EG2002: Process Engineering

Rev 4H by JC on 06/10/2011

Introduction to Material Balances (Material Balances - Session 1 of 6)

1. Introduction My name is John Cavanagh - your tutor for the next three weeks over which I will be introducing the concept of material balances. I am providing course notes and will be making recommendations for further reading so will use my lectures simply to introduce and discuss key concepts whilst hopefully providing a different perspective on some of the material. You will be expected to take notes during lectures as I will not be providing copies of my lecture slides.

2. Overview of the lecture series The course notes are divided into six sessions but will be delivered in nine lectures over the next three weeks. Session 1 - Introduction to material balances Session 2 - Material balances involving change of composition Session 3 - Degrees of freedom and problems involving multiple processes Session 4 - Material balances involving chemical reaction Session 5 - Material balances at the molecular level and problems involving recycles and purges Session 6 Solution of complex material balances

3. Recommended reading Whilst course notes are provided students are still expected to undertake additional reading in order to more fully understand the subject. However, as everyone learns in different ways it is important to find a reference book that meets your own personal needs. That said, I highly recommend that you consult the following two well established text books both of which are cited extensively throughout these course notes. Sinnott, R and Towler, G. eds., 2009. Chemical Engineering Design 5th ed. Elsevier Ltd. (ISBN 978-0-7506-8551-1) Felder, R and Rousseau, R., 2005. Elementary Principles of Chemical Processes 3rd ed. John Wiley and sons, Inc. (ISBN 978-0-471-37587-6) Page | 1

EG2002: Process Engineering 4. Learning Outcomes

Rev 4H by JC on 06/10/2011

As this is the first session it is appropriate to begin by outlining the learning outcomes for all six sessions. Having completed this course you should understand the importance and key concepts of material balances. Presented with a suitable problem you should be able to draw and mark-up simple flow diagram, select a basis of calculation, select suitable system boundary(s), analyse the degrees of freedom, write down the material balance equations to describe the process and solve these equations to determine any unknowns. Having done all this you should be able to present your results professionally in the form of a stream list. It is recognised that not everyone studying this course will have a background in chemistry but such students should leave with understanding of how to write down and balance an equation describing a simple chemical reaction. They should also understand and be able to make use of the concept of a mole. At the end of this first session you should understand what a material balance is and why they are so important within the process industries. You should also understand and be able to write down the general equation for conservation of mass.

5. Why are mass (and energy) balances so important to Process /Chemical Engineers? Imagine you are CEO of a company wishing to design and build a new process. In all likelihood you will only be considering such an investment because you hope to make a healthy profit that will pay back the initial investment in the shortest possible time. What do you need to know in order to make the right decision? A decision that could potentially make or break your organisation. Clearly you need to know what you are going to make and where you are going to make it so it might be useful, albeit outside the scope of this course, for you to spend a few moments thinking about what things that might influence your choice? What else do you need to know? The production rate of the new facility is important as it not only sets the scale of the investment and infrastructure requirements but also determines the quantities of products you will need to sell and raw materials you will need to purchase. OK, so you know the what, the where and the how much but what else do you need to know? You need to be sure that you can you make whatever it is safely without damaging the environment but you also need to know what it will cost you to make as only then can you value the investment and decide whether or not to go ahead. Questions you may have might include.. Page | 2

EG2002: Process Engineering

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What raw materials are required? At what rate? What by-products and/or waste streams are there? What are the energy requirements? What will it cost to build? What inventories and process conditions are required and what hazards do they present. What intermittent and continuous effluents are there to air, land and water?

