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DESIGN OF A 40,000 TONS CAPACITY MALEIC ANHYDRIDE PRODUCTION


PROCESS USING BENZENE AS FEEDSTOCK

Thesis · August 2017


DOI: 10.13140/RG.2.2.31284.55684

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TABLE OF CONTENTS
TABLE OF CONTENTS ............................................................................................................................... i
EXECUTIVE SUMMARY .......................................................................................................................... v
CHAPTER 1 ................................................................................................................................................. 1
INTRODUCTION ........................................................................................................................................ 1
1.1 PROJECT BACKGROUND............................................................................................................. 1
1.2 PROBLEM STATEMENT ............................................................................................................... 1
1.3 AIM AND OBJECTIVES ................................................................................................................. 1
1.4 SCOPE OF THE DESIGN PROJECT .............................................................................................. 2
CHAPTER 2 ................................................................................................................................................. 3
LITERATURE REVIEW ............................................................................................................................. 3
2.1 INTRODUCTION TO MALEIC ANHYDRIDE ............................................................................. 3
2.2 HISTORY OF MALEIC ANHYDRIDE PRODUCTION ............................................................... 4
2.3 DEMAND AND PRODUCTION OF MALEIC ANHYDRIDE ...................................................... 6
2.4 CONSUMPTION OF MALEIC ANHYDRIDE ............................................................................... 7
2.5 Availability and feasible process route to MAN production............................................................. 8
2.6 Economic study ................................................................................................................................. 9
2.7 Maleic Anhydride Production ......................................................................................................... 11
2.8 PROCESS CHEMISTRY FOR THE PRODUCTION OF MALEIC ANHYDRIDE .................... 13
2.9 EMISSIONS AND CONTROLS .................................................................................................... 15
CHAPTER 3 ............................................................................................................................................... 16
3.1 PROCESS DESCRIPTION ............................................................................................................ 16
3.2 DETAILED PROCESS DESIGN ................................................................................................... 20
THE CATALYST ....................................................................................................................................... 20
3.3 PROCESS DETAILS ...................................................................................................................... 20
PUMP (P-501) ............................................................................................................................................ 21
COMPRESSOR (C-501) ............................................................................................................................ 22
FIRED HEATER (H-501) .......................................................................................................................... 23
PLUG FLOW REACTOR .......................................................................................................................... 24
HEAT EXCHANGER (E-502) ................................................................................................................... 25
ABSORBER ............................................................................................................................................... 26
DISTILLATION COLUMN ....................................................................................................................... 27
CHAPTER 4 ............................................................................................................................................... 29

i
MATERIAL AND ENERGY BALANCE ................................................................................................. 29
MATERIAL BALANCE ............................................................................................................................ 29
ENERGY BALANCE ................................................................................................................................ 30
EQUIPMENT DESIGN .............................................................................................................................. 33
Reactor ........................................................................................................................................................ 33
Heat Exchanger Design............................................................................................................................... 35
Heater. ......................................................................................................................................................... 36
Fire Heater. ................................................................................................................................................. 36
Pump ........................................................................................................................................................... 37
Compressor ................................................................................................................................................. 37
Absorber...................................................................................................................................................... 38
Shortcut Distillation Column ...................................................................................................................... 38
CHAPTER 5 ............................................................................................................................................... 40
ECONOMIC ANALYSIS .......................................................................................................................... 40
THE PRICES OF PRODUCT .................................................................................................................... 40
PLANT SPECIFICATION ......................................................................................................................... 40
COST ESTIMATION ................................................................................................................................. 40
PROFITABILITY ANALYSIS .................................................................................................................. 42
CHAPTER 6 ............................................................................................................................................... 49
SAFETY ANALYSIS ................................................................................................................................. 49
REFERENCE.............................................................................................................................................. 54
APPENDIX ................................................................................................................................................. 55

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LIST OF TABLES AND FIGURES
LIST OF FIGURES
FIGURE DESCRIPTION PAGE
2.1 Structure of Maleic Anhydride 3
2.2 Demand and production capacity of Maleic Anhydride 7
2.3 World Consumption of Maleic Anhydride by end use in 2008 8
2.4 Block diagram for Maleic Anhydride plant configuration. 9
2.5 Global Consumption of Maleic Anhydride for Year 2015 10
3.1 Simulated process flow diagram for the maleic anhydride production 18
process from benzene feedstock using Aspen Hysys
3.2 Worksheet for the pump equipment (P-501) 21
3.3 Worksheet for compressor (C-501) 22
3.4 Worksheet for the fired heater equipment (H-501) 23
3.5 Worksheet for the plug flow reactor (R-501) 24
3.6 Worksheet for the heat exchanger (E-502) 25
3.7 Worksheet for the absorber (T-501) 26
3.8 Worksheet for the distillation column (T-502) 27
A1 Hysys simulation of the maleic anhydride production process using 55
benzene as feed stock.

iii
LIST OF TABLES
TABLE DESCRIPTION PAGE
2.1 Properties of Maleic Anhydride 4
2.2 Worldwide Maleic anhydride Production Capacity using butane and benzene 5
as feedstock.
2.3 Physical and Chemical properties of Maleic Anhydride 13
2.4 Composition of uncontrolled emissions from product recovery 15

3.1 Physical properties of catalyst. 19


4.1 Stream table for the maleic anhydride production process 28
4.2a Energy stream compositions 29
4.2b Energy balance for the various streams in the process. 30
4.3 Reactor specification table 31
4.4 Heat exchanger specification table 33
4.5 Heater specification table 34
4.6 Fire Heater specification table 34
4.7 Fire Heater specification table 35
4.9 Compressor specification table 35
4.10 Absorber specification table 36
4.11 Shortcut Distillation Column specification table 36
5.1 Plant specification 38
5.2 APEA result summary. 39
5.3 Unit operation cost analysis 40
5.4 Discounted cash inflow at 15% rate. 42
5.5 Discounted cash inflow at 18% rate. 43
5.6 Discounted cash inflow at 48% rate. 43
5.7 Discounted cash inflow at 54% rate. 44
5.8 Discounted cash inflow at 56% rate. 45
5.9 Concept Hazard Analysis Initial Review for MAN production plant 49

iv
EXECUTIVE SUMMARY
The aim of this project was to design a production plant capable of manufacturing 40,000
tons/year maleic anhydride from benzene feedstock. The process was simulated using Aspen
Hysys version 10. 93.4% conversion of benzene was achieved in the plug flow reactor. The
benzene feed requirement to produce 40,000 tons/year maleic anhydride was determined at 57.4
kmol/hr. The maleic anhydride produced had 99% purity. The economic evaluation of the
production process was carried out using the Aspen Process Economic Analyzer (APEA). From
the result, the calculated payback period (PBP) was approximately 2 years; the internal rate of
returns (IRR) for the project was 55%. The equivalent annual operating cost (EAOC) was also
evaluated to be -$77,549.17. The large negative value indicates that the project has a high profit
return. From the profitability analysis, it was concluded that the production of maleic anhydride
using the process conditions simulated is very feasible.

v
CHAPTER 1

INTRODUCTION

1.1 PROJECT BACKGROUND

Maleic anhydride is a chemical intermediate used in the production of unsaturated polyester


resins which have high structural strength and good dielectric properties. Maleic anhydride is
also used to produce surface coatings, lubricant additives and agricultural chemicals including
fumaric acid and succinic acid. The main feed stocks for the production of maleic anhydride in
the industry are benzene and normal butane. This projects purpose is to do a preliminary analysis
to determine the feasibility of constructing a chemical plant to manufacture 40,000 tons/year
maleic anhydride. The raw material selected is benzene. The project analyses a simplified maleic
anhydride production process, and suggest profitable operating conditions.

