodynamic terms, the reason for this is that the free energy of acetic acid in water at concentration Cw is the same as it is the benzene at Cb. How the transfer of acetic acid is across the interface to be handled before equilibrium is set up? We refer again to our experience of heat and recall that, in heat transfer across a boundary (e.g. fluid to tube wall), the temperature of the fluid at the interface is equal to the temperature of the surface of the wall. At the interface, the two phases are in thermal equilibrium; this must he the case for a continuous temperature profile to exist. If there were
Interface
94
a discontinuity, heat transfer rate would become infinite at that point. The situation for mass transfer is analogous and the concentration profile shortly after transfer has started is shown in Figure 6.3(a). The dotted line in the benzene phase represents the concentration of acetic acid in water which would be in equilibrium with the actual concentration, represented by the full line. The dotted lines meet the full ones across the interface. There still remains a gradient discontinuity across the interface because in general the diffusion coefficient on the two sides is different.
Concentration of acetic acid
enzene phase
Figure 6.5. Mass transfer composition curves
It is by this subterfuge, of dealing with the concentration in the other phase that would be in equilibrium with the concentration in the given phase, that the chemical engineer is able to treat theoretically the mass transfer across the interface. This is applicable not only to the system of two liquid phases by use of the partition coefficient, but also to liquid-gas systems by use of the equilibrium constant between the gas and liquid. his is the Henry's law constant, which relates the partial pressure in the gas phase to the concentration in the liquid phase with which it is in equilibrium. Partial pressure of component i in gas / molar concentration of i in liquid = H1 (6.2)
We should now consider the situation when the two phases are both in motion. Again, the similarity to heat transfer is marked. If conditions in each fluid are appropriate to turbulent flow then the bulk of each will have constant concentration due to the equalizing effect of the turbulent eddy motion. On either side of the interface, however, laminar flow exists since at the interface friction between the two phases prevents slip. In the two laminar films a concentration gradient exists and mass transfer is by the normal diffusion mechanism. The concentration profile is shown in Figure 63(b). This theory of mass transfer, due to Whitman, is by no means the only one. It does, however, give results which can be usefully applied in plant design and the mathematical derivation resulting from it is relatively simple.
6.3 ABSORPTION
The Whitman two-film theory can be applied to absorption. In Chapter 3, the type of rate equation found in chemical engineering was explained and we shall expect this to apply to absorption. In Figure 6.3, we shall study first transfer through the gas film of thickness zg. Although the gas film is in motion, in the laminar section there is no contribution due to convective motion,
95
and transfer results from molecular diffusion only. We shall assume that the system is composed of the gas species A and B and the non-volatile liquid L. A is soluble in L but B is not. The gas A will flow through the film to be absorbed in the liquid. If we deal with unit crosssectional area of the interface, then at the interface Na moles per second of A are leaving the gas phase and going into the liquid (see Figure 6A(a)}.Na can be calculated in terms of the diffusion coefficient and thickness of the film zg. The calculation is straightforward; the differential diffusion equation (b.l) is developed for the point distance x into the film and then this is integrated between the limits of x = 0 and x = zg. In the gas phase the partial pressure of A may be used to represent its concentration. The calculation is simplified if A is present in relatively small concentrations.
Figure 6.4 Absorption: arrangement of absorption tower (b)
The Whitman two-film theory provides a method for calculating rates of absorption in terms of an overall transfer coefficient and the concentrations in the gas and liquid phases. Once again, we come back to the question of determining values of the coefficients. As in the case of heat transfer, this is done by reference to experimental results. The theoretical derivation so far, however, is applicable only to instantaneous rates of transfer. Before it can be applied to a complete absorber, the types of absorber must be reviewed and the theory extended to cover the complete equipment. The rate of absorption depends on rate constant, driving force, and surface area, and it is only the last variable which is readily within the control of the designer. Absorption equipment must be designed to give a high interfacial area and, of course, to ensure that the bulk liquid and gas phases have access to this interface. Absorption equipment generally provides for a flowing layer of liquid with gas traveling past it counter-currently. To provide the surface area, the liquid is made to flow over a packing material in a column. The flow of liquid is down the column, gas up. The most common type of packing is rings made up of porcelain, ceramic, or plastic. The rings are in the form of right cylinders. A wide variety of other types of packing is usedwooden slats, packings made up of shapes other than rings, granular material, etc. A schematic arrangement of an absorption tower is shown in
96
Figure 6A(b). The absorption interface area in a tower of a given size can always be increased by reducing the size of the packing material. Two major limits to the packing size exist. The first is concerned with strength; the packing elements must be able to support the weight of packing above without breaking. The second is that the pressure .drop across the packing increases as the size of packing is reduced. As in most other design situations, an economic balance must be struck between the requirement for surface area and the pressure drop. The packed tower is not the only type of equipment used for absorption duties. Others are:
Plate Columns. There are a number of plates in the column across which the liquid
flows and the gas bubbles through the liquid on the plate. These will be described in more detail in the next section.
Wetted Wall Column. The liquid flows down the wall of the column and the gas
passes up the middle. This is a system used experimentally, as it is reasonably simple to treat mathematically.
Spray Tower. The liquid is sprayed in at the top and the gases flow up through the
spray of droplets.
Bubble Column. The gas is made to bubble up through a column of the liquid.
6.4 SOLVENT EXTRACTION

The process of solvent extraction applies the same principle as is used in carrying out 'extractions' in the laboratory. The solvent and the liquid bearing the solute, with which the solvent is immiscible, are brought into intimate contact. The two liquids are then separated. The operation may be repeated by bringing more solvent into contact, and so on. In a chemical plant it is desirable to carry out the process continuously and a counter-current flow arrangementsimilar to the absorption tower-can be adopted. Each stage consists of a mixing step and a separation step. The theoretical treatment of solvent extraction depends mainly on knowledge of equilibrium between the two phases. If sufficient time is allowed in the mixer for equilibrium to be established and in the separator for complete separation of the two phases, then knowledge of equilibrium alone is sufficient. In fact each mixer-separator stage is called a theoretical stage and the number of theoretical stages required can be calculated graphically.
(a)
97
Raffinate Concentration
acetone per mole benzene
Figure 6.5. Solvent extraction: diagram for graphical estimation of number of theoretical stages.
Theoretical Stages
Figure6.5 shows the equilibrium curve which relates the concentration of solute in the raffinate phase (X) to the concentration in the solvent phase (Y). 'Raffinate1 is the term used to denote the liquid which remains after some of the solute has been removed from it into the solvent. The 'extract phase' is the solvent containing the solute after the process of extraction. The object of extraction is to remove solute from the raffinate phase into the solvent or extract phase; i.e., referring to Figure 6.5(/>), the value of X will be decreased as the feed moves from left to right and the value of Y increased as the solvent goes from right to left. The extent to which the value of X can be reduced in any one step depends on the relative flow rates of the feed solution and the solvent. The performance of a solvent extraction unit of this type depends on two factorsthe equilibrium between the two liquid phases and the flow rate ratio of the two phases. What the designer wants to do is find out how many theoretical stages are needed to reduce the concentration of solute in the feed from a given initial value to a specified lower value using a certain quantity of solvent. As an example, the system acetone-benzene-water can be used. Acetone is more soluble in benzene than in water; this can be seen from the equilibrium curve in Figure 6.5. If water is to be used as the solvent in extracting acetone from benzene, then it must be used in a quantity much larger than the flow of benzene. Suppose, for instance, that 10 moles of a solution of acetone in benzene is to be fed to a solvent extraction unit. The mole ratio of acetone to benzene is 0.3; the benzene feed rate is 10 X 1 /1.3 = 7.69 mole/s. The acetone content is to be reduced to 0.02 by extraction into water which is fed to the unit of 48 mole/s. How many theoretical stages are needed?
98
The first step is to plot the equilibrium curve of Y against X (see Figure 6.5). Y = mole ratio, acetone -water X - mole ratio, acetone-benzene Acetone extracted into the water = 7.69 (0.3 0.02) 2.16 mole/s Thus the ratio of acetone to water in the extract is Yo = 2.16 / 48 = 0.045 We can now plot the two points A and B on the graph which represent the two ends of the extraction unit. If the points A and B are joined by a straight line, then the material balance ensures that other intermediate points between extraction stages also lie on the same line called the operating line. Starting from the point A, we know that the raffinate leaving theoretical stage 1 is in equilibrium with the final extract. If we draw a horizontal line from,4 to meet the equilibrium curve we find the raffinate composition after the first stage; then, by dropping vertically to the operating line, the composition of the extract from stage 2 is found. The stepping procedure is repeated until point B is reached and the number of theoretical stages is foundin this example, four stages. The reader will see that this example has been rigged' to give an exact number of stages, but it is quite possible for the last stage to be a part stage. This simply indicates that, by taking the next integral number of theoretical stages, a slight lowering in the desired final acetic acid in water concentration is possible alternatively, a lower benzene feed rate could have been selected. The method of determining stages above is appropriate to the case where the solvent is totally insoluble in the feed liquid. This is not a normal situation, so the raffinate usually contains some solvent and the extract some of the original solution. In this case the determination of theoretical stages can still be carried out graphically, but the method now uses the triangular composition diagram.
Equipment Used for Solvent Extraction

The mixer -separator is the simplest type of solvent extractor to treat theoretically but any equipment in which the two liquids can be brought into contact with a large interfacial area between them can be used. The mass transfer process is then similar to that in an absorption column. A packed column can be used, with the lighter liquid flowing upwards and the heavier down, or a spray or bubble column, in which one Liquid is divided into fine droplets and passes counter-current to the other. Columns with various types of plate are also possible. The theoretical treatment of such columns leads to an equation for the height analogous to Eq. (6.10) for absorption. The height of a transfer unit and number of transfer units can be calculated. (It may be noted that Figure 6.5) could still be used to determine the number of theoretical stages, since the overall balance can be carried out, A and B can be plotted, and the operating line drawn. We have no way of calculating the amount of packing required for
99
each theoretical stage. In general, the number of transfer units is not the same as the number of theoretical stages, and the height of a transfer unit does not give the amount of packing needed for a theoretical stage.) In determining the size of column needed, experimental work must be consulted to evaluate overall transfer coefficients, as is done in the case of absorption. In a packed column, the rates of relative flow of the two liquids that can be achieved under gravity is related to the difference in density of the two liquids. In order to improve the relative rates of flow, equipment has been designed to use centrifugal force instead of gravity; a number of proprietary types are available. One of the problems in using columnsparticularly spray columns without packing-is the tendency for the dispersed liquid to coalesce, and various devices may be used to prevent this. One method is to place a central shaft through the column which rotates and creates a stirring motion. This shaft may have discs attached to it. A second method is to pulse the flow with a reciprocating motion; the agitation hinders coalescence.
6.5 DISTILLATION
When a liquid containing two or more volatile components is boiled, the vapour generally has a composition different from the liquid. This fact is the basis of the use of distillation to separate the components from one another. Distillation of a two-component liquid is simpler than either absorption or solvent extraction. In all cases there are two phases, but in twocomponent distillation there are only two components, whereas solvent extraction and absorption involve a minimum of three. If a two-component liquid is distilled as a batch, the more volatile component tends to distil first, so that the vapor is rich in that component and the liquid becomes gradually richer in the less volatile component. The vapors composition also changes slowly, with the concentration of the less volatile component increasing; but the vapor-phase concentration of the less volatile component always remains less than that in the liquid. Ultimately, the liquid is almost entirely the less volatile component, which is distilled almost pure. Although some separation is achieved in this waythe initial distillate may be almost pure and also the final distillatea lot of the distillate will contain both components. What the chemical engineer wishes to do is adapt this process, so that he can get each component almost in the pure state and not have a fraction left still containing both components. One could imagine doing this in a series of stills working rather like the mixerseparator tanks of the solvent extraction process. The vapor from one still would be condensed and put in the next one, while the liquid was taken back into the previous still. In this way, an enriching vapor stream would be taken forward and a weakening liquor stream would flow in the reverse direction. This is, in effect, how continuous distillation or fractionation is carried out but without the need to condense and distil at each stage. Figures 6.6(0, c) show how the process works. The mixed liquid is fed into the middle of the column. The volatile vapour comes out at the top and is condensed and the liquid of lower volatility comes out at the bottom. Inside the column is a series of perforated plates or trays and the vapour passing up the column bubbles through the liquid passing down. Theoretically, vapour V is in equilibrium with liquid L at each stage, and the vapour has a
100
higher concentration of the more volatile component than the liquid. Going up the column from the feed tray, both liquid and vapour are richer in the volatile component, while going down the column they are weaker. At the top some of the condensed liquid is fed back to provide liquid for the top tray, while at the bottom some of the liquid is boiled to provide a vapour flow to the bottom tray. This process is now seen to be very similar in principle to solvent extraction; at each stage the liquid and vapour are put in intimate contact for mass transfer to occur and they are then separated theoretically in equilibrium with each other. By plotting the equilibrium and operating lines and stepping off the stages, we would expect to be able to determine the number of theoretical stages as for solvent extraction. This can be done, but the derivation is more complicated because heat transfer for condensation and vaporization on a tray must be considered in addition to mass transfer. Furthermore, there is one operating line for the upper section of the column and another for the lower section.
Theoretical Plates Determination