All reasonable questions but how will you answer these? If what you are proposing is very similar to something you (or someone else) have done before it may be possible to start by making comparisons then scaling up or down for factors such as size or complexity. However, you will rapidly need to get into more detail, initially to provide better estimates of capital expenditure (CAPEX) and operating expenditure (OPEX) but then to actually specify and build the equipment. Without material and energy balances it would be very difficult if not impossible to answer many of these questions. Material and Energy balances are the starting point and fundamental building blocks of most, if not all, process designs. Most projects are aborted based solely on initial material balances and the associated economic case. For the few that continue material and energy balances are the starting point for pretty much every aspect of the design, be it process, mechanical, civil or electrical in nature. Even once a process is operational the material and energy balance is the basis for production monitoring systems and any troubleshooting that is required to resolve emergent process issues. This is something that engineers from all disciplines will need to grasp in order to function effectively in the process industries be it oil and gas, chemicals, petrochemicals, pharmaceuticals, food and drink, utilities or waste treatment.

6. Mass and Energy According to Sinnott and Towler (page 52) the loss of mass associated with the production of energy, as described by Einsteins equation E=mC2, is only significant in nuclear reactions. In fact whilst Einstein proposed the concept of mass-energy equivalence he also proposed that both total mass and total energy are in fact conserved separately. This, albeit a very interesting discussion, is only mentioned here in this context as justification for why the conservation of mass and that of energy are always, with the possible exception of the nuclear industry, dealt with separately. That said, in reality, it is almost always necessary to carry out a material balance in order to carry out an energy balance as the latter is usually reliant on data generated by the former. In this series of lectures we deal exclusively with material balances but return to discuss energy balances later in the course.

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EG2002: Process Engineering 7. Material, Mass and Weight

Rev 4H by JC on 06/10/2011

Material is anything made of matter( a somewhat poorly defined concept), Mass is a property of matter and weight is the force exerted by a mass on earth as a consequence of it mass and acceleration due to gravity. In studying this area and in industry you will come across references to material balances, mass balances and less commonly weight balances. However, unless there is some specific reason to believe otherwise you can generally consider these terms as equivalent and interchangeable. In the case of mass and weight the fact that both sides of the balance are subject to the same force of due to gravity mean that this term can be cancelled making any disambiguation rather pointless.

8. What do we mean by Mass Balance? 8.1 Conservation of Mass Imagine you are inside a bubble which has permeable membrane such that material can enter and/or leave as necessary. Now consider the fate of a molecule of oxygen which passes through the membrane in to the bubble. There are a number of different things that might happen next. The molecule can pass back through the membrane and out of the bubble back to whence it came remain within the bubble (accumulate) be used up by your breathing perhaps (consumed)

Now consider the fate of a molecule of carbon dioxide which also enters the bubble It can also course pass back out of the bubble or accumulate within it and whilst it cannot realistically be consumed by the human body it could be consumed if you happened to be holding your favourite potted plant. On the other hand it could gain a friend as carbon dioxide is made (generated) by the same process which consumed the oxygen. If we had knowledge of the material entering the bubble, the capability of the human body to convert oxygen to carbon dioxide and the capacity for the bubble to accumulate gases we could perhaps predict both the quantity and composition of the air leaving the bubble. In doing so we would in effect be conducting a simple material balance over the bubbles membrane. It has already been said that mass can neither be created nor destroyed (other than in a nuclear process) and based on the above, albeit rather simplistic example, it is possible to write the following expression to describe this conservation of mass.

Material Out = Material In + Generation Consumption Accumulation

(Sinnott & Towler, 2009 page 53)