1.2 PROBLEM STATEMENT

Maleic anhydride was traditionally manufactured by the oxidation of benzene or other aromatic
compounds. As of 2006, only a few smaller plants continue to use benzene due to the rising
benzene price. Advances in catalyst technology, increased regulatory pressures, and continuing
cost advantages of butane over benzene have led to a rapid conversion of benzene to butane
based plants (Timothy et al., 2001). The advent of patents for the catalytic oxidation of benzene
coupled with improvements in the vanadium oxide catalysts was integral to the creation of a
commercially viable process for MAN (Guliants et al, 1999). A more simplified and profitable
maleic anhydride plant using benzene as feed stock is necessary to enable its continued use as
feedstock.

1.3 AIM AND OBJECTIVES

The aim of this project was to design a production plant capable of manufacturing 40,000
tons/year maleic anhydride from benzene.

This was achieved by the following specific objectives;

1
 Simulation of a maleic anhydride production process using aspen HYSYS version 10.
 Carrying out the material and energy balance calculations for the process.
 Designing the major process equipment of the process.
 Performing a detailed economic evaluation of the process plant using Aspen Process
Economics Analyzer.
 Analysis and suggestion of profitable operating conditions.

1.4 SCOPE OF THE DESIGN PROJECT

The scope of this work is restricted to the following:

 Collection of preliminary design data from literatures.


 Simulating the maleic anhydride production process using aspen HYSYS.
 Carrying out economic evaluation of the plant designed.

2
CHAPTER 2

LITERATURE REVIEW

2.1 INTRODUCTION TO MALEIC ANHYDRIDE

Maleic anhydride (MA) is the cis-butenedioic acid (maleic acid) anhydride, and is one of the
intermediate products with the highest expected demand for the next four years (Brandstädter
and KraushaarCzarnetzki, 2005; Cortelli, 2006; Gascón et al., 2005). Maleic anhydride occurs as
colourless or white crystalline flakes with strong acrid (pungent) odour. MA is toxic and an
irritant to the skin and mucous membranes leading to burning and ulceration. Other names for
maleic anhydride are 2,5-furandione, dihydro-2,5-dioxofuran, toxilic anhydride, or
cisbutenedioic anhydride (Sajjad, 2016). The structural formula for maleic anhydride is given
below.

Figure 2.1: Structure of Maleic Anhydride (source: Sajjad, 2016)

It is considered an excellent joining and cross linking agent due to its three active sites (one
double bond and two carboxyl groups). Besides that, due to its cross linking abilities, it is widely
used in the manufacturing of unsaturated polyester resins. Maleic anhydride is used as a
chemical intermediate in the synthesis of fumaric and tartaric acid, certain agricultural chemicals,
resins in numerous products, dye intermediates, and pharmaceuticals ((Timothy R. Felthouse,
2001).

3
Table 2.1: Properties of Maleic Anhydride

2.2 HISTORY OF MALEIC ANHYDRIDE PRODUCTION

Maleic anhydride was first synthesized in the 1830’s, but was not manufactured commercially
until about 1930. It was initially commercialized in the early 1930s through the selective
oxidation of benzene. Prior to 1930, MA was formed only in small quantities as a by-product of
the phthalic anhydride process. This can be converted to maleic anhydride. The use of benzene
as a feedstock for the production of maleic anhydride was dominant in the world market well
into the 1980s. However, the usage of benzene started to change and was replaced by n-butane in
1974 because of its toxic effects and economic aspects. Several processes have been used for the
production of maleic anhydride from benzene with the most common one from Scientific
Design. The advent of patents for the catalytic oxidation of benzene coupled with improvements

4
in the vanadium oxide catalysts was integral to the creation of a commercially viable process for
MA (Amanda Lee, 1991).

Initially, maleic anhydride was produced by the partial oxidation of benzene using a vanadium
oxide catalyst. Rapid increases in the price of benzene and the recognition of benzene as a
hazardous material strictly regulated by the EPA and OSHA, efforts to find a suitable
replacement have been pursued. These factors led to the first commercial production of maleic
anhydride from butane at Monsanto's J. F. Queeny plant in 1974. In 1983, Monsanto started up
the world's first butane to maleic anhydride plant, incorporating an energy efficient solvent-based
product collection and refining system. This plant was the world's largest maleic anhydride
production facility in 1983 at 59,000t/yr capacity. Advances in catalyst technology, increased
regulatory pressures, and continuing cost advantages of butane over benzene have led to a rapid
conversion of benzene to butane based plants. By the mid-1980s in the United States 100% of
maleic anhydride production used butane as the feedstock. Over the years, n-butane has been
utilized with increasingly successful results and is gradually overtaking benzene as the reactant
of choice (Timothy et al., 2001).

Meanwhile, Europe has also converted from benzene-based to butane-based maleic anhydride
technology starting from the construction of new butane based facilities by CONDEA-
Hunstman, Pantochim and Lonza. The growth in the industry turned to the butane-to-maleic
anhydride route, usually at the expense of benzene-based production. Table 2.2 below shows the
worldwide maleic production capacity broken down into fixed-bed benzene, fixed-bed butane,
fluidized-bed butane, and phthalic anhydride (PA) co-product.

5
Table 2.2: Worldwide Maleic anhydride Production Capacity using butane and benzene as
feedstock

It can be seen from the table that both fixed-bed and fluidized-bed butane routes have increased
dramatically with the fixed-bed route adding 336 kiloton/year capacity compared to 90
kiloton/year for the fluid-bed process. Only a few newer benzene-based fixed-bed processes have
been built with a difference of 63 kiloton/year since the early1980s and the reason it was built
was due to limited resource of butane (Timothy et al., 2001).