For this calculation we work in moles and mole fractions. L and V are liquid and vapour mole flow rates and y represents the mole fraction of the more volatile component in the vapour; A" is its mole fraction in the liquid. H represents molar liquid enthalpy, H molar vapour enthalpy. Material balance Ln+1 x Xn+1 + Vn-1 x Yn-1 = Ln x Xn + Vn x Yn Thermal balance Ln+1 x hn+1 + Vn-1 x Hn-1 = Ln x hn + Vn x Hn + losses and heat of mixing
Feed
101
Figure 6.6. Distillation: (a) general column arrangement, (b) tower annotation, (e) flow arrangement for plates, (d) plate annotation
The thermal and material balances must be carried out for each plate in order to calculate compositions and flow rate step-wise from plate to plate. This is an unwieldy calculation, and it is possible to make simplifying assumptions which do not invalidate use of the method. These assumptions are 1. No heat losses reasonable for a well-lagged column. 2. Heat of mixing is neglectedtrue for an ideal mixture. 3. Molal latent heat of vaporization independent of composition hn = hn +1 and Hn = Hn + 1
The effect of this last assumption is that V and L are both constant in each section of column. The objective is to be able to decide the number of theoretical plates when the design duty of the column has been specified. The duty of the column is to separate a feed liquid of F mole/s containing a mole fraction Xf of the more volatile constituent into an overhead stream with composition xD and a bottoms stream composition xw. A material balance on the whole column enables the overhead D and bottoms W flow rates to be calculated. If the material balance is carried out on the section of the column above section A in Figure 6.6(b), we have Vn = Ln+1 + D Vn x Yn = Ln+1 x X n+1 + DxD Since Ln = Ln+1 Yn = (Ln x Xn+1) / (Vn) + DxD / Vn and a similar balance on the bottom section below B gives Ym = (Lm x Xm+1) / (Vn) + Wxw / Vm
102
If the equilibrium relationship for the vapour and liquid phases is plotted as a curve relating/ to .x, then these equations are the operating lines for the two sections of the tower. Figure 6.7 shows the equilibrium line and the operating lines. Considering the upper part of the column, we know that the point representing xd lies on the 45 line, since xd is also the liquid composition at the top plate. Also, the intercept on the jy-axis is given by DxD/Vn and the upper operating line can be drawn between these two points. The lower line is fixed in a similar way. The values of W and D were calculated from the overall balance but, before the lines can be plotted, Ln, Vn and Lm, Vm must be specified. For the moment, we shall assume they are known and return to this point shortly; given the values of Ln, Vn and Lm, Vm the two operating lines can be drawn. The theoretical plates are stepped off on the equilibrium diagram between the two lines as shown in the figure. This method of determining the theoretical plates is called the McCabeThiele diagram after its originators. We return now to the question of plotting the operating lines. To plot the upper line we need to know D/Vn, to plot the bottom we need W/Vm. In fact, D/Vn is a variable which is in the control of the designer; he can decide what proportion of the vapour reaching the top of the tower is to be condensed and returned to the tower. The liquid returned to the top plate is called the reflux and the ratio of the reflux flow to D is called the reflux ratio (R). When the reflux ratio is specified by the designer, this fixes D/Vn and Ln/Vn. since mole flow of vapor and liquid is constant in the top section. Ln = RD and Vn =(R + 1)D so D/Vn =1 / (R + 1)
Figure 6.7 Graphical determination of theoretical plates (McCabe Thiele method). .V - mole fraction of more volatile component in liquid, y = mole fraction of more volatile component in vapour
The flow ratios in the lower half of the column now depend on the form of the feed. If the feed is liquid at its boiling point, it simply results in an increase in the flow of liquid in the lower half of the column.
103
Lm = Ln + F, Vm = Vn W/Vm = W/Vn = W/(R + 1)D The lower operating line can therefore be plotted between the points (Xw, Yw) on the 45 line and [0, -(WXw / Vm)] on the y-axis. (Each operating line could, alternatively, be plotted by using a single point and the slope.) In doing the stepwise construction on the diagram, the change from the upper to lower line is made at the plate to which the feed liquid is supplied. To minimize the number of plates, this should be the plate at which the intersection of the two lines is passed as is indicated on the diagram. The reflux ratio is an important variable for the designer because of its influence on cost. If the reflux ratio is reduced, the slope of the operating line changes and the number of plates is increased; the capital cost of the tower also goes up. The energy consumptions for reboil and cooling water load are both reduced, so that operating cost go down. The reflux ratio therefore must be based on a balance between increasing capital costs and decreasing operating cost. A further constraint lies in the fact that there is also a minimum reflux ratio, below which the slope of the upper operating line is such that the line crosses the equilibrium line before the feed composition is reached: under these conditions the column will not achieve the desired separation, however many plates it has. This estimation of the number of theoretical plates leads us to a theoretical design of the column. We could not expect a practical plate to give perfect equilibrium between the liquid and vapour leaving it; there are a number of seasons for this, and the designer now needs some estimate of (he efficiency of the plates, so that he can decide how many real plates to put in the column. There are many methods for calculating the plate efficiency. Some are based on mass transfer considerations on the plate; others are based on correlating experimental results from both laboratory and full-scale plant tests. These will not be discussed here but, since plate efficiency can vary from as low as 20% up to 80'/', the value used has an important effect on the size of the tower. The most simple expression of plate efficiency is to apply an overall efficiency to; the column. Then Number of theoretical plates = Efficiency X actual number of plates
DESIGN OF DISTILLATION COLUMNS

A number of inter-related factors have to be taken into account in addition to t he reflux ratio, number of plates, and feed plate discussed above. These ate type of plate, plate spacing, and tower cross-sectional area.
Plate Type
Plates are designed lo allow the vapour to bubble up through a layer of liquid on the plate while the liquid flows across. The liquid is turned into a very turbulent layer on the plate by the vigorous action of the vapour bubbles. Liquid is retained on the plate by the weir W and than flows down the down-comer D under the seal S and onto the next plate. The downcomer usually forms a segment of the tray and liquid flows alternately in opposite directions across the plates. There are two main types of plate. The simplest the sieve plate--is a plate composed of a mesh or grid. The other type has special bubble caps fixed to the plate, as
104
shown in Figure 6.8. There may be a thousand or more caps to each plate. Obviously, the former type is much cheaper but suffers from less flexibility and greater tendency to choke should the liquid become dirty.
Plate Spacing
The turbulence on the plate causes considerable splashing and entrain-ment of liquid droplets in the vapour. If the entrained droplets are returned to the plate above, the efficiency is reduced because of the recycling of liquid. Sufficient space must be allowed for the majority of liquid droplets to fall back. A second factor in spacing is the need to have sufficient head of liquid in the down-comer to act as an effective seal and prevent vapour passing up the down-comer.
Tower Diameter
Reduction in tower diameter increases vapour velocity, so the plate spacing needed to prevent entrainment must be greater and some smaller droplets may inevitably be carried up to the next plate. Furthermore, the head of liquid in the down-comer to seal the plate becomes greater. A balance must be made between these factors when the tower diameter is being chosen.
Figure 6.8 (a). Distillation: bubble cap plate. When the plate is fitted into a column the notched sheet at the front is the weir; liquid flows off the plate and over the weir down to the next plate. A large plate ma y contain several hundred caps.
105
Figure 6.8(b). Distillation: typical bubble caps.
Other Design Aspects

Like absorption and solvent extraction, distillation is a mass transfer process. Just as it is possible to replace the series of mixerseparator units used for extraction by a packed tower, so the plates in a distillation tower may be replaced by a packed bed. Generally speaking, the methods used for designing absorption columns may be applied, but the sections above and below the feed point must be treated separately. The treatment of distillation discussed above was for two-component liquids where certain simplifying assumptions were possible. Frequently, there are three or more components in the liquid and the assumptions cannot be used. Other methods have therefore been devised for handling the design of columns for these more complicated systems. Figure 6.9 shows a typical set of distillation columns used in the heavy organic chemicals industry.
106
Figure 6.9. Xylene separation plant which consists of a set of distillation columns. An individual column may contain over a hundred plates set about 0-5m apart. The separation is necessary to allow de-entrainment of liquid droplets which can be carried up from the turbulent liquid on the plate in the vapour phase
107
6.6 CRYSTALLIZATION
Crystallization is the process by which the solute and solvent of a solution are separated from one another. It can also be used for separating one material from another by virtue of their different solubilities in the liquid. Most materials become more soluble as the temperature of the solvent is raised. Consequently, as a solution is cooled, a temperature will be reached at which the solution becomes saturated and crystals of the solute are then formed. The stages of crystallization are saturation, nucleation, and crystal growth. Saturation may be brought about by change of temperature, as mentioned above, or by evaporation; in any case, heat transfer is necessary and a heat transfer surface must be provided in the crystallizer. We will return to this point shortly. A further way to achieve saturation is to add a material to the solution which results in its becoming saturated; for example, the addition of a barium chloride solution to ammonium sulphate solution causes the solution to become saturated with respect to barium sulphate. Although saturation may be reached, crystallization does not begin at once. Saturation is simply the point at which no more solute will dissolve. Thermodynamically, the free energy of the solid solute is equal to the free energy of the solute in the solution at that concentration and temperature. In the case of saturation brought about by cooling, for example, crystallization can occur only if further cooling is carried out below the saturation point. The first effect of this further cooling is to produce an unstable, super-cooled solution in which crystallization is possible, i.e., the free energy of the solution is higher than that of the solid. Whether crystallization takes place depends on whether nucleation occurs. In order that crystals may grow in a solution, nuclei which act as centers for the growth of crystals must be provided. The nuclei may be present in the solution as impurity particles during cooling, or they may be added to the super-cooled liquid as crystals of solute or impurity particles. Finally, they may arise by spontaneous nucleation of crystals within the super-cooled solution. This spontaneous nucleation may be brought about either by a relatively high degree of cooling or by turbulent motion such as stirring within the liquid. If the number of nuclei formed in a supersaturated solution is plotted against the degree of super-cooling, then the result is approximately as shown in Figure 6.1. To explain this result we should look at some of the properties of solids and solutions which affect crystallization.
1. Latent heat. When a material crystallizes heat is given up. The molecules in the crystal are in a less energetic state than the molecules in solution.
108
_ O ^
Figure 6.10 Mechanism of Crystallization
2. Size effect. The next atom or molecule to be bound to a very small crystal, which is
made up of just a few atoms, is not so firmly bound as when it becomes attached to a large crystal. This can be seen schematically from Figures 6.10. The stronger attractive forces of the large surface also apply for the surface of impurity particles.
3. Energy distribution of solute molecules. There is a distribution of the energies

about a mean. We shall expect the least active molecules of the group to form the beginning stages of nuclei.
4. Energy distribution of solvent molecules. This is similar. Interaction of a newly

formed nucleus, in which one solute molecule is weakly bound to another solute molecule, with an energetic solvent molecule would cause the 'incipient' nucleus to be broken up. The nucleation phenomenon can now be explained. Solute molecules at (he lower end of the energy spectrum can interact to form an incipient nucleus. Solvent and solute molecules at the high end of the energy spectrum can break up the incipient nuclei before they grow to a critical size. The critical size is reached when all subsequent molecules becoming attached are bound strongly enough to prevent even the most energetic molecules from breaking up the incipient nucleus. The effect of lowering temperature, i.e. raising degree of super-saturation, is to: 1. increase rapidly the number of low-energy solute molecules the curve in Figure 6.10 is displaced to the left; 2. decrease rapidly the number of high-energy molecules for the same reason; and
109
3. reduce the minimum size of incipient nuclei which can withstand interaction with energetic molecules. The nucleus-forming interactions therefore begin to gain ground relative to the disintegrating interactions and nuclei start to be formed. Further reduction of temperature results in very rapid increase in the number of incipient nuclei that survive. In this situation, the effect of turbulence is to increase greatly the number of solute-solute interactions. Only the same fraction of incipient nuclei may survive, but this fraction becomes an appreciable number, whereas in the absence of turbulence it was not. If the nuclei are present, then the growth of crystals will continue until the supersaturated solution reaches normal saturation conditions. While supersaturation exists, individual nuclei of a given size in the bulk of solution will grow largely independently of one another. The total rate of crystallization within a supersaturated solution is dependent, then, on the number of growing nuclei or crystals present and the individual rate of growth of these. The growth of the crystal requires mass transfer of solute ions, atoms, or molecules to the crystal surface and heat transfer away from the surface. Furthermore, all solute molecules arriving at the surface will not be bound. Heat transfer is not usually a limiting factor but a mass-transfer concentration profile is set up as shown in Figure 6.10(r). This indicates that the crystallization rate is dependent on the difference in concentration between the solution and the saturation concentration, under the specified temperature conditions. The total crystallization rate then depends on 1. the number of crystals present, 2. the active surface area of these crystals, 3. the extent of supersaturation, and 4. the turbulence within the liquid since this increases the mass transfer rate. It is quite possible to derive mathematical expressions for crystallization rates in terms of these variables. These, however, prove to be of limited value, for reasons discussed in the next section.
PRACTICAL CRYSTALLIZING EQUIPMENT

Crystallization can be carried out as a batch process or continuously. Batch operation on a modern chemical plant is usually a last resort if particularly careful control of crystallizing conditions is required. A major problem in crystallizers, whether batch or continuous, is the removal of heat where cooling is used to achieve and maintain saturation-and the supply of heat where evaporation is used. In either case, the heat transfer surface is the point of maximum supersaturation and nucleation. Crystal growth on this surface is a major problem, since it causes reduced heat transfer coefficient due to the presence of the crystal film. In continuous crystallizers, this has been overcome by various types of scrapers, which keep the surface relatively clean. Alternatively, the cooling tubes may be divided into batches and a supply of heating fluid passed through individual batches in sequence. During the heating cycle the crystal film is dissolved off
110
that batch of tubes. If batch crystallization is adopted, the heating effect can be provided by the introduction of the fresh batch slightly below saturation conditions. Perhaps the most serious problem in crystallization is the control of crystal size and shape. This is of importance because crystallization is almost invariably followed by centrifuging or filtration; both of these unit operations perform best with well-shaped crystals of uniform size. In a continuously operating crystallizer, crystal size is dependent on the rates of heat transfer, degree of turbulence, and supersaturation. Because of the shape of the nucleation curve (Figure 6.10(a)), quite small changes in operating conditions in a crystallizer can drastically alter the nucleation rate and the size of crystals produced. Two types of continuous crystallizer are used. They correspond to the tubular reactor. The first type consists of a trough with hollow walls through which coolant can be passed. The liquid enters at one end and passes through the trough; a screw is rotated in the trough and forces the crystallizing liquid through, as well as scraping the trough walls clean. The Oslo crystallizer consists of a tank into which liquid is fed continuously; crystallizing liquid from the tank is circulated at high rate through a cooler and back into the tank. The largest crystals settle to the bottom of the tank where the take-off point is placed. Crystal shape is also important so far as filtration is concerned. Short stubby crystals arc usually most easily filtered while long thin ones produce a loose, low-density filter cake and tend to block the filter cloth. Crystal shape can be markedly affected by the impurities present in the liquor; ions which are co-crystalline can alter the shape and filtration properties of the crystals.
6.7 FILTRATION
Filtration is the process of separating a solid from the fluid in which it is suspended (liquid or gas), by passing the suspension through a porous medium which does not allow passage of the solid particles. In the mass transfer operations discussed in previous sections, the equipment design was fairly stereotyped and interest lay in the application of chemical engineering principles to design. In filtration, the processes are not those of mass transfer and the theoretical basis of the operation is a study of the flow of fluids through packed beds. The residue on the filter is a bed of small particles through which the filtrate must be made to flow. A pressure difference must be established across the bed to overcome the viscous drag of the fluid percolating through the tortuous channels made by crystals deposited previously. The theory of the process is relatively straightforward and in this section we shall discuss the equipment used, as this is of greater interest. The simplest types of filter do not operate continuously; they approximate to the laboratory filter funnel in design. Such a filter will consist of a tank with a grid near to the bottom of it; on the grid is placed the filter medium. This could be a cloth, a porous plate, or a bed of graded solid particles. If particles are used, they are arranged with large ones resting on the grid and with particles of decreasing size above them. Slurry to be filtered is passed into the tank and flows through the filter medium under gravity. As a layer of solid builds up on the medium, the rate of filtration decreases. When the minimum acceptable rate is reached, filtration is stopped (flow being diverted to another filter unit if it is a continuous stream). The filter cake is then washed and removed from the tank by backwashing. for example. In this type of filter, filter area is limited to the size of the vessel. A development of the process which allows a large area to he placed in a relatively small size piece of equipment is the plate and frame filter. Again, this is neither a
111
constant-rate filter nor is it continuous in operation, since filtration must be stopped to allow washing and removal of the solids from the filter. The workhorse of the filters in modern chemical industry is the continuous rotary filter (see Figure 6.11), This consists of a horizontal drum around which the filter cloth is placed. The drum rotates in a trough into which the slurry is fed. The inside of the drum is maintained below atmospheric pressure: while a segment of the drum is under the liquid surface, slurry is drawn through the filter and, as the cloth emerges from the slurry, it holds a layer of filtered solid. During the next section rotation fins can he washed by a water spray, which is also drawn through the cake and cloth. Finally, the cake is dried by drawing through air. Before the cake can re-enter the slurry, it is pared from the drum by a discharge knife which runs the length of the drum. The cake falls onto a conveyor which carries the solid to the next processing stage. This filtration process, then, is continuous, and constant, conditions ensure constant rate. There are a number of variants on this type of filter which provide for different mechanisms of discharge of the filter cake, for a sequence of washing, etc. Apart horn a number of other specialist types of filter for filtering liquids, the hag-filter (as used in a vacuum cleaner) is commonly used in the chemicals and minerals industries for separating dust from gases. In this application, the bag-filters are used to back up cyclones which remove the largest proportion of the dust from a gas stream. Again, with bag-filters it is possible to arrange for temporary reversal of flow to separate the dust from the bag and cause it to fall into a collecting hopper.
Figure 6.11 ROTARY VACCUUM FILTER
112
Chapter 7
PLANT SERVICES AND PLANT CONTROL