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EG2002: Process Engineering

Rev 4H by JC on 06/10/2011

Where, Material Out refers to material leaving the system boundary whilst Material In refers to material entering the system boundary. Generation and Consumption refer to material generated and consumed within the system and Accumulation refers to an increase of material within the system although this can also decrease (usually expressed as negative accumulation). The above expression known as the general mass balance equation can be applied (and holds true) across any given boundary whether considering overall flows, component flows or flows of individual elements. It no doubt holds true even at the subatomic level although this is not considered within this course since modelling at this level would serve no useful purpose in the context of industrial processes.elder and Rousseau (page 86) define two types of balances; 1. Differential balances indicate what is happening at an instant of time where each term of the balance equation has a rate such as kg/hr. - usually applied to continuous processes. 2. Integral balances indicate what happens between two instants in time where each term of the balance equation may be stated as some given quantity per batch or per day or even per hour provided it is recognised that the flow throughout the period being studied may well not be uniform- usually applied to batch processes Felder and Rousseau correctly obverse that differential balances are generally applied to continuous processes whilst integral balances are generally applied to batch processes. However, it is worth noting that integral balances can be (and are) easily derived from differential balances produced for continuous processes in order to produce balances showing such things as annual production figures. This information can be far more useful than instantaneous balances for evaluating the financial performance of a particular unit as they take into account on stream time (the proportion of the year the process is running) and the proportion of maximum capacity that the process is operating at which may be limited by technical or commercial constraints. Differential balances are often more useful for design and troubleshooting of continuous processes as they provide information about what is happening at a particular period of time which may well be masked by the averaging which can result from integration over time. Having introduced the general mass balance equation it is worthwhile pausing to examine it in more detail. This expression is the foundation on which the next five lectures are built so it is essential that everyone has a clear understanding before we take the next step.

8.2. Material OUT = Material IN Consider a simple pipe, just like the copper ones in figure 1 (overleaf) which most of you will have supplying water to your bathroom at home.

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EG2002: Process Engineering

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Fig. 1: Selection of Copper Pipes

Imagine you are filling your bath and water is flowing through such a pipe. This can be represented diagrammatically as in figure 2, with the arrow indicating the direction of flow.

Supply

Bath

Fig. 2: Cross-section of a pipe with water flowing through it

As you we see over the coming sessions we ALWAYS start by converting a written problem into a process flow diagram. A good process diagram is clear and concise showing all relevant items of equipment and direction of material flows. All streams should be labelled and information such as flow rate and/or process conditions marked (although the same information could be presented in a stream list as we will see later). This helps in clarifying the problem, structuring your calculations and (importantly) communicating your approach and findings to the reader. This is regarded as a critical part of any mass balance calculation for which marks will always be awarded. Expectations will become clearer over the next few lectures as we cover some examples. Having drawn our diagram the next step is always to mark on the boundary(s) over which we will be conducting our material balance. In this example it is rather obvious but it is best to develop good habits right from the start. So lets draw our boundary as shown in figure 3, marked in red where M1 and M2 represent the mass of material entering and leaving the chosen boundary in any given time. This boundary is analogous to the permeable skin of the bubble we discussed earlier. You should also note that the streams have been given numbers to uniquely identify them and arrows to indicate the direction of flow.

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EG2002: Process Engineering

Rev 4H by JC on 06/10/2011

M1

M2

Fig. 3: Cross-section of a pipe with water flowing through it showing mass balance envelope and stream numbers

The rate water enters and leaves the boundary in fig 3 should be the same (unless we have a leak!) or in other words; Mass of water leaving per unit time= Mass of water entering per unit time (Interestingly this still applies even in the case of a leak although the mass of water leaving through both the end of the pipe and the leak would then equal the mass of water entering) Or expressing this more generally we have Material OUT = Material IN

This is a material balance in its simplest form although if you compare this formula with the generalised mass balance formula described earlier there are some other terms (shown in brackets below) which are missing.

Material Out = Material In (+ Generation Consumption Accumulation)

We will now go on to discuss the missing terms in turn.

8.3. Accumulation In this context accumulation is essentially the build-up of material In order to investigate this concept let us return to the previous example but this time consider a situation where the copper pipe is initially empty (and to simplify things) oriented vertically with water entering from the bottom as in figure 4 (overleaf)

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EG2002: Process Engineering

Rev 4H by JC on 06/10/2011

2 System boundary for Mass balance purposes

fig.4: Cross-section of a pipe with water flowing through it showing mass balance envelope with inlet marked as stream 1 and outlet marked as stream 2 So does material OUT = material IN still hold true in this example? What do you think? In order to answer this question we should consider what happens over time. This is shown in Figure 5 (below) which assumes that the pipe holds 20kg of water when full and water is entering at the rate of 10kg/hr.