2.3 DEMAND AND PRODUCTION OF MALEIC ANHYDRIDE

Maleic anhydride has become the third biggest acid anhydride only next to phthalic anhydride
and acetic anhydride and its application sector is constantly expanding. Since 14 the construction
of the first maleic anhydride unit using the fluidized bed n-butane process by BP in 1988, the
process has made a rapid development due to its great advantage and development potential and
become the main trend in the development of maleic anhydride production processes. Maleic
anhydride world demand primarily depends on unsaturated polyester resins (UPR) production,
lube oil adhesives synthesis and maleic and fumaric acids formation. (Nexant ChemSystems,
2005). Global demand of maleic anhydride in 2008 approximately 1.7 million metric tons while
production capacity is about 1359000 tone/year. Maleic anhydride demand is expected to grow
an average 5.7% per year from 2008 to 2013, then slow to around 2.5% per year from 2013 to
2016 (Sajjad, 2016). The constant demand increase in 1, 4-butanediol and tetrahydrofuran in
recent years has led to a stable demand increase of maleic anhydride in the world. European MA
demand is typically lower than the U.S., at 2.5%-3%/year. European and North American market

6
conditions are balanced, while Asia is long (Sri Consulting, 2009). The graph below shows
global demand and production capacity of MA.

Figure 2.2: Demand and production capacity of Maleic Anhydride (Sri Consulting, 2009)

2.4 CONSUMPTION OF MALEIC ANHYDRIDE

About 51% of global maleic anhydride consumption in 2008 was for the production of
unsaturated polyester resins (UPR), followed by 1,4-butanediol with around 13% of total
consumption. Other applications for maleic anhydride include agricultural chemicals, maleic
acid, fumaric acid, lube oil additives, maleic anhydride-based copolymers, alkenyl succinic
anhydrides, reactive plasticizers, sulfosuccinic acid esters, and a number of other specialty
chemicals and organic intermediates (Sajjad, 2016). The pie chart below shows world
consumption of Maleic Anhydride by end use in year 2008.

7
Figure 2.3: World Consumption of Maleic Anhydride by end use in 2008 (Sri Consulting, 2009).

Unsaturated polyester resins will continue to have the largest market share and will drive refined
maleic anhydride consumption on a global scale.

2.5 Availability and feasible process route to MAN production

Maleic anhydride is a very versatile molecule that lends itself to many applications requiring a
number of properties and functionalities. With three active sites (two carboxyl groups and one
double bond), it is an excellent joining and cross linking agent. Its major end use, representing
well over half of global demand, is in the manufacturing of unsaturated polyester resins where its
cross-linking abilities are important. Maleic anhydride is an important intermediate in the fine
chemical industries particularly in the manufacturing of agricultural chemicals and lubricating oil
additives. It is also a component of several copolymers in the engineering polymer sectors.

Two main type of feedstock have been used for commercial maleic anhydride production:
benzene and n-butane. Irrespective of the raw material, the oxidation technology and separation
technology for both feedstock is usually almost the same. A simple block diagram of the
production process is shown below;

8
Feed Preparation

Oxidation Reaction

Crude Maleic Anhydride Energy Recovery


Recovery

Crude Maleic Anhydride


Purification

Figure 2.4: Block diagram for Maleic Anhydride plant configuration.

2.6 Economic study

In most regions of the world, the largest market for maleic anhydride is unsaturated polyester
resins. Demand for unsaturated polyester resins is influenced by the health of the construction
industry and overall state of the economy.

In recent years, demand for maleic anhydride has been growing at modest rates in North America
and Europe, but more vigorously in the Middle East and Southeast Asia. In China, growth has
slowed after years of strong increases. The largest market for maleic anhydride is unsaturated
polyester resins, which accounts for 60% of the total production of maleic anhydride, where
China controls most of the world production of about 40%

The following pie chart shows the world consumption of maleic anhydride;

9
Figure 2.5: Global Consumption of Maleic Anhydride for Year 2015.

Unsaturated polyester resin production will continue to have the largest market share and will
drive refined maleic anhydride consumption on a global scale. The developing regions will
experience the highest growth in maleic anhydride for unsaturated polyester resin production
because a considerable amount of unsaturated polyester resin goes into infrastructure. Overall
economic health will affect the unsaturated polyester resin market because it is tied to the
construction, automotive, and marine industries.

Global producers of maleic anhydride are numerous, and even the largest producer, Huntsman,
accounts for only a little more than 7% of the world market. However, the company has the
largest share of the combined United States and Western European market, with about 35% of
the total. There are many producers in China, most with relatively small capacities.

Overall, maleic anhydride is expected to grow by modest rates in most of the world. Several new
markets show some potential for above-average growth, but from small bases:

 Use of More Environmentally Friendly Materials: Maleic anhydride compatibilizers can


be used to modify polyolefin like polypropylene or polyethylene to improve adhesion and
dispersion to natural fibers for better strength for construction or automotive applications.

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 Use with Bio Feedstock-Based Polymers: Maleic anhydride can be used with polylactic
acid or other bio feedstock-based polymers to improve properties for use in agriculture,
automotive, or packaging applications.
 Increase Rates of Recycling: Maleic anhydride is used to make compatibilizers that
facilitate the mixing of dissimilar materials, including plastics.

Regionally, smaller end-use applications will experience higher-than-average growth, such as


maleic copolymers in the United States. New product development driven by increasing the use
of renewable or replacing one petroleum-based chemical with a more environmentally friendly
one will drive maleic anhydride consumption in this application. The use of maleic anhydride
and maleic anhydride copolymers will stand to gain from the increasing importance of
recyclability, biodegradability and the use of more sustainable chemicals (Greiner, E., et al.
2002).

However, world demand for maleic anhydride in the last five years is growing rapid at an annual
growth rate of 7.3%. The average annual growth in North American demand for maleic
anhydride rate of is 4%, while demand in Western Europe and Japan are 12% and 6.5%
respectively.

2.7 Maleic Anhydride Production

MA can be produced either by selective oxidation of n-butane or by selective oxidation of


benzene. The reactor technology involves both fixed-bed and fluidized bed configurations,
moreover it has been also developed a circulating fluidized bed, as discussed below. For the
selective oxidation of benzene, that is the older process developed for MA production, the
reactor technology is a fixed bed configuration: the reaction occurs in the gas phase, at 400-
450°C, in a multi tubular plug flow reactor. Catalyst (essentially a V/Mo mixed oxide) is
deposed on an inert and high-conductive support (i.e. steatite) to permit a better heat removal,
coming from the selective reaction but also from undesired reactions (total combustion of
benzene and products). At these conditions, benzene conversion is almost total (about 96%) and
MA selectivity can reach 73%. Due to environmental regulations (limit emission in the
atmosphere of 5µg/m3) (Decreto Ministeriale, 2012), the small quantity of unreacted benzene

11
must be treated: adsorbed and recycled, or burned. The quantity of heat generated for this
reaction is about -447 kcal/mol of benzene.

C 6 H 6(g) + 4.5O 2(g) 


K1
 C 4 H 2 O 3(g) + 2CO 2(g) + 2 H 2 O(g)
Benzene MAN

In the case of Polynt’s process, the so-called High-Load-Technology is used, which allows
operation up to 210 g/h/tube (2% mol. concentration) of benzene. The reaction gases are cooled
down by means of gas coolers and crude MA is partially recovered by condensation and partially
as maleic acid solution, in a water scrubber. Off gases leaving the scrubber, are sent to a catalytic
incinerator. Pure MA is obtained in a distillation column operated batch wise (www.polnt.com).