There is no very good reason for bringing together the two topics of services and control into this chapter. The chapter, however, deals with practical topics which are applicable to all plants on a factory site. The instrument systems used for control are closely linked with the power and compressed-air service to the plant and this is some justification. The modern chemical factory site is a complex of many plants making interrelated products. The byproduct from one plant is the raw material for its neighbour- frequently the main product from a plant is merely the feedstock for the next plant in line. Certain services are provided on the site as utilities commonly available to all plants. These utilities always include the standard public utilitieselectricity, gas, water, communications, drainage. The major additions on a chemical plant site are concerned with the energy aspects of plant operations: Steam systems, Condensed steam system, and Cooling water. In addition, purging gas services -air and nitrogen-are usually provided. In this chapter each of the services will be discussed briefly and from a practical viewpoint. First, however, in view of the major significance of energy considerations, we shall discuss some general principles of the use and production of energy in a chemical works.
7.1 STEAM ENERGY

The thermal energy released by a chemical reaction (the heat of reaction) can be used for production of power and for heating duties in other parts of the plant. The production of power is almost entirely limited to raising steam under pressure and at high temperature. This steam may then be used to drive turbines. The turbines will serve two types of duty, in the case of equipment requiring large amounts of power at fairly steady loads, i.e. compressors, large pumps, etc., the turbine will be coupled directly by a shaft to the equipment to he driven. Turbines are more expensive and more complicated to use for the smaller power duties on a plant pumps, fans, stirrers, etc.; these are therefore driven by electric motors. Electric motors are also more robust and will provide the varying load taken by large solids handling equipment such as driers, conveyors, crushers, etc. If sufficient steam energy can be raised on the plant, then turbines driving alternators can be installed and electric power can be produced. This electric power is supplied to the common factory power system, which in turn provides power at suitable voltage levels for the electric drives on the plant. It is more usual, however, for electric power to be produced centrally on a factory site, and any steam generated on a plant which is additional to the direct steam requirement of the plant is sent along pipelines to the central generating facility. In the central power station the fluctuating supplies and requirements of
113
plants on the site are balanced out, as we shall see in the next section. On an individual plant, then, the general principles are: 1. To generate steam at the maximum feasible temperature and pressure. 2. To use the high pressure steam on the plant for driving machinery, which can be driven economically by a steam turbine. 3. To use steam and heat available within the plant for plant heating duties. 4. To export to the central power station any surplus high energy steam. 5. To draw from the central power supply, electricity required for other types of machinery. Theoretically, steam can be generated in the plant at pressures up to the critical pressure 225 atm, at which the boiling point of water is 363 C. The actual steam generation pressures are limited by practical equipment considerations but have been increasing during recent years; increasing pressure leads to more efficient use of energy in turbines. Currently, pressures up to about 110 atm (boiling point 324 C) are being used. Process and flue gas streams are frequently available for steam raising at temperatures up to 1000 C. The materials available for pipes, valves, joints, etc., usually limit maximum temperature after superheating to 500-600 C. The basic process elements of a steam system are: 1. Preparation of suitable water. 2. Water pumping. 3. Feed water heating, 4. Boiling, and 5. Superheating. Figure 7.1 shows a schematic and simplified feed water and steam system. No attempt has been made to define process stream conditions or to calculate heat balances, but approximate conditions of suitable streams are shown for each duty. Softened water is pumped through a feed water heater to the head tank feeding the deaerator. Deaeration is necessary to eliminate gases from the steam system and to prevent corrosion. After deaeration, water is pumped up to pressure and through a second feed-water heater to the boiler drum, in which level is controlled by the level sensing device which adjusts valve B. Softened water, of course, contains dissolved salts. These become deposited on the tubes in the boiler if preventive measures are not taken. The preventive action is the addition of various salts ('dope') including phosphates, which cause the salts in the softened water to be maintained in forms which are not deposited on boiler tubes. A continuous stream of water is taken from the drum the blow-down to purge out dissolved solids. The water then circulates from the steam drum to the boiler. In the boiler, water is evaporated and mixed steam and
114
water flow back up to the drum where steam is separated. The steam flows to the superheater. Temperature of the superheated steam is automatically controlled by allowing some saturated steam to bypass the superheater. These are the basic elements of a steam system. Minor changes in process flow conditions will not alter pressure or temperature of the steam but will merely change its rate of production. The steam raised in the plant is used for power and heating duties. Two types of turbine are commonly used; these are "pass-out" and 'condensing' turbines. The condensing turbine has a heat exchanger following the turbine; in the exchanger, cooling water causes the steam to condense. This causes the pressure on the steam exit side of the turbine to be reduced to a minimum, and the maximum possible quantity of work is extracted from the steam; a drawback of this system is that the remaining thermal energy-latent heat -of the steam is lost to the cooling water. In the case of the pass-out turbine, the exit pressure of the steam is controlled to be above atmospheric pressure. Depending on this pressure, the steam may be used for a subsequent condensing turbine or to provide heat to a process stream. The nitric acid plant provides a typical example of integration of the energy system with a chemical plant. In a nitric acid plant there are a reactor and an absorber; the remainder of the plant is the energy system. Nitric acid is produced by reacting ammonia with air over a platinum catalyst to form oxides of nitrogen and then absorbing these oxides into water to form nitric acid typically containing 55-60% by weight of HNO3. Until recently the process was invariably carried out at atmospheric pressure. Advantages in operating under pressure, typically of about 47 atm, were then found. These lie in reduced cost of equipment especially in the absorption stage. Although ammonia consumption and platinum losses per kg of nitric acid are higher, consideration of overall economics results in the use of the pressure process for new plants.
115
Boiler feed pump
Figure 7.1. PLANT FEED WATER AND STEAM SYSTEM
116
The impact of energy considerations is shown in the flowsheetFigure 7.2. Gaseous ammonia is mixed with air delivered by the compressor. It passes through the platinum catalyst gauzes in the reactor and reaches a temperature of about 900 C. The mixed nitrogen oxides and nitrogen stream is cooled by boiler A and then feed water heater B and finally in the gas cooler. The gases then pass to the absorption tower. The pressure energy of the gases leaving the tower can be utilized by passing the gases through the tail gas turbine, which provides part of the power needed to drive the compressor. More energy is made available if the gases are heated first and this is done in the tailgas heater, from which the gases pass through the turbine and then to atmosphere. This power-recovery turbine is not capable of providing all the compression energy needed and a further turbine on the same shaft, driven by steam raised in the process, makes up the power needs of the compressor.
Figure 7.2. NITRIC ACID PLANT FLOWSHEET
117
Any surplus steam is exported from the plant. A minor complication to the process is the secondary air. This air is taken from the compressor delivery and is used in the bleach tower to strip dissolved nitrogen oxides from the acid; it then passes into the absorption tower for further oxidation during the absorption process. The interconnection with the factory steam system enables steam to be brought into the plant to drive the turbine and operate the compressor during start-up. The balance of components then is
Process:
Reactor Absorber Bleach tower Turbine compressor set with intercooler (not shown) on compressor Boiler water system and pump Boiler and feed-water heater and steam drum gas cooler coolers on absorption plates in tower (not shown) tail-gas reheater
Energy considerations:
It is quite usual for a factory to have two or three steam systems operating at different pressures. The highest pressure system will be for power generation only and the intermediate pressure steam will be used partly for driving smaller machinery, partly for heating duties. Lower-pressure steam is used entirely for heating duties. The factory network of steam pipelines will interconnect plants, receiving steam from some and delivering it to others. The central power station will maintain the steam balance. There is no way to store steam, so that steam generation rate must always balance steam usage. In practice, fluctuations in demand and production do occur and these temporarily result in changes in steam pressure in the factory distribution system. Ultimately, the central power station controls pressure by increasing or decreasing its supply of steam. A sudden loss of steam production will cause a reduction in steam pressure, until the balance can be restored by shutting down machinery using steam or increasing steam production elsewhere. Sudden decrease in demand for steam results in increased steam pressure and, if necessary, this is controlled by opening valves in the steam system and blowing steam to atmosphere at a controlled rate.
7.2 ELECTRICAL ENERGY

A factory electrical system is the same as the steam system in one respectit must remain balanced at all time, with electrical consumption equaling electrical production. The power station itself is the main electricity producing and distributing centre.
Generators
118
Electricity is generated by steam-driven, turbine- alternator sets which produce threephase alternating current at suitable voltage. Voltage can be adjusted to suit the design of the factory electrical system by choice of alternator design. These machines produce very high currents which are fed into copper bar conductors.
Circuit breakers
The current is taken from the conductors through circuit breakers to the electrical cables which transmit the current to substations. The circuit breaker is a switch designed to limit and contain the electrical arc which attempts to maintain the current when the circuit is broken. Supply cables to the various substations on the factory site have their own circuit breakers so that they can be disconnected from the main distribution bars in the power station. Subsidiary equipment at the central power station provides for emergency operation of the circuit-breaker by the central staff, or automatically if excessive current is taken.
Substation
The substation is usually the plant distribution centre. The cable to it will carry power at high voltage. In the substation the supply is subdivided and transformed to provide lower voltages. Large machines will be driven by high voltage, each with its own supply direct from the substation. The supplies for smaller equipment are taken from the substation again through circuit breakers to distribution boards in a 'switch house'. Here, individual switches or 'contactors'for each item of equipment are provided. From the contactors, power cables run direct to the motors. Electrically operated stop and start buttons are usually provided in the plant control room and, for safety, adjacent to the motors on the plant. The stop-start button systems are of low voltage and wires run from them to the contactor in the switch house to enable the contactor to be operated. In the case of low-current machines, a simple switch in the motor supply circuit is all that is needed.
Overload Relays
Throughout the system, in order to protect equipment, 'overload relays' provide protection against excessive current. The overload relay automatically opens the appropriate circuit breaker when abnormal current flows. Small motors, which operate on low voltage, can be stopped and started simply by the operation of the contactor. Large motors must be provided with starting equipment which controls the feeding of power to the motor. As in the case of the steam system, the larger the overall system, the less it will be affected by the changes in load caused by starting and stopping equipment. The factory system is usually balanced by connection to the national grid. Increases in power consumption in the factory will cause power to be taken from the grid, while reduction in consumption will allow current to be fed out into the national grid. If this is not done, the balance is held by the voltage tending to fall when consumption is increased suddenly: when consumption is suddenly reduced, the load on the generators is reduced, and the fluctuation is taken in the steam system. Reduction of the alternator electrical load reduces the steam demand of the turbines, pressure in the steam mains will rise, and blow-offs will open until steam production can be reduced.
119
7.3 STEAM - WATER SYSTEMS

Intimately related to the steam system are the factory boiler water and condensate systems. All water to be used in boiler systems must be softened so that scaling of heat transfer surfaces does not occur in the boilers. All plants in the site having boiler systems require a supply of softened water. It is economically attractive to soften water in a single softening plant at the power station, where the largest proportion is consumed. This water is then pumped to the various consuming plants. Potable (tap) water from the local water board supplies the softening plant. The ultimate end of most of the steam raised is that it is condensed back to water ('condensate'). Condensate is distilled water, which is highly suitable for use as boiler feed water. Condensate return pipes take the condensate back from plants, where it has been made, to the power station. There it is reused together with the quantity of softened water needed to make up for losses and consumption of steam and water in processes.
7.4 COOLING WATER SYSTEMS

A variety of cooling water systems exist, some of which are operated on a factory service basis while others are local to individual plants. Chemical plants are almost invariably situated beside rivers, lakes, or on the coast. The sea, lake, or river water is an excellent cooling medium. A pumping station is built to pump this water into mains which feed the plants on the site. The water flows from the mains through the coolersheat exchangers of the shell-and-tube type. The water is made to pass upwards through the cooler and it can then return by gravity flow through return mains. A major problem with this type of cooling is the dirtiness of the cooling medium and, with sea-water, its corrosiveness. The most common cooling system on the plant scale is the closed-circuit cooling tower system. The circuit for this system is as shown in Figure 7.3. Water from the cold well is pumped through the rising main and then upward through the various coolers on the plant. It then flows back through the falling main to the hot well. From the hot well it is pumped into the cooling tower, where it flows over the packing and then runs into the cold well.
120
Figure 7.3. COOLING WATER CIRCUIT DIAGRAM
There are two types of cooling towernatural draught and forced draught. The water flowing down through the tower transfers some of its heat to the air and loses some by the latent heat of evaporation of a part of the water into the air stream. The air becomes warm. Its density decreases owing to both the introduction of water vapor and its rising temperature. If the tower is sufficiently tall, the reduction of density of the air is enough to create sufficient natural draught to cause air to flow up the tower. If the tower is short, fans at the top must draw air through- such towers are called forced-draught towers. As in the case of absorbers, good airwater contact and inter-facial area are necessary. To provide this, towers are packed with treated wooden slats. To make up for the water evaporated, additional potable water is fed into the pond. The pumping rates are set so that the cold well is kept full and some cold water overflows into the hot well in which the level is controlled by addition of extra water. Water in this type of system must be treated against two features. Firstly, inhibitors are added to prevent corrosion, and second algae growth must be prevented. Various types of chemical treatment are available for these purposes. The water evaporated in the tower does not take with it the dissolved salts which are present in the feed water. There is therefore a tendency for the concentration of the salts to build up in the cooling system; if no action were taken, they would precipitate out and cause scaling. To prevent this, a purge stream is run from the cooling system. The cooling water is analyzed for dissolved salts content at regular intervals of time. The third type of cooling system is an entirely closed one with no evaporation losses. Water is pumped around the system continuously, and air coolers are installed to cool the water. If there are a number of rather small cooling duties to be carried out, this procedure provides a
121
well-controlled system. It is more economic than the installation of a number of rather small air coolers for each duty.
7.5 OTHER FACTORY SITE SERVICES

Most chemical plants require supplies of compressed air. This is used for many purposes on a plant including cleaning, purging vessels, and for pneumatic instrumentation and air-driven tools. Nitrogen is also often used as a purging gas particularly for tanks which have contained inflammable gases or liquids. Nitrogen and compressed air are normally provided as factory services. Fuel gas is treated similarly. Some plants use fuel gas, while others produce vent gas streams suitable for use as fuel. Again, the balance is easily maintained on the site, either by bringing in town gas or by burning surplus gas to raise steam in the power station. Finally in the factory systems we come to drainage. The factory drains take waste water streams, spillages, overflows, etc., from plants and convey these to discharge into the nearby river or sea, or alternatively into the public sewers. The conditions under which such effluents may be discharged are being restricted because of the serious effect of effluents on public waterways, resorts, etc. Both liquid and gaseous effluents from the chemical plant must be rigorously controlled.
7.6 INSTRUMENTATION AND CONTROL