2= 0kg/hr

2= 0kg/hr

2= 0kg/hr

2= 10kg/hr

1= 10kg/hr

1= 10kg/hr

1= 10kg/hr

1 1= 10kg/hr Time = 3hrs

Time = 0hr

Time = 1hr

Time = 2hr

Figure 5: Mass balance after 0, 1, 2 and 3 hours where n = mass flowrate of stream n

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EG2002: Process Engineering

Rev 4H by JC on 06/10/2011

To start with the pipe is empty and must be filled. After 1hr the pipe is half filled but nothing has left the system boundary at this point. After 2hrs the pipe is completely full but again nothing has actually left the system boundary. Clearly, up until the point when the pipe is full Material OUT Material IN But rather Material OUT = Material IN - Accumulation This type of situation where flows can change with time is known as an un-steady state. The modelling of such is often described as dynamic modelling. However from 2hrs onwards water cannot enter without displacing an equal amount of water out the other end. Once the pipe is full it is again true to say that Material OUT = Material IN The process is now said to be in steady-state In real life situations a process is always in unsteady state to some degree especially during startup and turn down. However, due primarily to the difficulties associated with modelling the steady state the vast majority of process modelling has to date been done on a steady state basis with appropriate design margins and the assumption that appropriately specified control systems will keep us at least close to steady state for the vast majority of the time. In reality the use of steady state modelling has proven itself successful over the years when linked with good engineering judgement and input from experienced plant managers and control engineers as required. Only occasionally do we get caught out but when it happens it tends to happen big-time causing major operating difficulties and/or delaying plant start-up by weeks or even months whilst appropriate modifications are made to equipment and control systems. In most, though not all, problems encountered it will normally be safe to ignore accumulation but you will be expected to state the assumption of steady-state at the start of any calculations as part of simplifying general mass balance equation. In order to further illustrate this concept let us consider a cylindrical vessel similar to the one shown below.

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EG2002: Process Engineering

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We can represent such a vessel, which we can assume is partially full, as shown in the diagram below.

Vent

1 1

2 2

In steady state the level remains constant and material OUT = material IN 2= 1

However, if we increase the flowrate of stream 1, whilst holding that of stream 2 constant, we will observe the level in the drum will start to rise and we will no longer be in steady state. The vessel will continue to fill until the excess flow spills out of the vent at the top unless or until the flowrate of stream 1 is reduced or conversely that of stream 2 is increased to the point where the flows again balance. Steady state is restored but it should be noted that the level in the vessel is now higher than it was before. In order to restore the level to its original position one would have to temporarily reduce the flowrate of stream 1 or increase that of stream 2 until the level returned to its original position.

8.4. Generation and Consumption Returning to the full material balance equation Material OUT = Material IN + Generation- Consumption Accumulation. From an either overall or an elemental material balance perspective both Generation and Consumption are always zero. This is because mass can neither be created nor destroyed, other than in a nuclear reaction. However if a chemical reaction takes place one chemical species can of course be converted to another chemical species. When we burn methane, for example, it reacts with oxygen to produce carbon dioxide and water. In effect methane and oxygen are consumed whilst carbon dioxide and water are generated. The overall mass and elemental balance is of course still preserved but we exchange one molecule for another so if we are looking only at a balance on a Page | 10

EG2002: Process Engineering

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particular molecule we can have both generation and consumption. Only if we have no chemical reaction, are ignoring changes in composition or are balancing down at the elemental level can we cancel out these terms from the general mass balance equation. As always it is essential that all assumptions are stated when carrying out calculations. Marks will be awarded for assumptions and conversely deducted where they are either lacking or not explicitly stated. 9. Example Problems The following examples are rather simplistic but are intended to get you thinking along the right lines and for you to start to develop a structured methodology for answering such questions. Mass balance problems can get very complicated and if you want to have any chance at solving them you should try to develop a standard approach that works and stick with it. You will note that Sinnott and Towler tend to prefer a more ad hoc approach to solving their examples and whilst this can be an effective way of solving simple problems it is suggested that you try to adopt a more structured approach even when, as will often be the case to start with, the examples seem to have an intuitive solution. In going through the following example try not worry too much about the nomenclature as we will standardise this at the start of the next lecture.