Around 1970, the possibility of using n-Butane as a feedstock in MAN production instead of
benzene became popular. The catalyst is vanadium phosphorus oxide with a heat generation of
about -300kcal/mol for butane reaction. The reaction employs both fixed or fluidize bed
configurations, with a conversion which varies from 53 to 65% and MAN selectivity that doesn’t
exceed 86% (Esama, 2012).

C4H10 + 3.5O2 C4H2O3

The use of n-butane instead of benzene involves many advantages:

 Lower cost of the reactant: n-butane is present in natural gas and also produced by steam
cracking of oil.
 Better safety and lower environmental impact: benzene is a proven carcinogenic
compound.
 Better atom economy (“E factor”, ratio of waste mass per unit of product): for benzene
oxidation two of the six C atoms are transformed to CO2.
 Lower costs of MA separation and purification: starting from benzene some heavy
compounds (such as benzoquinone and phthalic anhydride) form as by-products.

12
Nowadays, approximately 80% of MA is produced from n-butane, the remaining 20% is
produced starting from benzene (Tecnon Orbichem): only a few smaller plants in Asia, Europe
and in the U.S. A continue to use benzene, due to rising and volatile benzene prices (Dummer et
al, 2011).

2.8 PROCESS CHEMISTRY FOR THE PRODUCTION OF MALEIC ANHYDRIDE

Chemically, Maleic-Anhydride has been understood to be 2,5 furandione or cis butane-dioic


anhydride. It is sometimes referred to as toxillic anhydride, malic acid anhydride or Malic
anhydride. It is a white crystalline solid and forms orthorhombic crystalline needles (Trivedi et.
Al., 2009).

Maleic anhydride can be produced either by vapor phase oxidation of n-butane or from benzene.
The commendable change is that the overall process converts the methyl groups to carboxylate
while the backbone is dehydrogenated. Small amounts of Maleic anhydride are also produced as
a by-product during the production of phthalic anhydride. It is a solid at room temperature but a
liquid or gas during its synthesis (McKetta, J.J. 1985).

Table 2.3: Physical and Chemical properties of Maleic Anhydride (McKetta, J.J. 1985)

Property Maleic Anhydride


Formula C4H2O3
Formula Weight, g 98.06
Melting Point, oC 52.85
Boiling Point, oC 202
Heat of formation, kj/mol -470.41
Heat of combustion, kj/mol -1389.5
Heat capacity, K mol
Solid 0.1199
Liquid 0.164
Heat of sublimation, Kj/mol 71.5

13
Heat of Vaporization, Kj/mol 54.8
Heat of fusion, Kj/mol 13.55
Heat of hydrolysis, Kj/mol 34.9

The chemistry of in the production of Maleic anhydride from benzene explains that, benzene is
being fed into a stream of hot air, and the mixture is passed through a catalyst bed at high
temperature. Vanadium pentoxide and molybdenum trioxide are the catalysts used for the
process. The ratio of air to hydrocarbon should be controlled in order to prevent the mixture from
igniting, as any ignition within the system is hazardous (S. Danshefsky. Et.al., 1983).

Anhydrides are compounds that have two acyl groups attached to oxygen. They can be cyclic in
the form of maleic anhydride or not in the form of acetic anhydride.

Anhydrides are derivatives of carboxylic acids and all derivatives of carboxylic acids can be
converted to the corresponding acid through reaction with water. Whenever a cyclic anhydride,
such as maleic anhydride, is the dienophile in a Diels-Alder reaction, the product is also an
anhydride. But whenever it is hydrolysed, It hydrolyzes, producing maleic acid, cis-HOOC–
CH=CH–COOH. With alcohols, the half-ester is generated, e.g., cis-HOOC–CH=CH–COOCH3 .
Thus due to its instability as an anhydride, its being stored as an acid, and exposed to distillation
when needed in the form of anhydride.

Maleic anhydride is produced by the controlled air oxidation of benzene, illustrated by the
following chemical reaction:

14
Within the process aporized benzene and air are mixed and heated before entering the tubular
reactor. Inside the reactor, the benzene/air mixture is reacted in the presence of a catalyst that
contains approximately 70 percent vanadium pentoxide (V2O5), with usually 25 - 30 percent
molybdenum trioxide (MoO3), forming a vapor of MA, water, and carbon dioxide. The vapor,
which may also contain oxygen, nitrogen, carbon monoxide, benzene, maleic acid,
formaldehyde, formic acid, and other compounds from side reactions, leaves the reactor and is
cooled and partially condensed so that about 40 percent of the MA is recovered in a crude liquid
state (B. Dmuchovsky et.al., 1967).

The effluent is then passed through a separator that directs the liquid to storage and the
remaining vapor to the product recovery absorber. The absorber contacts the vapor with water,
producing a liquid of about 40 percent maleic acid. The 40 percent mixture is converted to MA,
usually by azeotropic distillation with xylene. Some processes may use a double-effect vacuum
evaporator at this point. The effluent then flows to the xylene stripping column where the xylene
is extracted. This MA is then combined in storage with that from the separator. The molten
product is aged to allow color-forming impurities to polymerize. These are then removed in a
fractionation column, leaving the finished product. MA product is usually stored in liquid form,
as acids although it is sometimes flaked and pelletized into briquettes and bagged (J. F. Lawson,
1978)

2.9 EMISSIONS AND CONTROLS

Nearly all emissions from MA production are from the main process vent of the product
recovery absorber, the largest vent in the process. The predominant pollutant is unreacted
benzene, ranging from 3 to 10 percent of the total benzene feed. The composition of uncontrolled
emissions from the product recovery absorber is presented.
Table 2.4: Composition of uncontrolled emissions from product recovery absorber (J. F. Lawson,
1978)

S/n Components Wt%


1. Nitrogen 73.37
2. Oxygen 16.67

15
3. Water 4.00
4. Carbon dioxide 3.33
5. Carbon monoxide 2.33
6. Benzene 0.33
7. Formaldehyde 0.05
8. Maleic acid 0.01
9. Formic Acid 0.01

CHAPTER 3

3.1 PROCESS DESCRIPTION

Maleic anhydride is produced by the controlled air oxidation of benzene, illustrated by the
following chemical reaction:

Main Reaction:

C6H6 (g) + 4.5O2 (g) C4H2O3 (g) + 2CO2 (g) + 2H2O (g) (1)
Benzene Maleic Anhydride
Side Reactions:

C6H6 (g) + 7.5O2 (g) 6CO2 (g) + 3H20(g) (2)


Benzene
C4H2O3 (g) + 3O2 (g) 4CO2(g) + H2O(g) (3)
Maleic Anhydride
C6H6(g) + 1.5O2(g) C6H4O2(g) + H2O(g) (4)
Benzene Quinone

Where

−ri = kiCbenzene or − r3 = k3Cmaleic anhydride (5)

And

16
k1 = 7.7 ×10 exp (−25,143/ RT) (6)

k2 = 6.31×10 exp (−29,850 / RT) (7)

k3 = 2.33×10 exp (−21,429 / RT) (8)

k4 = 7.20×10 exp (−27,149 / RT) (9)