The purposes of instrumentation on the chemical plant are threefold. 1. To enable the plant to run automatically without continuous attention from operators. 2. To enable the necessary adjustments to operation to be made from a central point. 3. To ensure safety in operation by providing warning of abnormal conditions and automatically taking corrective action. The operating conditions of a plant which it is necessary to control are flow rates, temperatures, pressures, compositions, and interface positions-level of liquids, etc. The values of each of these variables can be measured using a suitable type of instrument, but only flow rate can be controlled directly. Flow rate is measured by one of the methods described in Chapter 3 and can then be adjusted by the opening or closing of a valve. A man could read the flow indicator and adjust the valve by hand; alternatively, an instrument can be designed to read the flow, decide what valve movement is needed, and adjust the valve. All the other variables listed above must also be controlled by adjusting flow rates. As we saw in Figure 7.1, the temperature of the superheated steam was controlled by bypassing cooler steam around the superheater into the superheated stream. Both the provision of automatic control and the ability to carry out remote adjustment are provided by 'controllers'. The basic layout of a 'control loop' is shown in Figure 7.4. As
122
chemical engineers, we do not need to be concerned too much with the internal electrical and mechanical details of the equipment in the control loop; we are concerned with the principles of operation. The pipeline carrying the process fluid is on the plant and the detecting unitsays an orifice plateis situated in the pipe. The controller instrument is in the control room and the valve it must operate is again in the pipeline. The first important problem, then, is to transmit information from plant to control room and back again. Until about 1960, transmission was invariably done by air-pressure signals. The measurement made on the plant was converted from a pressure difference (in this case) to an air pressure. The range 3-15 lbf/in2 was normally used. The converting equipment was set to make zero flowno pressure dropequivalent to 3 lbf/in2 and the maximum expected pressure drop (maximum flow) equivalent to 15 lbf/in2. A constant pressure supply of air was provided to the transducer, at a higher pressure, to enable it to produce this pressure signal. The pressure signal was then transmitted along small-bore (6 mm) copper pipe. The controller was designed to produce a similar 3-15 lbf/in2 signal back to the control valve. This is the pneumatic system. The modern alternative to air-pressure signals, however, is to use electrical signals. The principle of this system is very similar, but a 10-50 mA signal is transmitted through wires, in place of the 3-15 lbf/in2 signal in tubes. These, then, are the transmission systems.
Air supply to provid e pressu re for signal
Air supply to operate valve
Figure 7.4. FLOW CONTROLLER - CONTROL LOOP
MEASURING DEVICES Information from measuring devices can be used in a variety of ways. It may simply be converted into a reading on a dial on the plant for use by men working on the plant, or the information may also be transmitted to the control room to give the operator there
123
necessary data about how the plant is behaving. It can be used, as we have seen above, for control purposes and, finally, it could be used to actuate safety devices mentioned earlier. The use of each particular measurement is specified by the designer, whose decisions are based on the way he wishes the plant to be operated.
Flow Measurement
As mentioned in Section 3.6, flows are almost invariably measured by orifice plates. These give a pressure difference (p) signal proportional to the square of the volumetric flow rate. Standard orifice plate installations are available and for these there is an accurate equation which relates flow rate to p.
Figure 7.5. CONTROL ROOM OF PARA-XYLENE PLANT.
The operator in the foreground is working at the computer console
This is used to set up the flow indicator so that the p signal becomes a needle position on a scale, which is marked in flow rate units. The operator simply reads the scale of the indicator as so many cubic meters per second.
Level Measurement
The level of liquid in a tank is also measured as a p. Two connections are made into the tank, one of which will always be above the liquid level, the other below. The difference in pressure between the two points is a measure of the head of liquid above the lower point. In this case, therefore, p is proportional to level position.
Pressure Measurement
Pressure is usually measured on the aneroid barometer principle. The pressure to be measured is transmitted to the outside of a Hat, closed capsule. As pressure is increased,
124
the capsule becomes distorted and the movement of the capsule is a measure of the pressure applied. The movement may be mechanically transmitted to an indicator needle or converted to a pressure or electrical signal for transmission.
Temperature Measurement
Temperature is almost invariably measured by means of thermocouples. The constant for conversion of milli-volts to degrees is used to enable the indicator to show temperature directly. Temperatures are not transmitted as air pressure signals. Instead, the milli-volt e.m.f. itself is transmitted electrically to the point where the information is required.
Composition Measurement
Composition is in principle easy to measure by chemical analysis in the laboratory. To obtain continuous indication of composition for control purposes is more difficult; a number of methods of continuous analysis are available, based on the principle of using a physical property of the stream. A solution of a solid in a liquid, for example, has changing density with composition. A variety of physical properties can be used for both liquids and gases to obtain a continuous measurement of the composition. Automatic methods are available for frequent analysis of gas, liquid, and solid streams. In the case of gases and liquids, chromatographic methods are available. The chromatograph will take samples and provide analyses at ten- to fifteen-minute intervals. In the case of solid streams, use may be made of the auto-analyzer. A sampling device on the solids stream feeds a sample to the auto-analyzer, where it is automatically dissolved and put through the analytical procedure. The result of the analysis can be presented on a recorder. The use of results from chromatographs and auto-analysis is greatly eased if the plant is controlled by a digital computer. In this case, the analytical results can be stored and processed in the computer and appropriate control action decided. VALVES AND VALVE ACTUATING DEVICES Many types of control valve are available. The essentials are the internal arrangement of the valve and the sealed, actuating spindle. The inside of the valve consists of a 'plug', which either moves up and down or rotates within the valve body to restrict, and ultimately to stop, flow as the valve is closed. The "plug' is moved by the valve stem. Seals are provided where the valve stem emerges from the valve body to prevent leakage of the process fluid. The stem is moved by the valve actuating device. The energy required to move the valve stem and in turn the plug can be provided pneumatically or electrically, but in either case the 3-15 lbf/in2 or 1050 mA signal is insufficient. Assume the movement is to be provided by air pressure and inwards and outwards movement of the valve plug is to be used; then what happens is this. The valve actuator is a mechanical device designed to set the valve in a certain position appropriate to each pressure signal it receives. In order to carry out this work, it is equipped with an air supply at, say, 7 atm. Suppose the valve is part-way open, and the valve actuator signal is suddenly changed by the controller from 7 lbf/in2 to 3 lbf/in2, which corresponds to the closed position. The valve actuator now opens a small internal valve, which supplies 7 atm air to the top of the valve and the valve is closed by air pressure. Using the supply of 7 atm air, the valve actuator is able to hold the valve plug in any position
125
the controller instructs it to. If the movement of the valve plug is carried out by an electric motor, then the principle of operation is exactly the same. CONTROLLERS The controller is the most complicated item in the loop. It receives information continuously from the measuring device, and must send out a continuous signal back to the valve actuating device. The job of the controller is to compare the 'measured value' with the 'desired value' (supplied to it by the process operator); the difference between them is the deviation, The controller instructs the valve actuator how to adjust the valve to keep the deviation as small as possible. The process controllers for the whole plant are usually situated together in a panel in the control room (see Fig.7.5). Figure 7.6 is a photograph of a controller. The process operator sets the 'set-point' (desired value) of the controller at the position he wants by turning the knob; the controller then knows what to aim for. In an ideal world, the measuring unit would instantaneously measure any flow rate change and immediately inform the controller, which would respond at once by readjusting the control valve position. If this were possible in a real system, the controller's job would be easy. In practice, none of the instruments making up the control loop has an instantaneous response, and time lag in the control loop must be allowed for. In the flow control case, there is no time lag in the plant itself; owing to the continuity of the fluid, a change at one point means a similar change throughout the plant.
Controller output signal to valve
Desired value set by knob
Set-point adjusting knob
Figure 7.6. TAYLOR TRANSCOPE PNEUMATIC RECORDER / CONTROLLER. The instrument will record the information from two measuring instruments on the plant. It will also provide an output signal to one control valve.
When other variables are being controlled-temperature, for example-there is a delay in the plant. In Figure 7.7(a), temperature is being measured at point C and controlled by
126
increasing or decreasing the flow of a small control stream through the valve at A. C must be well downstream of B to allow for good mixing of the two streams prior to the measurement point. When the valve at A is opened slightly, the flow of hot water entering the main stream at point B increases at once, but no change will be detected at C until time equal to the B -> C flow time has elapsed. This sort of time lag is called distance-velocity lag because the delay introduced is the ratio of distance to velocity. A further type of delay, which is encountered in chemical plant control loops, is capacity lag. This can be encountered in both the instrumentation and the process sectors of the control loop.
Figure 7.7 CONTROL SYSTEMS
A thermocouple placed in the fluid, for instance, will be enclosed in a sheath to protect it from the fluid. This sheath will have a thermal capacity and there will be a time delay (capacity lag) between a change in the fluid temperature and the detection of the change by the thermocouple. Similarly, if the level control loop is considered, an increase in the flow rate to the tank will not result in an immediate change in level. Also, when the control valve is opened the level will not return immediately to the desired level. There is a capacity lag in the process section of the control loop. Because of these time lag factors it is not sufficient for the controller to give a simple proportional response to the deviation. The controller must be able to compensate for the distance-velocity and capacity lags in the control loop. In the tank level control case we can see that, if the controller could determine the rate of change of level from the information it was given, it could determine the increase in flow rate through the valve which would be needed and could adjust the valve accordingly. In practice, the various delays encountered in the control loop are compensated for by providing the controller with the ability to relate its output signal to the input signal in three ways:
1. Proportional the controller output signal is proportional to the deviation. 2. Derivative the controller output signal is related to the differential with respect to
time (rate of change) of the deviation.
3. Integral - the controller output signal is related to the integral with respect to time of
the deviation.
127
All controllers are equipped with these facilities, and the controller is made to give a total response, which is made up of a component from each. The controller is equipped with internal adjustments which enable the three components to be set.
If the response equation for each item in the control loop is known, it is possible to calculate the best values of the controller constants. Since these values are not critical, however, it is usual for the instrument engineer commissioning the equipment to set each controller on the basis of his experience of the control loop concerned. The settings would only be adjusted if
the control was found to be unsatisfactory. (c) During normal operation of the plant, the operator will adjust flow rates, temperatures, levels, etc., by altering the set-point (see Figure 7.6) of the appropriate controller and allowing the controller to adjust the valve position until the new set-point is reached. There may be occasions, howeverperhaps during start-up or shutdownwhen the operator wishes to be able to move the valve himself directly. Provision is made for this in the controller design. The operator moves a lever or switch from 'automatic' to 'manual' and then movement of the set-point knob allows the operator to send a direct signal to the valve actuator to set the valve in any position desired.
Computer Control
A typical plant may have twenty-perhaps up to fifty-automatic controllers. Once the plant is running, the process operator in the control room will leave these controllers working automatically to keep operation steady throughout the plant. The operator must constantly survey the conditions in the plant in the same way that a pilot or driver watches the instruments in his dashboard. The process operator can only do simple calculations about how the plant is performing. There are some chemical plants in which the alteration of a set of process conditions, say temperatures at several points, can affect the efficiency or safety of operation quite significantly. The two jobs of 1. Continuous surveying of operating conditions, and 2. Frequent calculation of optimum set of operating conditions and adjustment of controller set-points to give these conditions are tasks readily performed by a computer. When an on-line computer is installed, two things are done: 1. The inputs from the measuring units are fed as electrical signals to the computer where they are stored, and 2. The computer is able to adjust the set-points of the controllers.
128
The first requirement for a computer control installation is a mathematical model of the process. This enables the computer to be programmed to calculate the behavior of the plant in response to changes in such conditions as feed rates, temperature, pressure, etc. The computer can therefore simulate plant performance and determine optimum operating conditions. Having done this, it will set the controller set-points in accordance with its findings. It is also possible to design the programme to update itself. Then the computer will use the sets of plant data it obtains to re-evaluate, from time to time, such variables as catalyst activity, fouling factors, pressure drops, etc.; the latest values will be used for the next optimization calculation. In addition to this optimizing control function, the computer will also perform a lot of mundane functions previously carried out by process operators. It will survey operating conditions and indicate any irregularities to the operator, provide logs of present or past operating data, provide economic information for management purposes, control analytical sequences, take emergency shutdown action if necessary, and even print polite messages of welcome, or otherwise, for visiting dignitaries Each function, of course, must previously be programmed into it. In the case of a computer-controlled plant, each individual automatic controller can be switched from "computer' to 'automatic' or 'manual' should the process operator need to take over. Various self-checking methods are written into the computer programme so that faults can be detected before serious results are caused to the plant.
129
C HAPTER 8
DESIGNING AND BUILDING A CHEMICAL PLANT

In earlier chapters there are some examples of flowsheets. The chemical industry itself can be represented by a flowsheet (Figure 8.1). Production of chemicals is a type of industrial enterprise which requires for success a high degree of technical skill. It is not easy for a new company to enter into chemical production and, for this reason, most new plant is constructed for existing manufacturers. Plants are also built for government-controlled industrial organizations; just occasionally new companies enter into chemical production for the first time. Examples of the latter are the farmers' co-operatives set up by groups of farmers in the U.S.A. to produce fertilizers for the farmers to buy themselves. Plant construction projects can vary tremendously in scope from the small pilot plant to develop a new process to an entirely new chemical factory in a new site incorporating a number of plants; such a new factory would also require the erection of a wide range of service facilities called 'off-sites'. The so-called 'green field site', calls for construction of many facilities in addition to those on the factory site. It is often necessary to provide road and rail transportation systems, housing, community services, etc. New construction projects are increasingly being undertaken in the developing countries. In checking the viability of such projects a number of largely non-technical factors must be carefully reviewed. 1. What will be the cost of construction of the factory, production costs, and selling prices of products? Is the local market capable of sustaining the production capacity proposed? On these figures, is the project profitable? 2. Can raw materials and equipment be transported to the site? How will products be marketed and delivered to the consumer? What is the competition likely to be when the plant is operating? 3. Are the necessary supplies of water available and can effluents be disposed of? 4. Is adequate labor available locally for plant construction and operation? If not, is it economically feasible to attract people to the site? 5. How does this project relate with other known developments in the area? 6. Political factors!
130
Figure 8.1 FLOWSHEET OF CHEMICAL INDUSTRY
Such considerations also apply in developed countries, but there are a surprising number of instances where plants were never completed or are unprofitable because such basic questions were not asked or, more often, not answered. Once the decision is made to proceed with a project, the company whose plant it will be must either undertake the construction itself or call in a contracting company. Few chemical manufacturing companies employ sufficient staffs to undertake their own construction work and even those that do rarely carry out all their plant construction. It is not usually economic for the chemical company to employ sufficient expert staff to be able to erect all their own plants because of the relatively low frequency with which they need to construct any single type of plant. The contracting company, on the other hand, maintains a team of expert staff to undertake the work. The contractor will build several plants a year of the same type, while the chemical manufacturer may need only one every five years. Generally, the chemical manufacturing company which does have construction staff will use them for construction of plants based on the company's own developments. In these cases the close contact between the development, design, and construction staffs of the company means that the company may have a significantly greater chance of success than if a contractor were employed. But whether the work is done by the company itself or by a contractor, the basic procedure adopted for the design and building of the plant will be very similar. Let us suppose that the project has been defined and it has been decided that a contractor will be asked to carry out the job. The next step is to define all the details of the site and the project. Climatic design conditions must be specified, ground load bearing conditions determined, availability of factory services fixed, etc. In addition, the details of the 'battery limits' for the enquiry to the contractor must be chosen. Battery limits define the precise details of the plant the contractor must supply, the availability and conditions of utilities, transport systems, etc. The company's own staff for the project (for liaison and supervision) must be chosen and briefed. There are now several ways in which arrangements for the contract can be made. One method is to select one contractor and carry out a joint design and estimating study on which the contract terms will be based. An alternative is to prepare enquiry documents, specifying the details of the project outlined above, and request tenders
131
from selected contractors. The contractor's proposals are then reviewed and a contract made with the preferred contracting company.
8.1 DESIGN INFORMATION