[PTO]

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EG2002: Process Engineering Example 1 Question

Rev 4H by JC on 06/10/2011

The flowrate into and out of a 1m3 vessel is 10kg/day and 5 kg/day respectively calculate how long it will take to fill the vessel if it is initially empty. Density of water = 1000kg/m3 Solution As always, start with a flowsheet. Flowsheet Tank 1 1 = 10 kg/day Basis: Differential, Mass kg/day General Equation Material OUT = Material IN + Generation- Consumption Accumulation. But assume no chemical reactions (Generation and Consumption = 0) reducing the above formula to Material OUT = Material IN Accumulation Overall mass balance 2 = 1 Accumulation Rearranging Accumulation = 1 - 2= 10-5 = 5kg/day Time to fill vessel = 1000/5 = 200 days Capacity = 1m3 = 1000 kg 2 2 = 5 kg/day

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EG2002: Process Engineering Example 2 Question

Rev 4H by JC on 06/10/2011

The flowrate into and out of a process is of 10 kg/hr of Reactant A 20kg/hr of Reactant B. Carry out a mass balance to determine the amount of product assuming that the flow of both reactants increases by 1 kg per hour for each hour of the day returning to the original rates at the start of each day. The cycle is repeated for 5 out of 7 days and the plant shuts down for three weeks overhaul every year. Solution As always, start with a flowsheet. Flowsheet Reactant A m1
1

Process
3

m3

Product

Reactant B

m2

Basis = Integral, 1 year and mass (tonne) The calculation could be done on a differential basis at a specific rate e.g. maximum and /or minimum rates however the answers would differ. This is explored in the problems set at the end of these lecture notes but think about the value of doing it? General Equation Material OUT = Material IN + Generation- Consumption Accumulation. But assume steady state (Accumulation = 0) and no chemical reactions (Generation and Consumption = 0) reducing the above formula to Material OUT = Material IN Overall mass balance m3= m1 + m2 Next we need to calculate m1 and m2 Over each day 1 increases from 10 to 34 kg /hr which is an average of (10+34)/2 = 22te/hr so total daily flow = 22 x 24 = 528 kg. This could have been calculated by adding up the flow over each hour or even by integration as the flowrate increases linearly (shown below).

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EG2002: Process Engineering

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Since flow increases linearly over time using formula for a straight line 1 = gradient x time + intercept Over 24 hr flow increases from 10te/hr to 34te/hr so gradient = 24/24 = 1 with intercept = 10 1 = t+10 So total flow over 1 hour is found as follows m1 (daily basis) = = = = 528kg

m1 (annual basis) fed to process per year = (52-3) x (5/7) x 528 = 18,480 kg Similarly for m2 Over each day m2 increases from 20 to 44 kg /hr which is an average of (20+44)/2 = 32te/hr so total daily flow = 32 x 24 = 768 kg. m2 (annual basis) fed to process per year = (52-3) x (5/7) x 768 = 26,880 kg So returning to the mass balance formula m3= m1 + m2 = 28880+18480 = 47,360 tonne (annual basis) Example 3 Question Water flows into a 1000 tonne tank at 100 UK Gallons per minute whilst water leaves the same tank at 240 m3 per day. If the tank is initially half full how long will it take to completely fill the tank? (Assume 1US Gallon = 3785 cm3) Solution To start with draw a flowsheet labelling the streams and indicating the direction of flow.