Vaporized benzene and air are mixed and heated before entering the plug flow reactor. Inside the
reactor, the benzene/air mixture is reacted in the presence of a catalyst that contains
approximately 70 percent vanadium pentoxide (V2O5), with usually 25 to 30 percent
molybdenum trioxide (MoO3), forming a vapor of MA, water, and carbon dioxide. The vapor,
which also contained oxygen, nitrogen, benzene, maleic acid, from side reactions, leaves the
reactor and is cooled and partially condensed so that about 40 percent of the MA is recovered in
a crude liquid state. The effluent is then passed through an absorber where it is contacted with
the solvent dibutyl phthalate. About 99% of the maleic anhydride in the reactor effluent stream is
absorbed in the dibutyl phthalate solvent and the mixture is separated in a distillation column.
The column runs at 1atm and about 99% dibutyl phthalate is recovered in the bottom section.
This is then recycled to the absorber. The top product from the distillation column contains about
99% maleic anhydride which is recovered in a crude liquid form.

The inlet reaction temperature was at 380°C which agrees with the typical reaction inlet
temperature of 350°C to 400°C. The catalyst is placed in 25 mm diameter tubes that are 3.2 m
long. The catalyst pellet diameter is 5 mm. The maximum temperature that the catalyst can be
exposed to without causing irreversible damage (sintering) is 650°C.

The model maleic anhydride plant, as described in this section, has a benzene-to-maleic
anhydride conversion rate of 93.2 percent, a capacity of 40,000 tons of maleic anhydride
produced per year, and runs for 8000 hours per year.

17
18
Figure 3.1: Simulated process flow diagram for the maleic anhydride production process from benzene feedstock using Aspen Hysys.

19
3.2 DETAILED PROCESS DESIGN

ASPEN HYSYS was used to model and simulate the maleic anhydride production process. The
fluid package was chosen to be NTRL which works well for ideal gaseous systems.

THE CATALYST
The catalyst contains approximately 70 percent vanadium pentoxide (V2O5), with usually 25 to
30 percent molybdenum trioxide (MoO3) on an inert support. The maximum temperature that the
catalyst can be exposed to without causing irreversible damage (sintering) is 650°C. The catalyst
diameter is 5 mm, and the void fraction of the bed is 0.5 (Felder et al., 2000). The table below
shows the physical properties of the catalyst.

Table 3.1: physical properties of catalyst. (Source: Aspen Hysys)

CATALYST DATA

Particle Diameter 5.000e-003 m

Particle Sphericity 0.800

Solid Density 2500kg/m3

Bulk Density 1250kg/m3

Solid Heat Capacity 250.00kj/kg-C

3.3 PROCESS DETAILS

Feed Stream and Effluent Streams

Stream 1: Benzene – stored as a liquid and a pump is used to simulate the increment in pressure
to the desired pressure of the reaction.

20
Stream 2: Air or “pure” oxygen – fed in at 200% excess based on maleic anhydride formation
reaction.

Stream 9: This stream contains dibutyl phthalate solvent which is a make-up stream for amount
lost in Streams 11 and 14 and recycled dibutyl phthalate recovered from the distillation process.
The stream also contains some maleic anhydride lost in the distillation column.

Stream 11: Waste gas – contains unreacted benzene and O2, N2, CO2, and H2O, plus some
dibutyl phthalate lost during the absorption process.

Stream 14: This stream contains Maleic anhydride product along with Quinone byproduct.

PROCESS EQUIPMENTS

PUMP (P-501)
The pump is used to increase the pressure of the liquid benzene feed from atmospheric pressure
to the inlet reaction pressure. This was added to the equipment design to account for the pressure
drop within the reactor vessel. If the inlet reactor stream pressure is below atmospheric pressure,
pressure drop within the reactor will cause shrinkage and lead to possibly catastrophic events.
The figure below shows the worksheet window in hysys. Input stream to the pump is benzene
and only the pressure is increased as shown below. The energy requirement was calculated by
hysys solver based on the delta P specified in the design.

21
Figure 3.2: Worksheet for the pump equipment (P-501)

COMPRESSOR (C-501)
The compressor is used to increase the air feed pressure to the inlet reactor pressure
specification. A centrifugal compressor was used and the adiabatic efficiency was set at 80%.
The energy requirement of the compressor was calculated by the hysys solver.

22
Figure 3.3: Worksheet for compressor (C-501)

FIRED HEATER (H-501)


The benzene and air feed mixture is heated here with natural gas as the fuel for heating. The
natural gas composition specified for the simulation were ethane and propane with compositions
of 0.97 and 0.03 respectively. Increasing the flowrate of the natural gas increased the benzene/air
mixture stream to the inlet reactor stream temperature. The efficiency of the fired heater was set
at 80%.

23
Figure 3.4: Worksheet for the fired heater equipment (H-501)

PLUG FLOW REACTOR


This is where the reactions in Equations 1-4 occur. There reactor configuration chosen is an
adiabatic reactor, in which there is no heat removal. The reaction begins to occur at about 388oC.
The heat generated by the reaction raises the temperature of the exit stream. However, the
temperature constraint described for the catalyst could not be modelled because cooling inside
the reactor could not be simulated. Typical outlet temperature in such conditions is about 1000 –
1700oC which is above the catalyst deactivation temperature of 650oC.

From the simulation, it was observed that increase in flowrate of the natural gas in the fired
heater increases the temperature of the inlet stream. The percentage conversion of benzene is a
function of the reaction kinetic data. At the specified data provided, 93.2% benzene conversion
to maleic anhydride was realized. This is in coherence with standard literature data of about 90-
95% conversion in the reactor. The reaction in equation 1, 2, and 4 occurs in the reactor with the

24
remaining benzene being converted to combustion product. The reaction conditions minimized
the conversion of maleic anhydride to combustion products. Thus the reaction in equation 3 had
negligible conversion rate.

Figure 3.5: Worksheet for the plug flow reactor (R-501)

HEAT EXCHANGER (E-502)


The heat exchanger is used to cool the reactor effluent stream from 1335oC to 54.30oC by
passing cooling water through the tube side and the process stream through the shell side. The
cooling water entered the condenser at 30oC room temperature and 101.4kpa atmospheric
pressure. The mass flowrate of the cooling water was set by heuristic method based on the
temperature decrease desired. The process fluid condensed to liquid after passing through the
heat exchanger.