At the end of his university course the chemical engineer may feel that design of almost any plant is a straightforward procedure based on the principles he has learnt. Broadly speaking, this is so, but the company building the plant and spending many millions of pounds on it wants assurance that it will work. Equally, the plant contractor wants this assurance because he must guarantee the performance of the plant. Although the principles of design are well known, a mass of detail about the particular process is needed before an assured design can be made. Practically speaking, this situation restricts the design of a new plant either to those companies which have designed similar plants before or, in the case of a new development, to the company which has made the invention and carried through the development. The company that wishes to build a plant to manufacture product X must either 1. Provide the design details (know-how) itself, or 2. Employ a contracting company which has the necessary know-how, or 3. Obtain the know-how directly, or via the contractor, from a company which has plants for product X. The last type of arrangement is very common and leads to a variety of types of licensing arrangement. Licensing is a major factor in all fields of industry. Once a development has been made, and usually patented, it is cheaper for other companies to purchase the right to use the knowhow rather than carry out the same programme of development themselves. License agreements do not necessarily require that the licensor has patents. He may simply have expertise and know-how which is valuable to another company. Patents are national rather than international, although certain international conventions apply to them. Many countries subscribe to a convention which allows the inventor the same priority date in other countries as he has in his home country, provided that he files his patent application within one year of his application at home. A company will rarely file patents in every country of the world; filing in the major industrial countries is usually sufficient to discourage another company from undertaking the same development. Furthermore, once a patent is published in any countrythis can be from about nine months to three years after the date of filing, depending on the countryit is no longer possible to obtain a patent on that invention elsewhere. Patent rights are an important aspect of a license agreement, but not essential. The most important feature is that the licensor has know-how and expertise in the design and operation of a certain type of plant which he allows the licensee to use in return for payment. Payments may be either a single license fee when the plant is built, or in the form of a royalty paid in respect of each unit of product, or indeed both.
132
When a company develops a new process, the company itself will normally build plants using the process and then set out to license the process to other companies. One obvious way to do this is to make licensing arrangements with one or more major international contracting companies. Contractors are in a strong position to promote such processes, because they maintain contact with a large number of chemical manufacturing companies and also have the skills needed to adapt the process to the individual requirements of each client.
8.2 PROJECT PROCEDURE

The scope of the project is defined and the details of the site conditions, utility requirements, chief project personnel, etc., are all fixed. The next step is the planning of the project. Various modern planning techniques are available to assist the project manager in specifying the timing of the project and the allocation of resources to different tasks in the project. These planning techniques are only as good as the data fed into them, and so accurate information on the time, cost, and manpower requirement of each task is required. The information used here is largely the result of experience on similar jobs. The resulting project plan will only be a sensible and useful tool if the estimates made at the planning stage are good. The plan of the project controls the timing of both mental and physical work. It specifies the dates for decisions as well as for completion of equipment, construction, etc. Delays in reaching decisions are as crucial as delays in equipment. Difficult and complicated problems always arise in chemical plant projects, but decisions must be taken in the time specified by the programme, if completion of the project is not to be delayed. Of course, occasions do arise where such delay is justified and it is here that the project manager must decide the overriding priorities. The project plan covers the main project activities listed below.
Process Design
The process design work starts from a sketch of the process flowsheet; this forms the basis for carrying out detailed material and thermal balances and the development of the exact plant flowsheet. During the fixing of the flowsheet a certain amount of design work on equipment is carried out. Once the flowsheet is finalised, the process design of equipment is completed. During this work the process engineer must take into account the subsequent activities of mechanical design, layout, construction, etc.; this must be done at least to the extent of ensuring that the process design does not make impractical or uneconomic demands of the subsequent design functions. The process design also includes outline specification of the control systems for the plant and the instrumentation and, finally, the preparation of operating instructions.
Engineering Design
The process design has provided the skeleton of the plant; now the rest of the body must be designed. The details of the equipment must be worked out. The types of instrument to be used are specified. The layout of the plant is developed and the pipe work needed to interconnect vessels and equipment is designed. During the whole procedure the design is committed to paper in the form of engineering drawings: flowsheets, line diagrams,
133
equipment drawings, instrument drawings and control diagrams, electrical diagrams, and layout drawings and piping diagrams. The drawings are the 'blueprints' of the plant.
Civil Design
The civil design work can be done once the majority of engineering design and layout work are complete. It involves the specification of foundations, building design and any major concrete or brick work structures. In addition, plans must be made for site leveling, roads, railways, drains.
Procurement
It will be necessary to purchase most of the equipment from suppliers. Drawings are sent to them and quotations of price and delivery date requested. Suppliers for all items are selected and orders placed. Orders for major items must be followed through the supplier's workshop. His drawings must be checked; the equipment must be inspected at various stages during manufacture and progress must be followed in relation to the project plan.
Construction
As soon as civil design work is sufficiently advanced, site preparation can be started. Again, the construction follows a plan in which all the details of provision of site equipment, manpower, services must be included. Normally, a plant will be in operation between one and two years after the order is placed.
Commissioning
Completion of construction is followed by inspection to ensure that assembly is in accordance with the design and then the pre-commissioning work. All moving items motors, pumps, compressors, valves, control valves, conveyors, etc.-must be checked out for satisfactory operation and also to acquaint the plant operating staff with their working. Training of these staff will have gone on during the latter part of the construction period. In addition to the machinery, the subsidiary equipment-such as the cooling water systemis commissioned. All vessels are cleaned out, reactors charged with catalyst, etc. The start-up procedures will have been decided during the process design stage and start-up and operating manuals will be available. Once as many subsidiary sections as possible have been commissioned, the start-up usually becomes a stepwise procedure. The first section in the process is commissioned and set in working order before the second section is started, and so on. Start-up has to be done in this way because it is not until the first section is working correctly that the product from it is acceptable to the next section. After a period of time, the whole process will be operating under reduced rate and production rate is gradually increased throughout the plant until full capacity is achieved.
8.3 PROJECTS DEVELOPMENT
INVOLVING
PROCESS
UNDER
134
It has been mentioned before that the chemical engineer's major role in plant construction lies in the development and process design stages. This section of the chapter is concerned with the passage of a process from a laboratory discovery to the full-scale plant. One of the problems in this chapter has been to give meaningful, up-to-date examples. The reason for this is the high commercial value of chemical engineering data on new processes. A new process for a large-tonnage product may cost $2 3 million to develop, excluding the cost of the new plant. Data on newly developed processes are disclosed, but details of equipment, reaction rates, and operating conditions are not. Even in cases where the actual new development applies only to a very small section of the whole process, development costs can be high and information a correspondingly valuable commodity. Just as it is often difficult to find the exact source of a river, so it is difficult to define the point of origin of a new process. The idea often starts as a result of 'fertilization'. Very frequently, an idea developed by one person as an unsuccessful solution to his own problem is a highly successful solution to another problem. To be an effective inventor, two things are necessarythe ability to devise methods and the ability to recognize their value. After the invention has been born, it is hard work all the way. For the invention to be used successfully it must be developed, and this needs confidence and enthusiasm. In chemical process development the first steps are taken in the laboratory. The invention is put to the test and two questions must be asked. 1. Does the process work? 2. If so, what are the reaction rates? Given the answers to these questions, the development engineer can make a first evaluation of the process. The majority of new processes, except in the pharmaceutical industry, are new processes for making existing chemicals. The development engineer therefore evaluates the capital and operating costs and product quality of the new process and compares them with existing processes. It does not pay to be too critical at this stage, since the new process is being compared with an existing process which is probably highly developed and optimized. If the new process looks reasonably promising, it is worth while persisting; during the course of development it will most definitely be improved. The evaluation based on laboratory results simply indicates whether the process has any prospect of being competitive. Another purpose the evaluation will serve is to highlight points which may become critical as design points or process problems later. Assuming a favorable outcome of this study, the laboratory work will be extended to improve the scope and reliability of the work. In addition, the search for improvements will be started; further laboratory work may be undertaken to study the product characteristics, the side reactions, and the main reaction in simplified stages. One of the greatest problems in research and development is the question of scale-up. In the laboratory, the process may have been operated on the kilogram-per-day scale, whereas plants operate at hundreds of tons per day. The decision has to be made as to whether the small-scale work will provide sufficient confidence and information for full-scale plant design, or whether an intermediate step is necessary. The intermediate step is the pilot, or semicommercial, scale plant operating at a few tons per day. The factors on which such a
135
decision are based are manyboth technical and commercial. Where the product is new as well as the process, pilot-scale operation is almost invariably desirable. It will be necessary to develop the market, for customers to test out the product, etc. Also, in a case where a variety of side reactions is possible or where purity of the product is critical, again the pilotscale unit will provide opportunities for examination of the effect of scale on these problems, without undue commitment of resources to the process. Until recent years, new processes invariably went through the pilot scale and this is still the case with those which are less amenable to thorough chemical engineering analysis, particularly those processes involving solids in the reaction or product separation stages. Nowadays, chemical engineering has been taken to the stage where the jump from the laboratory to the full-scale plant can be made with confidence if the development work in the laboratory is undertaken with adequate skill and thoroughness. A different process has been developed by ICI to produce methanol. Previously methanol was made by causing carbon monoxide-to react with hydrogen at 250-300 atm pressure and at 300400 C. The reaction was a gas-phase heterogeneous catalytic reaction. Even under the conditions quoted, only a rather low degree of conversion was possible (about 5% methanol in gas leaving the reactor). The methanol produced as the gases pass through the converter was removed by cooling the gases and condensing out the methanol; the remainder of the gas was recycled with fresh gas. ICI set out to devise a catalyst which was active at a much lower temperature, down to 220 C, and they succeeded. The lower temperature means that a much higher degree of conversion can be achieved at 250-300 atm but, what is more important, it means that it is possible to operate the methanol process at 50 atm. Another advantage of the new catalyst is its ability to hydrogenate carbon dioxide to methanol-as well as carbon monoxide. Here what is basically, a catalyst development but the consequences are so far-reaching that process conditions are changed to the extent that the lower-pressure (L.P.) methanol process is a new process. I do not intend to use the process as an example of process design, but rather to examine the steps of development and the integration of this work with the design. Before doing so, let us look more closely at the reaction itself. CO + 2H2 <=> CH3OH CO2 + 3H2 <=> CH3OH + H2O H98=-91.0 H98 =-49.3 kJ/mole kJ/mole
In a single bed of catalyst the operation is nearly adiabatic and temperature of the gas rises as the gas passes through the catalyst and reaction occurs. The equilibrium conversion we remember decreases as temperature rises. This sort of reaction requires the multi-bed type of reactor described in Section 5.5 and Figure 5.3. The inter-bed cooling is carried out by introducing cold unreacted gas-the reactor is called a 'quench' or 'cold-shot' reactor. The flow diagram for the synthesis section of the L.P. methanol process is shown in Figure 8.2. The reactants, except for the quench gas, must be heated to about 220 C for reaction to start, while the gases leave the final bed at a higher temperature than this. It is therefore possible to use the inter-changer principle-heating the feed gases to the reactor with the reactor exit gases. The gases which feed the reactor loop can be produced by the endothermic reaction of hydrocarbons-naphtha or natural gaswith steam. This reaction gives a gas mixture mainly composed of oxides of carbon and hydrogen.
136
Figure 8.2 L.P. METHANOL PROCESS-SYNTHESIS SECTION
137
The hydrocarbon-steam reaction is carried out at a much lower pressure and the gases must be compressed to the methanol synthesis gas pressure. A large cost saving then results from compressing only to 50 atm instead of 250 atm. The two reaction equations above produce a solution of water and methanol in the catchpot which must be distilled to give a pure methanol product. We might then divide the L.P. methanol plant into three sections: synthesis gas making unit, reaction section, and distillation section. This provides sufficient detail about the process for the stages of development and design to be discussed. It is not necessary to define the exact moment at which the L.P. methanol process changed from being an interesting laboratory development to being a commercial proposition. ICI has produced methanol for over forty years and having conceived the idea it was natural to proceed with the development work. During the course of the work the need for expansion of Id's methanol production capacity became apparent. At this stage, a careful technical and economic comparison had to be made between H.P. and L.P. processes. The scales came down on the L.P. side and the decision was made to design the new plant for the L.P. process. The change in scale was from the laboratory (kilograms per day) to 300 tons per day. The development work was now forced ahead to meet the design programme. Only the catalyst had been changed, but for design purposes it was a new process. Every piece of information the designer required he must obtain from work in the laboratoryor calculate from theory.
REACTOR DESIGN
First, let us look at this reactor itself-the problems of design and the laboratory work. What does the designer need to know about the catalyst? 1. How active is it, and what are the kinetic equations for the reaction on this catalyst? 2. Is the reaction rate affected by particle size? 3. How strong is it? What depth of catalyst can be accepted without breaking pellets at the bottom of the bed? 4. Is it stable or does activity and/or strength decrease with time? 5. Does it become poisoned or is its activity unaffected by impurities in the feed gas? 6. What is the pressure drop across a given bed of catalyst? Is it consistent or does it vary according to how the catalyst is charged? These are problems the designer needs answered, but equally the R&D engineer has questions to ask about the catalyst. He had made it in the laboratoryprobably with pure starting materials. Will it be possible and economic to make the same catalyst on a tonnage scale from commercial materials and will it have the same activity? (The days are not so long past when the appropriate quantity of waste horse-shoe nails was an essential ingredient of an ammonia catalyst recipe!)
138
How are the designer's questions about the catalyst answered? The laboratory scale apparatus consisted of three essentially adiabatic beds of catalyst-each about one liter in size-operated in series. The gas was fed through and inlet and product streams could be analyzed and temperatures in the catalyst measured and controlled, Pressure could be varied up to about 100 atm. The catalyst volumes of the multi-bed reactor for the full-scale plant were based on data obtained in the laboratory under essentially the same conditions of composition, flow rate per unit volume, pressure, and temperature. The catalyst performance in terms of poisons, age of catalyst, operating temperature, etc., had to be determined by inspired testing; Inspired' because only materials likely to poison this particular catalyst which might arise from a hydrocarbon-steam plant were studied. In conjunction with this, very careful analysis was carried out on existing gas-producing plant to determine all the components which appeared in the gas from such plants, even in very minute quantities down to a few parts per hundred million. The new catalyst was known to be sensitive and such work was necessary. Running laboratory equipment steadily for months at a time is a difficult task. In practice, the results of a few months' work had to be extrapolated to determine expected catalyst performance over longer periods. It was necessary, of course, to consider not only changes in activity with time but also the way in which the catalyst stood up physically to the changes which occurred during ageing. I mentioned the question of the effect of particular size on activity. In principle, the largest reasonable size of catalyst particle is desirable because the pressure drop in the gases passing through the reactor decreases as particle size is increased and the cost of making the catalyst is reduced. It was pointed out in Chapter 5, however, that the reactants must diffuse through the pores into the catalyst particle to reach all of the active surface area of the pores. As the particle size increases the diffusion path of the gases becomes longer and the diffusion rate slower; a stage is reached at which the rate is not limited by the speed of adsorption and reaction on the catalyst but by the diffusion rates in the pores. It is by balancing such factors as these against each other that the physical details of the catalyst are fixed. During the development phase, the method by which catalyst would be made had to be decided and plans were made for its large-scale production. Having chosen the catalyst size, and having selected reactor operating conditions on the basis of the laboratory work, the designer can calculate the catalyst volume for the given plant capacity (300 tons per day). Now comes the question of calculating pressure dropnot only for new catalyst, but also for catalyst after a long period of operation; the circulator must be designed still to push adequate gas around the loop under the end-of-life condition. Using the methods of calculating pressure drop described in Chapter 3-extended to packed bedswe could calculate pressure drop in the catalyst under reaction conditions from measurements made under conditions more easily handled in the laboratory. Measurements were in fact made on a model section of catalyst using air at ambient conditions. The problem of scale-up, however, is complicated by catalyst shrinkage. The catalyst is produced in the chemical form of a mixture of metal oxides. The active catalyst is the mixed metals themselves and the catalyst is reduced in the reactor using hydrogen. This is a common feature of many metallic catalysts and does result in catalyst shrinkage. Careful examination of the dimensions of reduced catalyst pellets and of their behavior during catalyst ageing
139
enabled these factors to be compensated for in calculating the pressure drop to be anticipated at the end of the useful life of the catalyst. During the period of reactor design it soon became apparent that the design employed for the old process at 250 atm was not appropriate to the l.p. process. This conclusion arose from economic studies of the optimum reaction conditions and the interaction of those reaction conditions with the mechanical design of equipment for the plant. A previous principle of reactor design had been to enclose the catalyst and the inter-changer in a single vessel; in addition, it was necessary to design the h.p. process reactor so that the shell was kept cool by passing cold, incoming gas along it in annular space around the catalyst and interchanger. With lower temperature and pressure neither of these features was now incorporated. The reactor was totally redesigned to contain catalyst only with the shell operating at reaction temperature. A new method for introduction of cold-shot streams was also devised. The interchanger was designed as a separate shell-and-tube heat exchanger.
OTHER DESIGN CONSIDERATIONS