11
1

Tank Capacity = 1000 tonne

2

Volumetric Flow = 10 UK gal/min

Volumetric Flow = 1m3/day

The above flowsheet should be marked up with the givens which should be converted to the same basis. In this case a mass basis would seem most appropriate as we have the tanks capacity in tonnes. Basis is mass flow using units of tonne/hr Page | 14

EG2002: Process Engineering

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The next step is to convert the givens into the selected basis and mark these up on the flowsheet. In this question you have not been given the density of water. It is often the case that you do not have all the available data to hand in which case you can try to find it in books etc or if necessary make an intelligent assumption. As no data provided assume density of water as 1000kg/m3. Mass flow of stream 1 (1) = 100 US gal/min =100 x 60 US gal /hr = (100*60*3785)/1E6 m3/hr = (100*60*3785*1000)/1E6 kg/hr = (100*60*3785*1000)/(1E6*1000) tonne/hr = 23 tonne/hr (0 d.p.) Mass flow of stream 2 (2) = 240 m3/day =240/24 m3/hr = (240*1000)/24 kg/hr = (240*1000)/(24*1000) te/hr = 10 tonne/hr (0 d.p.) These figures can be marked up on the flowsheet or if necessary due to the quantity of data tabulated for ease of reference. Tank
1

1 = 23 tonne/hr

Capacity = 1000 tonne

2 = 10 tonne/hr

General Mass balance Equation is Material OUT = Material IN + Generation - Consumption Accumulation. This problem is clearly NOT steady state as there is an imbalance between the material entering and that leaving i.e. 1 = 23 tonne/hr 2 = 10 tonne/hr However, there is no obvious reaction so we can state Assume no reaction so Generation and Consumption = 0 thus reducing the general mass balance equation to Material OUT = Material IN Accumulation So substituting in the givens or 10 = 23 Accumulation Accumulation = 23-10 = 13 tonne/hr

The storage tank has a capacity of 1000 tonne and is initially half full giving an initial ullage (space left at the top of the tank) of 500 tonne. Time to fill tank, assuming given rates remain constant = 500/13 = 38 hrs (0 d.p.)

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EG2002: Process Engineering 10. Assignment 10.1 Reading

Rev 4H by JC on 06/10/2011

It is recommended that you take a look at Sinnott and Towler Chapter 2 and/or Felder and Rousseau Chapter 4 as early as possible within this series of lectures. You may well not understand much beyond the start of each reference at the moment but you can always revisit the relevant parts later and it will put you in a much stronger position to ask questions in lectures and answer tutorial questions. I will give more specific reading in later lectures. 10.2 Problems The following problems are quite simple and could easily be solved intuitively but as mentioned earlier, things get a lot more complex and so it is important to develop a methodology that works and stick with it. So in answering the following questions imagine ALL of the marks are for the method. Remember to include a marked up flowsheet, define your basis of calculation, write down your assumptions and solve the problem by application of the generalised mass balance equation. Try to attempt the question before the next lecture but if not make sure you attempt it and bring your efforts to the next tutorial for discussion and/or help as appropriate. 1. Sewerage flows into a primary treatment unit of a waste treatment facility from two sources. The first source is a continuous flow of 10 tonne/hr whilst the second is rather intermittent increasing linearly from 0 tonne/hr to 10 tonne/hr over a half hour period then reducing at the same rate over the next half hour. Perform a material balance over the primary treatment unit to determine the load on the secondary unit. Try this using both a differential and an integral approach (hint the key to solving this one is in the selection of a suitable basis). Which do you think is the most appropriate approach in this case and why? 2. According to Wikipedia Loch Ness has a total water capacity of 7.4 km3, as surface area of 56.4 km2 and a water catchment area of 1,775 km2. This had not been a particularly dry summer and the Loch is only 80% full so you remain concerned water maybe leaking away into a newly discovered system of underground caves. Your measurements indicate that the level is dropping at a worrying 1% per week. You estimate that water enters the river from at a rate of 1 litre per day for each m2 of catchment area and leaves via streams etc at a rate of 1000 tonne/hr. In addition you estimate that the loss due to evaporation is 1 litre per m2 of surface area. Carry out a mass balance in order to investigate the issue further and calculate any unexplained losses. Additionally you have been asked to consider what impact the large community of subsurface monsters drinking the water have on the situation? (Assume density of water = 1000 kg/m 3)

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