25
Figure 3.6: Worksheet for the heat exchanger (E-502)

ABSORBER
The absorber runs at 82kpa and 56°C (outlet streams and Stream 8). In the absorber, 99% of the
maleic anhydride in Stream 8 is absorbed into the solvent dibutyl phthalate. The condensed
stream 8 enters from the bottom of the column while dibutyl phthalate enters from the top.
Number of trays was determined by heuristic method using 12 trays as starting point based on
number of trays used by (Sajjad, 2014). The number of trays for the column was determined to
be 14 trays. Stream 11 from the absorber contains, nitrogen, carbon dioxide, oxygen, water and
the 1% maleic anhydride lost. This stream is considered a waste gas stream. Stream 12 contains
absorbed maleic anhydride, dibutyl phthalate and quinone. The formation of maleic acid during
the absorption process could not be simulated however as the addition of the maleic acid
formation reaction to the absorber column was not possible. Also the maleic acid formation
reaction set could not be added to a reactor which was added after the absorber to account for the
maleic anhydride formed. Overall, the maleic anhydride condensation to maleic acid during the
absorption process could not be simulated.

26
Figure 3.7: Worksheet for the absorber (T-501)

DISTILLATION COLUMN
A shortcut column was used to simulate the distillation column. This is because it allows the use
of less information to calculate and solve the column. This column runs at 1 atm. Separation of
maleic anhydride and dibutyl phthalate occurs in this column. Of the maleic anhydride in Stream
12, 99% enters Stream 14. Similarly, 99% of dibutyl phthalate in Stream 12 enters Stream 13.
Stream 13 is recycled back to the absorber. To stop the error of minimum reflux ratio less than
zero encountered during simulation in the column, a separator was inserted before the column to
remove water from stream 12.

27
Figure 3.8: Worksheet for the distillation column (T-502)

28
CHAPTER 4

MATERIAL AND ENERGY BALANCE

MATERIAL BALANCE
Desired production rate: 40,000 tons / year maleic anhydride.

Reactor condition: 93.5% conversion and temperature of 379oC.

Reactor Yield: 63% (0.63 kmols maleic anhydride per kmol of benzene feed reacted)

Feed to Reactor: 54.79 kmols benzene and 3280 kmols air in 200% excess is fed into the reactor.

Reactor Type: Plug flow reactor with fixed bed catalytic packing.

Table 4.1 gives the stream requirements for the production of 40,000 tons / year maleic
anhydride.

Table 4.1: stream table for the maleic anhydride production process

benzen
Stream number Unit e 1 3 air 4 5 6
30.176 120.27 139.95 138.55
Temperature C 30 4 6 30 1 1 371.19
6.9912 17.264
Pressure bar 1.014 3.014 3.014 9 5 3.014 3.014
3378.7 3378.7
Molar Flow kmol/h
54.79 54.79 54.79 3324 3324 9 9
4435.8 4435.8 4435.8 80780. 80780. 85216. 85216.
Mass Flow kg/h 7 7 7 8 8 6 6
Components Flowrate (kmol/hr)
Benzene 54.79 54.79 54.79 0 0 54.79 54.79
Oxygen 0 0 0 698.04 698.04 698.04 698.04
MaleicAnhydrid
e 0 0 0 0 0 0 0
MaleicAcid 0 0 0 0 0 0 0
CO2 0 0 0 0 0 0 0
H2O 0 0 0 0 0 0 0
2625.9 2625.9 2625.9 2625.9
Nitrogen 0 0 0 6 6 6 6
Quinone 0 0 0 0 0 0 0
DinC4Phthate 0 0 0 0 0 0 0

29
Table 4.1 continued.

Stream
number Unit 7 8 9 11 12 13 14
Temperature C 1511.03 36.8087 339.907 90.228 32.8367 173.775 339.907
Pressure bar 1.63505 1.32275 1.013 0.82 0.82 1.013 1.013
Molar Flow kgmole/h 3374.87 3374.87 23.6531 3339.24 132.983 109.418 23.5658
Mass Flow kg/h 85216.5 85216.5 6583.78 79524.6 12275.6 5716.14 6559.5
Components Flowrate (kmol/hr)
Benzene 1.3E-07 0 0 0 0 0 0
Oxygen 388.698 359.582 0 370.038 0.00075 0.00075 0
Maleic
Anhydride 55.6251 55.6251 0 0 46.7829 46.7829 1.9E-14
Maleic Acid 0 0 0 0 0 0 0
CO2 198.395 182.642 0 187.939 0.01126 0.01126 0
H2O 130.509 146.946 0 74.5994 62.6193 62.6193 0
Nitrogen 2625.96 2630.08 0 2706.56 0.00324 0.00324 0
Quinone 2.54926 3.4E-05 0 0 2.8E-05 2.8E-05 0
DinC4Phthate 0 0 23.6531 0.10675 23.5658 1.1E-10 23.5658

Most of the data have been calculated by hysys solver in the simulator, however Appendix 1
shows calculations of feed and material stream flowrates specified in the simulator.

ENERGY BALANCE
The tables below shows a summary of the energy streams heat requirement and energy balance
for the various streams of the maleic anhydride production process.

Table 4.2a: energy stream compositions

Stream Heat Flow


Name kcal/h

E1 2172247.314

Lps 566762.2828

30
P1 305.7845453

Q20 -403675.967

Q21 2916721.858

31
Table 4.2b: Energy balance for the various streams in the process.

Units benzene 1 3 air 4 5 ng air2 poc

Mass Enthalpy [kcal/kg] 154.2 154.3 282.041 1.208 28.23 39.076 -1087 1.208 -497

Mass Entropy [kJ/kg-C] -1.556 -1.439 4.40E-02 6.606 6.662 6.4038 10.57 4.529 9.18

Heat Capacity [kJ/kgmole-


C] 127.67 127.7 110.296 29.18 29.87 31.248 36.72 29.18 39.31

Mass Heat Capacity [kJ/kg-


C] 1.6346 1.635 1.41206 1.011 1.035 1.0539 2.226 1.011 1.421

Units 6 7 cw hw 8 9 11 12 13 14

Mass Enthalpy [kcal/kg] 104.04 104 -3774.7 -3722 -259 -735.4 -232 -881 -1359 -568.6

Mass Entropy [kJ/kg-C] 6.9182 8.224 0.43424 1.107 6.436 1.5658 6.66 0.324 0.99 3.2713

Heat Capacity [kJ/kgmole-


C] 33.553 33.48 76.0962 74.38 31.63 389.25 31.2 256.1 82.16 661.69

Mass Heat Capacity [kJ/kg-


C] 1.1317 1.126 4.22402 4.129 1.063 2.1149 1.051 1.694 1.573 2.3772

32
EQUIPMENT DESIGN

Reactor
The reaction set and kinetics are installed in the plug flow reactor. The calculated volume is set
at 0.024m and the maximum reactor temperature is 1800oC. The table 3.4 below show the
specification data sheet for designing the plug flow reactor.