The major development in the L.P. process was the catalyst and, consequently, the chief problems in design were those concerning the reactor. It was essential, though, to consider how the change of catalyst and operating conditions might influence the design or operation of the rest of the plant. The most important aspect of the development work was a very thorough examination of byproducts in the crude methanol. Methanol is required nowadays to a very high purity standard and this is achieved in the distillation section of the plant. The design of the distillation section would in any case be different because more methanol is produced from CO2 in the L.P. process and the crude methanol contains more water. The key question, however, was whether the L.P. process crude methanol contained byproducts which would be especially difficult to remove during refining. To answer this question, the laboratory product was put through exhaustive gas-phase chromatographic analysis. From this work and laboratory distillation tests it was possible to be certain that the refined product would meet the stringent analytical requirements. Such development and/or design projects for new processes always seem to those involved at the time to consist of a series of crises, each week or month bringing its new problem. Three attitudes are, however, most likely to bring ultimate success: 1. Recognition of key areas of process design. 2. Meticulous attention to detail in development work concerned with these areas. 3. An optimistic outlook.
8.4 AMMONIA PLANT DESIGN

In this section, the stages in the design of an ammonia plant are used to illustrate points made earlier in this chapter and some of the theory and techniques of chemical engineering described in earlier chapters. The complete design of a 1000 tons per day plant will take an experienced design team tens of thousands of man-hours. The methanol process was chosen to illustrate some of the problems in developing a design for a plant to operate a new process. The ammonia
140
process is so similar to the methanol process that the last section lays some of the groundwork for a study of it. Ammonia is made these days from hydrocarbons, air, and water but no one has found a way yet to carry out this reaction in a single step. CH4 + H2O + N2 + O2 CO2 + NH3 Ammonia is produced in a heterogeneous, gas-phase, catalytic reaction between hydrogen and nitrogen. The catalyst is iron with small amounts of other elements to increase its activity. The catalyst is poisoned by oxygen-containing compounds and the ammonia reactor feed gas must be a pure stream of hydrogen and nitrogen. The hydrocarbon, air and water are therefore converted to the hydrogen-nitrogen stream and purified. The ammonia reaction equilibrium is favored by high pressure and it is not economic to make ammonia below about 150 atm. A large number of plants have been built in this region but it is also possible to use higher pressures and about 300 atm is frequently selected. N2 + 3H2 <=> 2NH3 H98= - 92.0 kJ/mole
The catalyst is not very active below about 400C. The design of the reactor was described in Chapter 5, so in this chapter we shall deal with the other sections of the plant.
Figure 8.3 L.P. METHANOL PROCESS - PLANT.
141
Numbers on the plant equipment on the flow-sheet (Figure 8.2) are also used on the tracing of the photograph to indicate the same pieces of equipment. The plant was designed to produce 300 tons per day but plants can be built to produce up to about 1200 tons per day in a single stream
Firstly, let us look briefly at the stages of the process design. Invariably, the capacity of the plant is specified together with the hydrocarbon feedstock, availability of water, etc. The next step is to choose the basic arrangement of the flowsheet and then carry out the material and thermal balance on the plant so that temperatures, flow rates, and compositions are specified throughout the plant. In preparing the flowsheet and fixing operating conditions, there is a considerable degree of optimization work to do and we shall describe this in more detail shortly.
AMMONIA PROCESS
The flow diagram in Figure 8.4 shows a typical process arrangement for a modern ammonia plant using natural gas as the raw material, while Figure 8.5 is a photograph of such a plant. Natural gas contains sulphur compounds-mainly H2S-which are poisons for the catalysts used in the gas making reactions. These sulphur compounds are removed by absorption on to zinc oxide in the hydro de-sulphuriser. The reaction is ZnO + H2S ZnS + H2O This reaction is carried out at about 350 C, so the natural gas is first heated to this temperature. The hydro de-sulphuriser is designed to hold sufficient ZnO to remove all the sulphur compounds in the gas for a year. The natural gas, which will be regarded as pure methane for our example, now enters the series of reactions with steam and air which yield hydrogennitrogen gas stream. The first reaction is the endothermic 'reforming' reaction. Reforming is carried out at 500-750 C and pressure up to 30 atm in a tubular furnace-itself fired by natural gas. The gases pass through the tubes which are filled with catalyst. The reactions are CH4 + H2O <=> CO + 3H2 CO + H2O <=> CO2 + H2 H98 = 206.0 kJ/mole H98 = -41.5 kJ/mole (1) (2)
The reformer is operated to give an exit gas containing about 7 mole % CH4 which will be largely eliminated in the secondary reformer. (Note: Since gas analysis is carried out after removing H2O, analyses are quoted for dry gas.) At the top of the secondary reformer, air is mixed into the gas, which at this temperature burns. From the flame region the gases pass into the catalyst zone where the same reactions continue. Because the temperature is now much higher, the methane is reduced to a low concentration of about 0-3 mole %. As we shall see later, this is important because methane is 'inert' in the ammonia reaction. The gas leaving the secondary reformer at about 1000 C consists of H2, N2, CO, CO2, H2O, and a little methane and argon. In order to make the maximum amount of hydrogen in the process, it is desirable to make reaction (2) proceed as far as possible to the right. This is an exothermic reaction, whose equilibrium is favored by
142
low temperature. The gas is now cooled in the waste heat boiler and then passes through the first CO conversion catalyst, where CO is reduced to about 1%. After further cooling the gas enters the second low-temperature conversion catalyst, which reduces CO to about 0.1%. Before the gas can be compressed and fed to the ammonia synthesis loop, oxides of carbon must be removed. This is done in two stages. C02 is removed by absorption in a packed tower using a solvent, for which several choices exist. The heat required for stripping the solvent is partly provided by cooling the feed gas. The gas leaving this tower contains only about 0-1% each of CO2 and CO and these are removed in a final catalytic stage by converting them back to methane. CO +3H2 CH4 + H2O CO2 +4H2 CH4 +2H2O
143
Figure 8.4 AMMONIA PLANT FLOW-SHEET
Under the lower temperature conditions in the methanation catalyst, both reactions now go very nearly to 100% and the concentration of the carbon oxides left in the gas is less than 10 p.p.m. (0.001 mole %), which is insufficient to poison the ammonia catalyst. The gas is compressed and then enters the ammonia synthesis loop.
144
Figure 8.5 One of the ICIs ammonia plants. ICI is the world's largest ammonia producer.
PROCESS OPTIMIZATION
In designing the plant there are two levels at which optimization is done. The first is the choice of certain process design parameters which affect the design of the whole plant or a large section of it. The second is the optimization of the design of each individual item of equipment. The three parameters of the first type, which will be examined in this section, are the energy balance, the synthesis pressure, and the 'inerts' balance. The energy balance for the plant is very much dependent on local factors at the plant site. Energy is produced in the form of heat in the reformer flue gas stream and process gas stream. It is recovered from these streams primarily by raising steam at pressure. Thermal energy, which is recovered, is used in natural gas and air heating and in regeneration of C02 removal solution; power is used in synthesis gas and air compression, synthesis gas circulation and in pumping C02 removal solution. It is possible to design the plant so that the plant is 'energy balanced', i.e. just sufficient energy is extracted into steam to enable it to carry out both the thermal and power duties. Alternatively, if other plants which it is proposed to build on the site require steam, it is possible deliberately to design the reformer furnace for
145
a higher fuel burning rate and provide increased heat in the flue gas and therefore greater steam production. The steam system is designed so that heat, recovered in the cooler sections of the plant, is used to heat feed water; heat from intermediate temperature sections is used for boiling and heat from the hottest sections for superheating the steam. Closely related to energy considerations is the choice of synthesis pressure. As the synthesis pressure is increased, the cost of compression of the gas to that pressure increases. There are, however, several process advantages in increasing pressure. The equilibrium conversion for the reaction rises and the rate of reaction also increases; these changes result in both reduced circulation rate and a smaller converter. A second advantage of higher pressure arises from the method for removing ammonia from the synthesis loop after reaction. When the gas leaving the ammonia reactor is cooled, liquid ammonia is condensed from the gas stream as in the case of methanol. The liquid ammonia is separated and the gas is re-circulated. The partial pressure of ammonia over liquid at a given temperature varies little with total pressure and so, as total pressure increases, the concentration of ammonia in the recycled gas decreases. At 300 atm, this concentration is sufficiently low when the gases are cooled to ambient temperature. At 150 atm a considerable degree of refrigeration must be used to cool the gases and this absorbs power. In practice, the total power consumption in compression, circulation, and refrigeration (where required) tends to vary little with pressure and the choice of pressure becomes more a question of considering the capital cost of equipment. Now let us come on to the question of 'inerts'. Methane and argon are both present in the synthesis gas and are inert or unchanged in the ammonia reactor. What happens to them in the synthesis loop? Their concentrations in the loop would gradually increase if no provision were made to remove them. They are removed by taking a purge gas stream from the synthesis loop after their concentration in the loop has built up to a desired operating level. This purge stream results in the removal also of some of the reactant hydrogen and nitrogen. Suppose, for example, that methane and argon represent 1% of the synthesis gas and their concentration in the loop is allowed to run at 10%. To keep the loop steady at this 10% level, the purge stream must equal 1/10 of the feed gas stream to the loop and it therefore takes away about 9% of the hydrogen and nitrogen fed to the synthesis loop. The loop could be operated at a higher inerts concentration than 10% and the purge reduced, but this reduces the partial pressures of the reactants and leads to higher catalyst volume requirement. The cost of gas loss in the purge must be balanced against the cost of increasing the size of the reactor. The argon in the synthesis gas fed to the loop cannot be reduced, since it is in the fixed ratio to nitrogen that exists in the atmosphere. The methane, however, is variable and could be lowered by increasing the reforming temperature at the cost of extra fuel and higher cost of the reformer, or by reducing the C02 content of gas prior to methanation at additional cost in the C02 removal unit. In the case of the inerts, then, there are optimization studies to be done both on the loop itself and on the methane level in the synthesis gas.
MATERIAL AND THERMAL BALANCES

The optimization studies lead to decisions on the key process conditions in this case, the methane content of the synthesis gas and the inerts concentration and pressure in the synthesis loop. The next step is to carry out the detailed material and thermal balances
146
which determine the flow rate, temperature, pressure and composition for each item in the plant. In the ammonia plant this starts from the product ammonia stream. The material balance on the ammonia loop is done first. In doing this the designer specifies 1. The ammonia production rate, 2. The temperature to which the gas is cooled for ammonia condensation, 3. The concentration of ammonia in the gas leaving the reactor for which the reactor will be designed, 4. The concentration of inerts (argon and methane) in the loop, 5. The loop pressure, and 6. The concentration of argon and methane for which the synthesis gas production section will be designed. Given these, together with thermodynamic data and gas solubilities in the liquid ammonia, the synthesis loop flowsheet can be calculated; the calculations also determine the required synthesis gas rate. This is actually a simple but rather tedious trial-and-error calculationnow invariably carried out using a computer. Going back to the natural gas feed to the plant and starting with, say, 1 kg mole of natural gas, it is possible to proceed stepwise through the synthesis gas-making section and determine the quantity of synthesis gas produced per kg mole of natural gas. The ratio of this to the quantity required by the synthesis loop fixes the natural gas feed rate and also the flow rates throughout the gas-making section. This includes the air rate which must be in the correct ratio to the natural gas to give the 3 : 1 mole ratio of hydrogen to nitrogen required by the ammonia reaction. Gas compositions and temperatures are now determined by the designer in the rest of the gas-making plant. This is done largely by experience of what are optimum conditions; use is made of data supplied by manufacture of the catalysts used for the reaction stages, and of equilibrium data for the reactions. Typical, here, is the secondary reformer which is generally assumed to work with exit gas at equilibrium. The methane content of the gas is a variable which the designer selects. There is only one temperature at which the equilibrium conditions satisfy both this methane content and the material balances. The thermodynamic data needed for these calculations are readily available in published literature. Once temperature and compositions are fixed, the heat loads can be calculated and process design work on the equipment can be started.
REFORMER DESIGN
The reaction between methane and steam to produce hydrogen and oxides of carbon is endothermic. It is a heterogeneous, gas-phase reaction catalyzed by nickel which is impregnated on to a refractory, porous support material. The reaction starts at about 450 C, but a much higher temperature (about 700 C) is needed to get a satisfactory conversion of methane
147
CH4 +H2O <=> CO + 3H2 Higher pressure encourages reaction to go to the left, as do lower ratio of steam to methane. This means that, as pressure is increased and steam ratio is reduced, the temperature at the reformer exit must be increased if the same methane percentage conversion is to be achieved. Since both higher pressure and lower steam ratio contribute to improved overall process economics, there is a tendency for plants to operate at high temperature. The desulphurization of the methane is carried out at 350-400 C and steam raised in the heat recovery sections of the plant is available at about 500 C, so that the reactants are fed to the primary reformer at about 450 C. It is clear that a considerable amount of heat must be fed into the process during the course of reaction; part provides endothermic heat of reaction and part the sensible heat needed to heat the reactants from 450 to 700 C. A variety of types of reactor has been proposed to allow for the provision of heat to the reaction. In fact, this is a case where the design is primarily determined by this heat requirement rather than reaction rate considerations. The type of reactor most frequently adopted consists of several rows of vertical tubes (100-120 mm diameter) placed in a rectangular furnace box. Rows of downward-firing burners, in which natural gas is burnt, are placed between the rows of tubes. The tubes are packed with the catalyst and the methane and steam flow through the tubes also downwards. Heat from the burning gases in the furnace box is transferred through the tube wall to the reactants. As the reactants pass through the catalyst, reaction is initially quite slow and temperature rises rapidly. When the reaction becomes faster at the increased temperature, the temperature of the reactants rises very slowly as the heat entering the tube is used for the reaction heat input. This being a design in which heat transfer is the major consideration, it is in the heat transfer calculations and the mechanical design that the problems lie. Heat transfer from the burning gases to the tube wall is partly radiative, partly convective. Radiation to the tube walls is both direct from the flame, and also by reflection from the furnace walls which are made of mild steel, lined internally with refractory bricks. Inside the tube also, some heat is transferred by radiation; the inner wall of the tube radiates to the catalyst particle facing it and the gases pick up heat from both wall and catalyst particles by convection. The spacing of rows of tubes, tubes within the rows, and of burners is important in obtaining even temperature distribution over the surface of the tubes. In the mechanical design, tube wall temperature is a critical variable. The tubes operate at temperatures of 900-1000 C, at which the alloy steels used are subject to a phenomenon called creep. The pressure in the tubes may lie between 1 5 and 30 atm and the walls are under considerable stress. Creep is the gradual stretching of metal under stress at high temperature until it fractures. A creep failure in a reformer tube appears as a small longitudinal split through which reactants escape into the furnace. Creep tests on the steels used have established how long they will operate before failure under specified conditions of stress and temperature. Given the tube wall temperature, the designer can make the tubes sufficiently thick to have an acceptable life say 10-12 years. If we represent temperatures as follows: Tf Tw = mean furnace temperature = tube wall temperature
148
Tg
= reactant temperature inside the tube
Then the heat transfer to a given section of the tube is related to Tf - Tw, and transfer from that section to the gas is related to Tw - Tg; since the tube wall remains at constant temperature, the heat transfer to each section is the same as the transfer from that section to the gas in the tube. The tube wall temperature therefore balances itself out at each point in order to make the two rates of heat transfer equal. Since the heat absorbed by the gas depends on the two factorsrate of reaction (reaction heat) and rate of temperature increase (sensible heat)the calculation of the tube wall temperature requires a knowledge of the reaction process inside the tube, as well as the radiant and convective rates of heat transfer both inside and outside the tubes. These are the calculations the process design engineer carries out to calculate the tube temperature so that the mechanical engineer can specify its thickness. The primary reformer provides two hot gas streams-the process gas at about 700 C and the flue gas at about 900 C. The process gas goes to the secondary reformer, where it reacts with air and reaches about 1000 C. Economy in the process demands the recovery and utilization of the heat from these two streamsprocess gas and flue gas. The process gas undergoes two more stages of reaction during cooling down to the temperature of about 100 C at which CO2 is removed. Each stage of cooling liberates heat which is utilized for a process heating duty appropriate to its temperature at that stage. The heat in the flue gas stream is used to superheat the steam, part of which will be used in the primary reformer reaction, and also to preheat the air fed to the secondary reformer.
CARBON DIOXIDE REMOVAL