Table 4.3: Reactor specification table

Plug Flow Reactor


Name R-501
Pressure Drop [bar] 1.378951817
Reactor Volume [m3] 0.141
Tube Length [m] 14.35
Tube Diameter [m] 0.04
Void Volume [m3] 6.691278193
Particle Diameter [m] 0.005
Particle Sphericity 0.8
Solid Density [kg/m3] 2500
Solid Heat Capacity [kJ/kg-C] 250
Number of Tubes 1
Minimum Step Fraction 0.000001
Minimum Step Length [m] 0.00001475
Number of Segments 20
Wall Thickness [m] 0.005
Bulk Density [kg/m3] 1250

Determination of the volume of reactor:

FAO XA = (Moles of A fed / time) × (Moles of A reacted / Moles of A feed)


FAO – FAOXA = FA
FA = FAO (1 – XA)
FAO = CAOVO
But CAO = (PAO/RTO) = (YAOPO/RTO)
Recall the plug flow reactor equation

- (dFA/dV) = -rA

33
FA = FAO - FAOXA
dFA = -FAO dXA
- (dFA/dV) = FAO × dXA/dV = -rA

V = FAO∫

After integration, we have it that;

k‫ ( = ך‬1 + εA) in 1/(1- XA ) – (εAXA)

‫ = ך‬VCAO/FAO
On substituting and making V subject of the equation, we have;

V = FAO/ KCAO (1 + εA) In 1/(1- XA )

Where: P = 8.314 J/K/mol PAO = yAOPO = 8.86116KPa

T = 375.9oC
Po = 301.4KPa

yAO = 0.0294

CAO = (8.86116 × 103) = 1.642 mol / m3


8.314 × (375.9 + 273)
FAO = 54.79 Kmol/hr
Vo = 54.79 = 33367.84 m3 / hr
1.642 × 10-3
K= 747638 m3 gas/ m3 reactor
V = 33367.84 In (1/ 1-0.95) = 0.133703m3
747638

34
Heat Exchanger Design
The heat exchanger is used to cool the reactor effluent. The condenser configurations were
selected according to data specified by Sajjad (2014).

Table 4.4: Heat exchanger specification table

Heat Exchanger
Name E-502
Duty [kcal/h] 35698871
UA [kJ/C-h] 598359.6
Control UA [kJ/C-h] 598546.52
Tube Side Pressure Drop [bar] 0.79
Shell Side Pressure Drop [bar] 0.3123
Tube Side Delta T [C] 7.0847792
Shell Side Delta T [C] -1474.221
Uncorrected LMTD [C] 282.48971
LMTD [C] 249.54437
Ft Factor 0.8833751
Tube Side Zones 1
Shell Side Zones 1
Tube Side Volume [m3] 0.1
Shell Side Volume [m3] 0.1
Heat Trans. Area [m2] 60.318579
Minimum Flow Scale Factor 0
Shell side U [kJ/h-m2-C] 5842.8
Tube side U [kJ/h-m2-C] 43336.8
Overall U [kJ/h-m2-C] 9919.9883

35
Heater
Table 4.5: Heater specification table

Heater
Name E-501
Duty [kcal/h] 566762.28
Pressure Drop
[bar] 0

Fire Heater
Table 4.6: Fire Heater specification table

Fired Heater
Name FH-100
Number of Radiant Zone Streams 1
Number of Convective Zone Streams 0
Number of Economizer Zone Streams 0
Number of Radiant Zone Tubes 20
Ambient Temperature [C] 25
Oxygen Efficiency [%] 100
Tube Inner Area [m2] 21.225857
Tube Outer Area [m2] 24.258122
Tube Inner Volume [m3] 0.4717447
Shell Inner Diameter [m] 1.7
Shell Outer Diameter [m] 2
Zone Height [m] 4.28
Shell Inner Area [m2] 22.858228
Shell Outer Area [m2] 26.892033
Shell Net Volume [m3] 9.0985907
Shell Total Volume [m3] 9.714747

36
Pump
Table 4.7: Fire Heater specification table

Pump
Name P-501
Power [kW] 0.355389201
Delta P [bar] 2
Adiabatic Efficiency [%] 80
Duty [kW] 0.355389201
NPSH available [m] 10.10888401
Capacity [m3/h] 5.117604501
Delta T [C] 0.176415792
Pressure Head [m] 23.5286782
Velocity Head [m] 4.35069E-06
Transient Rotational Power [kW] 0
Friction Loss Power [kW] 0
Total Rotor Power [kW] 0.355389201

Compressor
Table 4.9: Compressor specification table

Compressor
Name C-501
Power [kW] 2524.6313
Capacity (act feed vol flow)
[ACT_m3/h] 10094.511
Adiabatic Efficiency 80
Polytropic Efficiency 82.3016
Compressor Volume [m3] 0
Delta T [C] 109.9506
Delta P [bar] 10.273191
Polytropic Head [m] 9442.3801
Adiabatic Head [m] 9178.2917
Dynamic Head [m] 9442.3801

37
Polytropic Fluid Head [kJ/kg] 92.598117
Adiabatic Fluid Head [kJ/kg] 90.008295
Dynamic Fluid Head [kJ/kg] 92.598117
Polytropic Head Factor 1.0004
Polytropic Exponent 1.5205388
Isentropic Exponent 1.3935261
PD Number of Cylinders 0
Transient Rotational Power [kW] 0
Friction Loss Power [kW] 0
Fluid Power [kW] 2524.6313
Duty [kcal/h] 2172247.3

Absorber
Table 4.10: Absorber specification table

Absorber
Name T-100
Number of Stage 16
Top Stage Temperature [C] 90.227989
Bottom Stage Temperature
[C] 32.836671
Top Stage Pressure [bar] 0.82
Bottom Stage Pressure [bar] 0.82
Reflux Flow/Total Liq Flow 0.0088815

Shortcut Distillation Column


Table 4.11: Shortcut Distillation Column specification table

Shortcut Distillation Column


Name T-101
Minimum Reflux 0.05029242
External Reflux 0.3
Minimum Trays 25.2818582
Actual Trays 48.3370411
Optimal Feed 0.00257094
Rectify Vapour Flow [kgmole/h] 142.242777

38
Rectify Liquid Flow [kgmole/h] 32.8252563
Stripping Vapour Flow [kgmole/h] 142.242777
Stripping Liquid Flow [kgmole/h] 165.808589
Light Key Mole Frac 1E-25
Heavy Key Mole Frac 1E-12
Condenser Pressure [bar] 1.013
Reboiler Pressure [bar] 1.013
Condenser Temperature [C] 173.774742
Reboiler Temperature [C] 339.90722
Condenser Duty [kcal/h] -403675.97
Reboiler Duty [kcal/h] 2916721.86

39
CHAPTER 5

ECONOMIC ANALYSIS

THE PRICES OF PRODUCT


The main product that produces from this plant is maleic anhydride. The price of maleic
Anhydride is $1.08/kg.

Molecular weight of maleic anhydride is 98 kg/kmol.

Price in cost per kilomoles becomes $1.08/kg x 98 kg/kmol = $105.84/kmol.

PLANT SPECIFICATION
Table 5.1: plant specification

Information Estimated Data


Plant life 10 years
Operating period 8000 hrs/year
Product price $105.84/kmol
Capital cost annuity interest factor 15%

COST ESTIMATION
For detailed sizing, costing, and economic evaluation including profitability analysis, the Aspen
Process Economic Analyzer was used.