The various stages of cooling of the synthesis gas are carried out in conventional shell and tube heat exchangers with the process gas stream inside the tubes. In the cooler following the low-temperature CO converter, condensation of some of the water vapour in the gas takes place. The gas and water flow into a separator pot, where the level is maintained by a controller which operates a valve at the exit of the pot. This valve allows water to pass away for subsequent reuse. All CO2 removal processes are based on a regenerative-solvent system. There are various solvents which will absorb CO2 -potassium carbonate solution, mono-, di-, and triethanolamine, etc. In the regenerative system shown in Figure 8.4, the process gas passes upwards through the absorption tower. This is either a packed or a plate column and the solvent solution flows down it absorbing the CO2 from the process gas. CO2 is removed from the gas down to a concentration of about 0-1 mole %. The solvent leaves the tower and is depressurized to almost atmospheric pressure to be regenerated in the stripping tower. Absorption is exothermic, causing the solution to be heated up, and regeneration requires a heat input. This is provided by a shell-and-tube re-boiler, in which the heat from the final stage of process gas cooling, before it enters the absorption tower, is used to boil the solvent at the base of the regenerator tower. The solvent stream leaving the regenerator is pumped back up to pressure and delivered to the top of the absorption tower. The final stage of gas purification is the methanator, where the residual oxides of carbon in the gas are converted with some of the hydrogen back to methane and water vapour. The
149
methanation reaction is carried out at 350-400 C, where the equilibrium is very much in favor of the methane-forming reactions, and carbon oxides can therefore be reduced to a few p.p.m. concentration. Because of the heat release in the reactor it is possible to use the interchanger principle which is applied to the ammonia reaction; the product gas is used to heat the feed gas to the methanator. The gas stream still contains water vapour, which is a catalyst poison. Most of this is eliminated in the cooling stages prior to and during compression. As the gas is compressed, the concentration of water in it which is required to reach the saturation vapour pressure decreases, and water therefore condenses out during the cooling of the gas between stages of compression. The water vapour in the gas is finally eliminated by scrubbing the gas with the product liquid ammonia before the gas enters the synthesis loop.
SYNTHESIS LOOP
We have already discussed reactor design in Chapter 5. All equipment in the synthesis loop operates at high pressure and must be enclosed in vessels capable of holding the pressure. The shell of the converter, for example, is likely to be mild steel 150 mm thick. The piping also has thick walls in order to withstand the pressure. In spite of using the multi-bed reactor design, it is still not possible to persuade more than about a fifth of gas fed to the reactor to be converted to ammonia. The ammonia must be removed from the gas leaving the converter and the unreacted gas recycled to the reactor together with the fresh gas. If the gas from the reactor is cooled to about 30 C at 300 atm pressure, the majority of the ammonia is condensed as a liquid which can be separated from the gas stream in a separator pot. The fresh gas is scrubbed in the ammonia separator and the mixed gas goes back to the reactor. Each stage of the synthesis loop results in pressure drop as the gas flows through it, and so the pressure of the gas stream must be increased before it can go back into the reactor. This is done in a single-stage, centrifugal compressor called the circulator. The synthesis loop consists then of 1. The reactor, containing catalyst beds and heat interchanger, 2. A shell and tube cooler in which the gases are cooled by water, 3. The separator pot, and 4. The circulator. As was mentioned earlier, a purge gas stream must be taken from the synthesis loop to remove the inertsmethane and argonwhich would otherwise reach a high concentration in the circulating gases. This gas stream is controlled to give 10 to 15% inerts in the loop. Since it is not possible to eliminate ammonia from the gas by cooling, this gas contains some ammonia. The purge gas also contains hydrogen and methane, and may be used as part of the fuel used in the primary reformer furnace. Before this is done, the ammonia is removed by scrubbing the gas with water in an absorption tower.
150
Chapter 9
THE CHEMICAL ENGINEERING PROFESSION

This chapter is intended particularly for those readers who have little knowledge of the organization of the chemical industry or of the chemical engineering profession. The ways in which it is possible to become qualified as a chemical engineer are described. The latter half of the chapter covers the type of organization and work which the newly graduated chemical engineer can expect to find in industry. The most usual route to a chemical engineering qualification is to take a degree course in chemical engineering at a university. The courses at different universities do vary considerably in content and emphasis. Some are three-year courses; others take four years. In some, chemical engineering is commenced immediately, while in others an initial period of one or two years is spent in a science or mechanical engineering faculty. In the latter cases, chemical engineering is started only after satisfactory completion of the initial period. The chemical engineering syllabus of the courses is largely an extension of the subjects for which Chapters 3 to 6 of this book provide a foundation. There is also a considerable mathematics content in chemical engineering courses. It is usual to cover elementary mechanical, electrical, and civil engineering and metallurgy. All courses have a large chemistry content extending the knowledge of inorganic, organic, and physical chemistry which the student brings from school. The second means of obtaining a professional qualification is by taking the examinations of the Institution of Chemical Engineers in the various stages prescribed. The successful completion of the examinations, together with experience in the profession, enables the student to become a graduate member and subsequently a Corporate Member of the Institution. Corporate Membership is recognized within the industry as a qualification equivalent to an honors degree; many regard it more highly because of the industrial experience requirement for Corporate Membership. In the case of a graduate chemical engineer, training cannot be said to be complete when university is left behind. What the engineer now requires is practical experience in industry. The experience he needs is not only concerned with the use of the techniques and theory learnt at university, but also with the actual equipment of the industry, the manufacturers of equipment and construction methods, management procedures, process control and instrumentation, etc. The list, of course, is long, as it is in any industry; in practice, the engineer gathers experience and confidence in the fields in which he works. In the older engineering disciplines it was mandatory for graduate engineers to undergo an apprenticeship to become familiarized with the hardware and procedures of their profession. This is not the case for chemical engineers, but many companies do run graduate trainee schemes for months of duration. For the majority of graduates such a scheme is to be recommended. The graduate chemical engineer leaving university is faced with a difficult problem. He must choose the section of industry he will join, the company within that section, and finally the type of work he wishes to do. For the less qualified engineer the available field may be rather restricted, but for the engineer with a good degree and personality the choice is his. The
151
exceptional engineer will progress quickly in the chemical industryas, of course, he would elsewhere; for the rest of us, a factor to bear in mind is that specific experience in specialist fields is likely to be valuable to an employer and, of course, lead to an interesting and satisfying career. The first objectives, however, must be twofold, 1. To gain experience of the application of chemical engineering methods to problems encountered in industry, and 2. To become broadly knowledgeable of the structure of the chosen industry including the non-technical aspects such as management structures, accounting methods, evaluation procedures for projects, etc. The second objective may seem unnecessary for the man specializing in research, for instance, but we emphasize that it is essential for progress. The reason is this. To be successful in industry the chemical engineer has to be able first to do his job well, second to influence his colleagues to act on the basis of his results. To do the latter he needs to recognize the implications of his proposals within the broad company situation so that he can discuss his proposals in their industrial context. A further most important requirement for success, which is a corollary of the need to influence colleagues, is the ability to write and speak clearly and logically. Brilliant research work will be considerably reduced in value if it is poorly reported and presented. The development of specialist expertise frequently goes hand-in-hand with the building of experience by the chemical engineer. The specialist expertise he obtains may be the ability to solve particular types of problem, detailed knowledge of a certain branch of the industry, skill in starting up plants, or intimate knowledge of particular areas of the world. All of these can be of value to a present or prospective employer. To summarize, then: the graduate chemical engineer should learn to apply the techniques of the profession, generate a broad knowledge of company and industry, and gradually develop specialist know-how or skills. Such, of course, are guidelines for satisfaction and success in any career; success in chemical engineering is certainly not more difficult to achieve than it is in other careers.
9.1 THE INSTITUTION OF CHEMICAL ENGINEERS

The objects of the Institution are officially summarized as follows: The Institution is first of all a qualifying body and, in the exercise of the responsibility of granting certificates of competence to chemical engineers, has a duty to prescribe courses of study, to hold examinations and to assess training and experience whereby professional qualifications may be conferred. The Institution is also concerned with facilities for chemical engineering education, chemical engineering research and associated documentation, the publication of papers and the holding of meetings on subjects of interest to chemical engineers and other matters relating to the promotion of chemical engineering science and its application.
152
The membership structure of all engineering Institutions at present is as follows. 1. Students. They must not be less than 18 and must be in course of training for the practice of chemical engineering. 2. Companions. They must be at least 25 and be connected with engineering or associated sciences. 3. Graduates. They must be at least 20 and must have received or be receiving suitable practical training in chemical engineering. Applicants for Graduate membership must have passed certain sections of the Institution's examinations. 4. Associate Members must be at least 20 and must have passed the Institution's examinations. They must have had a sufficient period of training and practical experience as a chemical engineer. 5. Members. Applicants must be at least 25 and have passed the appropriate examinations. They must also have undergone practical training and held a post of responsibility in chemical engineering for an adequate period. There are slightly revised conditions for older applicants. 6. Fellows. Applicants must be at least 33 and engaged in an important post of responsibility in chemical engineering. 7. Honorary Fallows are distinguished people whom the Institution wishes to honor. Through this impressive professional network, the practicing chemical engineer is able to maintain close contact with technical developments in both university and industry. The individual member generally finds himself much more concerned with the facilities the Institution provides for symposia, lectures, and technical publications than with its role in supervising the technical standards of the profession. The Institution is much younger than most of its fellow engineering institutions but it has a reputation for being a much stronger corporate entity. This is particularly evidenced by high percentages of members attending organized meetings. Although considerable rivalry has tended to exist between the various engineering Institutions, collaboration is now much improved and a Pakistan Engineering Council (P.E.C.) has been formed. The P.E.C, considers matters of common interest to all engineers, as well as organizing joint meetings. As a result of the formation of the P.E.C., members of Institutions comprising C.E.I have been granted the right to the title 'Chartered Engineer'. The C.E.I will ensure that this title covers men of a common standard of competence in the engineering profession.
9.2 THE CHEMICAL ENGINEER IN INDUSTRY

In earlier chapters we have seen the role of chemical engineering in industry, but have not yet considered what work a graduate chemical engineer may expect to do and how he fits into the organizational structure of industry. First of all, how is the industry organized? The majority of the chemical business of the country is handled by large companies and this is
153
particularly true of the large-tonnage basic chemicals. The reason for this is easily seen: the profitability of a chemical plant is closely related to its size and only large organizations can finance large-scale production facilities. The basic organization of all such companies is largely similar and that the work content of jobs within such organizations differs only slightly from one to another. What can vary is the degree of 'job satisfaction' the engineer achieves in his work. This is probably equally affected by the individual's personality and the degree of 'enlightenment' of the management of the company he joins. Firstly the industry itself may be split into the following groups: 1. Chemical product and intermediate product manufacturers. 2. Chemical plant contractors. 3. Chemical plant equipment manufacturers. 4. Consulting organizations. Chemical engineers are employed in all of these types of company. The chemical manufacturer's personnel are divided into 'payroll' and 'staff, although this distinction is now tending to become blurred and has been totally eliminated in some companies. Payrolls are hourly or weekly paid workers unionized and paid on the basis agreed in negotiation between unions and management. Staffs are monthly paid workers who generally agree their conditions of employment individually with their supervisors; salaries are progressive in accordance with age and performance. In practice, however, scales of payment and employment conditions are laid down for staff in large companies for the guidance of managers. Staffs are subdivided into technical and non-technical staff. Non-technical staff tend to deal with commercial aspects of the businesspurchasing of materials, marketing and distribution of products, general personnel matters, financial control; technical staff are responsible for the remainder of the company's business production, research and development, engineering, design, planning, and project management. It is also usual to find a high proportion of technically qualified men among the senior management of all departments of a chemical company. The manufacturing company will employ chemical engineers mainly in its technically oriented departments. At this stage, it is worth briefly reviewing the question of supervision and management. It is usual to find that there is within each department a management structure, with each manager or supervisor having about five or six staff responsible directly to him. This ratio tends to be lower at the higher levels of management, where staffs have a large number of non-supervisory responsibilities and where a man is becoming responsible for a large fraction of the company. Taking a ratio of five, however, the manager has only 20% of his time to devote to any single subordinate's activities. In fact, remembering that he is likely to have to spend a considerable proportion of his time on matters not connected with any of his staff's activities, the percentage of his time available to an individual is probably about 10%. This means that graduate chemical engineers must be self-sufficient and selfmotivating to some extent. The number of staff whom a newly qualified graduate will have responsible to him depends very much on the type of work he does; it is unlikely to be more than two or three unless he is concerned with plant operation.
154
A typical department management structure now appears. Chemical engineers who have been in the company only a few years can see a promotion ladder ahead of them of perhaps two or three levels within their own department, with the post of general managers and/or director above that. A good engineer can obviously expect to make progress up the ladder. (Such ladders appear in almost all concerns of any size including the universities and the civil and armed services.) It is wrong, however, to consider that a successful exciting and profitable career is entirely dependent on progression up the ladder. This is not so. In industry today, there is scope for considerable rewards for the engineer who develops an interest and specialization in a particular field affecting his company's activities. One does not have to be brilliant to do this and there is ample scope for any competent engineer. Continuing to discuss organization, we come now to the technical departments of a typical manufacturing company.
1. Production.
A manufacturing company's production facilities are generally subdivided. A group of plants operating in a similar chemical field will be designated a 'works' or 'factory'. Typically, each plant has a manager entirely responsible for the day-to-day operation of his plant. The manager is frequently a chemical engineer, and, depending on the size of the plant, may have an assistant manager and engineer working under him. Plants generally operate continuously and are, therefore, manned by shift teams of process workers or operators under the supervision of a shift foreman. With a forty-hour working week, four shift teams are required plus supernumerary men to make up for absence, holidays, etc.
2. Process Investigation.
Maintenance of economic operation of chemical plant requires continuous study and improvement of the plant. A manager will deal with minor investigations while more thorough studies covering the operation of more than one plant are dealt with by specialist PI staff largely chemical engineers.
3. Research and Development.

R&D is frequently both product- and technique-oriented, i.e. a department will include teams working on the development of new types of product and processes and also teams concerned with the development of specialist techniquesanalytical, process control, etc. An R&D department also includes its own service sections providing facilities required in common by the research teams. The services sections would include analytical, library, and abstracting, and an engineering service for the detail design and construction of pilot-scale plants and research apparatus.
4. Engineering.
An engineering department generally has the responsibility for all aspects of the design and construction of new plants and major overhauls of existing ones. This topic has been covered in detail in Chapter 8.
5. Technical Planning.
155
In the chemical industry it is essential to review past experience, keep abreast of new developments outside the company, and plan new activities and the expansion of existing ones. This work is often carried out by a team of experienced staff in a 'technical' or 'technical planning' department. Few chemical manufacturers can employ economically sufficient staff to carry out construction of all their new facilities. The company to which they turn is the contractor. A good contracting company will offer the chemical manufacturer almost any service concerned with a new plant he may require. The service varies, for example, from construction only to the provision of a complete, operating unit-the so-called 'turn key' plant. The chemical manufacturer pays the contractor for his services; payment may be made in a variety of ways and is the subject of negotiation and contract between the two parties. Because a contractor is a specialist in the provision of plant design and construction services, it is frequently to the chemical manufacturer's advantage to use a contractor even when he employs a competent engineering department of his own. Some contractors also have equipment manufacturing facilities; many do not, and they purchase all the equipment they require for the fulfillment of their contracts. The contracting company is departmentalized very much in accordance with the separate functions which it is necessary to fulfill in obtaining and executing contracts. Typically, departments would include: Sales Proposals Process Engineering Project Engineering Project Management Mechanical Engineering Design Procurement (Equipment Buying) Construction Commissioning Development with, of course, administrative control, personnel departments, etc. Contracting companies rarely employ large R&D teams; as was mentioned in Chapter 8, much of the process design know-how for plants built by contractors is derived from manufacturing companies. The contractor obtains the right to use chemical manufacturing companies' patented processes or know-how and, in return, the manufacturing company is paid fees or royalties. Of course, contractors also have their own expertise and know-how built up over a period of time for the processes in which they specialize. Before leaving contractors, consultants should be mentioned because they also provide services to the manufacturer. Their services are much more restricted. The services provided may be for the solution of a special problem, but they often include design or project management services.
156
Finally, we come to the equipment manufacturer. Equipment manufacturers tend to operate in a particular area, for example pumps, pressure vessels, heat exchangers, motors, or mass transfer equipment. Again, they have their separate departments for production, design, development, sales, etc. Chemical engineers are generally found in the sales and technical service departmentsdesign, development, and production being much more matters of mechanical engineering. Staffs in the sales and technical services departments are specialists in the applications of their equipment. In the case of mass transfer equipment, for instance, they will be prepared to quote column dimensions and type of packing required for a particular absorption, stripping, or distillation duty. They would then guarantee the performance of the equipment to the buyer. When buying equipment from a manufacturer, one is also obtaining, to a large extent, the manufacturer's experience in the previous application of equipment for similar duties.
Having outlined entry to the profession and the industry's organization from a chemical engineer's viewpoint we shall attempt to define in a little more detail a few of the jobs in chemical engineering, their responsibilities and work content. We shall not discuss the more senior managerial positions, in which the work content is similar to all other professions and the chemical engineering content is reduced.
The Plant Manager

The plant manager is responsible for all matters concerned with the operation of the plant. Before examining the responsibilities in more detail, we need to consider what experience and knowledge the plant manager requires. Typically, the plant manager will have spent some years in the industry-frequently in other departments of the company in which he works. He should be aware of the facilities provided by, or responsibilities of, other departments. He may well have previously worked as an assistant manager or as a process investigation engineer. He must have knowledge of the staff and payroll policies of his company. The manager's technical knowledge must include a detailed understanding of The process, Plant layout, The process flows and all service systems, The plant instrumentation and control, and The methods of operation and construction of all equipment. He should also know well, and have the respect of, the men who operate the plant. It usually needs two to three months to become reasonably well acquainted with a plant. The plant manager is responsible for continuity of operation of the plant. In case of serious defects arising either within or outside office hours, he is called upon by the shift personnel to take decisions. In the case of a breakdown he will find it necessary to go to the plant and take personal control of the situation. The life of a plant manager can, therefore, be
157
physically taxing, particularly when starting up new plant, where the shift staffs have no experience of the plant and frequent reference to the manager for guidance is necessary. When it is realized that a company may lose $5000 an hour due to an unscheduled shutdown, the importance of decisions taken by a manager can be seen. In plant shutdowns he may have only seconds or minutes to decide the course of action to be followed. The more routine aspects involved in the plant manager's job are largely administrative. The raw materials must be obtained and products dispatched at rates up to 1000 tons per day. The problems of managing shift personnel include recruiting, discipline, and the settling of disputes through defined union procedures. Here again the manager carries heavy responsibilities, since a wrong step can lead to withdrawal of labor from his plant in extreme circumstances. The manager, then, spends a lot of time in his plant, in discussion and planning with his staff and in making arrangements with other members of the company's staff for such matters as maintenance, transport, plant tests and investigations, etc; the manager also is the point of reference for all other departments with business concerning the plant. The desk work includes maintaining records of the plant, trying to improve efficiencies and reduce costs, and reporting to senior management on plant performance.
The Graduate Chemical Engineer in R&D

Research and development, process investigation, and process design are frequently the starting point in industry for the newly qualified chemical engineer. In these departments, he can exercise his skills, become acclimatized to industry, and get to know the organization of the company. Jobs in R&D vary greatly from company to company and from section to section within an R&D department. An R&D department can be a quiet backwater sheltered from the hurly-burly of business life, or it can be a lively busy, mainstream department. In the latter case, R&D acts as a driving spearhead of the company's future developments, project plans, etc.: a job in such a department can be extremely interesting and satisfying. The key point to remember is that the type of R&D department one finds depends on one thing onlythe caliber and initiative of the key personnel. The new graduate coming into an R&D department will joint a team of five to ten chemical engineers or chemists and chemical engineers with varied experience in the chemical industry. Such teams are usually led by a manager with broad experience of the company and industry. For the new recruit the manager is initially very much a supervisor suggesting lines for tackling problems, indicating sources of information, and making the necessary contacts outside the department. A project is assigned to each member of the team. Sometimes these projects are unrelated more frequently they are subdivisions of a larger development programme. The chemical engineer must plan his work programme and integrate it with others, arrange for the building of equipment, carry out and analyze experiments, and report the results of his work. At later stages in a development programme he will have considerable contact with other departments concerned with design, construction, and start-up of the process that has been developed. He may well work as a member of a formal team which is set in motion for the project.
158
The job, then, is not dissimilar from research in the university except that, of course, the relationship of the work to the company's objectives is kept in mind. R&D projects must be assessed and evaluated from time to time so that only those projects likely to give an adequate financial return are persisted with.
Project Manager
The project manager is responsible for the commercial and technical success of the project. His job is to coordinate the activities of the staff of the various departments of the company allocated to his project. The project manager's two primary objectives are to complete the plant within the time and cost estimated for the project. He must, therefore, constantly be aware of progress against the two factors of time and cost. Various planning techniques are used to check progress in time. One such technique is critical path scheduling. At the start of the project this enables the tasks on the project which decide the time it will take to be determined. It also enables the slack time for other tasks to be assessed. By maintaining a progress record, it is possible to ensure that tasks on the critical path are completed on time, to allocate additional effort if jobs seem likely to become delayed, and to update forecasts of the completion date. Similarly the project manager should constantly be aware of progress so far as cost is concerned. This is especially important for a contracting industry, since it is only by accumulating the up-to-date forecasts of performance of the contracts it has in hand that the company can estimate its future financial position. Furthermore, the project manager himself can base his decisions on knowledge of the current financial status of a project. Maintenance of up-to-date records on a project is usually carried out on a computer. The computer is programmed to receive and store information on a project and to process this data and print it out for the project manager in summary form. Critical features are also highlighted. The project manager can only perform his function successfully if he has a thorough knowledge of the jobs and working methods of the departments serving him on his project.
Process Design Engineer

The process design group of either the contracting or the manufacturing company is generally organized on similar lines. The group has a chemical engineer to lead it and, responsible to him are senior design engineers, each of whom is experienced in a particular type of plant design. The more junior engineers in the group work under the direction and guidance of the senior men. The work of a process design group falls broadly into two categories. 1. The more speculative work involved in preparation of process schemes for economic and feasibility assessments. 2. The actual design work carried out for a specific project.
159
The former type of work involves the careful definition of the proposed plant, the determination of raw materials available, and decisions on the optimum process route. In addition, it is often necessary to prepare flow sheets and cost estimates for alternative arrangements in order to choose the one which will result in the lowest cost of production. This type of work requires depth of process knowledge, experience of similar cases, and an inventive mind; such work is usually carried out by more senior engineers. The detailed design work for a project is based on flow sheets, material balances, etc., already carried out as part of the early feasibility or proposal work. The process design engineer must now complete the design in detail taking into account all the utilities required, the integration of the plant with existing facilities, etc. The senior engineer will finalize the overall process requirements. Individual engineers will produce material balances-flow rates, compositions, temperatures, pressures, etc. Each vessel or item of equipment must be specified. Its design duty is selected and safety margins decided. This information is set down on data sheets for each item. The data sheets will show the design duty, the method by which design is carried out, the dimensions of the item, and its material of construction. These data sheets are prepared by the process engineer and checked and coordinated with other parts of the plant by the design team leader. Once the data sheets have been prepared, these are passed to the specialist mechanical engineers, who draw up detailed equipment designs. Close collaboration between process design and mechanical design is essential at this stage to ensure that the process designer's basic intentions are met. The process design work does not finish here. The process operating instructions for the plant must be prepared and the design engineer assists in plant start-up and in trouble-shooting during commissioning. The work of a process design engineer is professionally satisfying and has a high degree of responsibility.
Sales Engineer
Selling in the chemical industry is very much a technical job. Sales effort is needed by the chemical manufacturer, the plant contractor, and the equipment manufacturer. Whatever he is selling, the salesman needs a thorough knowledge of his items and broad understanding of the whole range of his company's produce. Probably the most glamorous sales job is that of the chemical plant contractor's sales engineer. The sales engineers of these companies spend a lot of their time traveling the world, although in these days of jet air travel their percentage of time away from home need not be excessive. What does the sales engineer do? Firstly, he keeps himself in touch with the projects which are his concern. He does this partly by reading journals, but more generally through a range of personal contacts in the industry. An international company will maintain agents in many countries to help it with this work. Requests for tenders may be received from companies undertaking projects or, alternatively, must be sought. This preliminary sales and intelligence work is carried out using the usual communications media of letters, telephone, telex, and personal visits. Once the sales engineer obtains the enquiry for a project likely to be of interest to his company, the method of handling the project must be decided. There are various ways a client will wish to work, and his wishes must usually be defined in a meeting between the client and the sales engineer. This meeting serves to define the way the contractor is to present his proposals to the client and also the details of
160
the information about the project which the contractor needs. The sales engineer must then activate his company to prepare the proposal for the client. During this proposal stage, the sales engineer undertakes all client contacts, examines all commercial aspects, and defines and prepares contract documents. A successful sales campaign finishes with the negotiation of terms and signature of the contract. The two most common types of contract are 1. Fixed pricein which the contractor undertakes to carry out a carefully defined task at a 'fixed price'. 2. Cost plusin this type the client pays the cost of all equipment purchased by the contractor on his behalf plus charges for the work carried out by the contractor's staff at an agreed rate. The signature of the contract should not end the sales engineer's interest in the project. He should continue to ensure that his company provides the service to the client in accordance with the letter and spirit of the contract which has been negotiated. The chemical engineer can choose from a range of varied jobs in which his training and ability will be taxed to the full. As a leading technological profession, it has great importance in solving the problems of our age and advancing living standards. The best way of finding out more is to talk to a chemical engineer in industry about his work.
161
REFERENCE:
1.
Perry's Chemical Engineers' Handbook, 6th Edition, McGraw-Hill.

Perry, Robert H. and Green, Don W. (1984).
2.
Encyclopedia of Chemical Technology, 5th Edition,

Jacqueline I. Kroschwitz and Arza Seidel (2004).
3.
Elementary Principles of Chemical Processes 2nd Edition

R. M. Felder and R. W. Rouseau
SUGGESTED READING MATERIAL FOR FURTHER READING:
1.
Unit Operations of Chemical Engineering, 7th Edition, McGraw Hill

McCabe, W., Smith, J. and Harriott,
2.
Encyclopedia of Chemical Technology, 5th Edition,

Hoboken
3.
Heat Exchangers Sadik Kakat and Hongtan Liu
4.
Perry's Chemical Engineers' Handbook, 6th Edition, McGraw-Hill.

Perry, Robert H. and Green, Don W. (1984).
162
SAMPLE MCQS:
d) 1. Kinematic Viscosity is equal to? e)
10%
a. Density / absolute Viscosity
3. Mesh number is equal to?

b. Absolute Viscosity / Density
a)
No of holes per linear inch
c. (Density) X (Absolute Viscosity)
b)
No of holes per square inch
c)
d. None a, b & c of
No of holes per square foot
d)
No of holes per linear foot
2. The Pressure loss

from a venturimeter is about
4. With increasing temperature Viscosity of gases?
a) a)
20%
Decrease
b) Remain constant b)
5%
c) c)
25%
Increases
d)
Both a & c
163
5. Barometer
Pressure is equal to?
d) D / Ln V
7. Absorption of gas in solvent a) gauge

pressure + absolute pressure _______________________
increase
with
a) Increase in temperature
b) Decrease in temp b)
gauge pressure absolute pressure
c)
Increase in pressure
d) c)
absolute pressure + gauge pressure
Decrease in pressure
8. In laminar flow, heat transfer occurs only by
a) Radiation d)
None of a, b & c
b) Convention
6. Reflux
equal to?
ratio
is
c)
Conduction
a) Ln / D
9. A fluid is said to be compressible
b) Ln V / D
a. If density is little affected by moderate change in temperature and pressure
c) D / Ln
b. If the density is sensitive to change in temperature and pressure
164
c. If the density is sensitive to change in both temperature and pressure
1. 2. 3. 4. 5. 6.
b d a c b a c c c b
d. If the density is sensitive to change in pressure only
7. 8. 9. 10.
10. In
distillation column when feed is partly vapor then
a.
q>1
b.
0<q<1
c.
q=0
d.
q=1
Answers

Fundamentals of Chemical Engineering

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Fundamentals of Chemical Engineering

Uploaded by

Copyright:

Available Formats

FUNDAMENTALS OF CHEMICAL ENGINEERING

COMPILED BY: MUHAMMAD AFTAB AMIN

(COURSE MATERIAL FOR DEPARTMENTAL PROMOTION EXAMINATION (DPE))