Description of steps:

Step 1: Setting Up the Model for Process Economics

This step involves compiling all of the information that will be needed for this analysis and
creating a model that will be used for the economics analysis. While rigorous models are
recommended to reduce the number of assumptions that will be taken for equipment sizes,
existing process simulation models are usually the most time efficient start points. The startup
period, operating hours per year, operating life of the plant, the start of basic engineering, the

40
prices of raw materials needed for the process feed as well as any product information, costs of
the utilities were specified to run the economic analyzer in hysys.

Step 2: Mapping Unit Operations to Process Equipment

The APEA engine will automatically map the unit operations present in the process simulation to
constituent equipment according to the definitions within the economic template for the project.
A single unit operation can be mapped to one or multiple pieces of equipment. Examples: the
pump on the flowsheet was mapped to a pump equipment, while the distillation column was a
tower, a condenser, accumulator, reboiler and other equipment needed to make the distillation
column work properly.

Step 3: Sizing and Defining Process Equipment

The equipment sizing step is a crucial step in the cost analysis of a process model. Activated
Economics has an interactive sizing expert tool which automatically sizes unit operations based
on simplified routines to generate enough parameters to evaluate the cost of the item
successfully.

Step 4: Evaluating Cost and Investment Metrics

Once the mapping, equipment sizing and customization steps were complete, the cost engine
evaluates the cost of the process and its equipment. This delivered a final process capital and
utility cost along with a number of project investment metrics that can be used to compare
relative costs of process case alternatives.

RESULT OF COST ANALYSIS

The table below shows the summary of the result of the aspen plus economic analyzer (APEA).

Table 5.2: APEA result summary.

Summary
Total Capital Cost [USD] 5998280
Total Operating Cost [USD/Year] 4645885
Total Raw Materials Cost [USD/Year] 30268500
Total Product Sales [USD/Year] 35562240

41
Total Utilities Cost [USD/Year] 2304580
Desired Rate of Return [Percent/'Year] 50
Equipment Cost [USD] 5106700
Total Installed Cost [USD] 2862233

The next table shows a more detailed result of the equipment, installation and utility cost of all
the major unit operations in the process.

Table 5.3: unit operation cost analysis

Name Equipment Installed Cost Equipment Installed Utility Cost


Cost [USD] [USD] Weight [LBS] Weight [LBS] [USD/HR]
E-501 11100 65600 1500 9159 19.866468
R-501 3000000 250000 69000 105000 0
T-501 106600 298500 21900 48931 0
FH-501 95600 52300 0 0 0
P-501 4700 32200 200 3116 0.0434
RCY-1 0 0 0 0 0
E-502 65000 27533 1500 9159 15.56775
C-501 1823700 2136100 43400 98405 260.1675
M-501 0 0 0 0 0
TOTAL 5106700 2862233 137500 273770 295.645118

PROFITABILITY ANALYSIS
Profitability analysis was carried out based on a number of economic criteria such as payback
period, internal rate of return, and cash flow analysis. In addition, the following objective
function was used. It is the equivalent annual operating cost (EAOC), and is defined as

EAOC = − (product value – feed cost – other operating costs – capital cost annuity)

The capital cost annuity is defined as follows:

Capital cost annuity = FCI

42
where FCI is the installed cost of all equipment;

i is the interest rate;

and n is the plant life, in years.

For accounting purposes, i = 0.15 and n = 10.

Capital cost annuity = $2,862,233.00 x

Capital cost annuity = $2,862,233.00 x 0.19925

Capital cost annuity = $570305.83

PAY BACK PERIOD

For the analysis of the payback period, the following formula was used:

PBP =

Where II is initial investment and is assumed to be:

II = (Total Capital Cost + Equipment Cost + Total Installed Cost) x 5.

II = ($5998280 + $5106700 + $2862233) x 5

II = $13967212 x 5

II = $63,836,060.

Cash inflow = $35562240 (product cost per year) constant value annuity.

Therefore; PBP =

PBP = 1.79 years approx. 2 years.

INTERNAL RATES OF RETURNS (IRR)

Internal rate of return is gotten when the net present value of cash inflow is zero.

43
NPV = ∑PV - II

Where PV is present value of cash inflow and is evaluated as;

PV = ∑Cash inflow + PVIF.

Where PVIF is present value interest factor taken as;

PVIF =

Where i is 15% interest factor

And n is number of years, in this case 10 years.

Preparing the discounted cash inflow for a period of 10 years:

Table 5.4: Discounted cash inflow at 15% rate.

period
(n) cash inflow PVIF PV
1 35562240 0.8696 30924923.9
2 35562240 0.7561 26888609.7
3 35562240 0.6575 23382172.8
4 35562240 0.5717 20330932.6
5 35562240 0.4971 17677989.5
6 35562240 0.4323 15373556.4
7 35562240 0.3759 13367846
8 35562240 0.3269 11625296.3
9 35562240 0.2842 10106788.6
10 35562240 0.2471 8787429.5

∑PV = $178,465,545
NPV = $178,465,545 - $63,836,060
NPV = $114,629,485

44
Note that $114,629,485 is positive and very far away from zero. So we will take three steps
further i = 18%.
Discounting again with 18% interest rate.
Table 5.5: Discounted cash inflow at 18% rate.

period
(n) cash inflow PVIF PV
1 35562240 0.8475 30137491.5
2 35562240 0.7182 25540247.1
3 35562240 0.6086 21644277.2
4 35562240 0.5158 18342607.8
5 35562240 0.4371 15544582.9
6 35562240 0.3704 13173375.3
7 35562240 0.3139 11163877.4
8 35562240 0.266 9460913.03
9 35562240 0.2255 8017722.9
10 35562240 0.1911 6794680.43

∑PV = $159,819,775

NPV = $159,819,775 - $63,836,060


NPV = $95,983,715
Note that $95,983,715 is positive and very far away from zero. So we will take thirty steps
further i = 48%.
Discounting again with 48% interest rate.
Table 5.6: Discounted cash inflow at 48% rate.

period
(n) cash inflow PVIF PV
1 35562240 0.6757 24028540.5
2 35562240 0.4565 16235500.4
3 35562240 0.3085 10969932.7

45
4 35562240 0.2084 7412116.68
5 35562240 0.1408 5008186.94
6 35562240 0.0952 3383910.1
7 35562240 0.0643 2286425.74
8 35562240 0.0434 1544882.26
9 35562240 0.0294 1043839.36
10 35562240 0.0198 705296.867

∑PV = $72,618,631.5
NPV = $72,618,631.5 - $63,836,060
NPV = $8,782,571.5
Note that $8,782,571.5 is positive and still far away from zero. So we will take 6 steps further i =
54%.
Discounting again with 54% interest rate.
Table 5.7: Discounted cash inflow at 54% rate.

period
(n) cash inflow PVIF PV
1 35562240 0.6494 23092363.6
2 35562240 0.4217 14995041.3
3 35562240 0.2738 9737039.82
4 35562240 0.1778 6322753.13
5 35562240 0.1155 4105683.85
6 35562240 0.075 2666028.47
7 35562240 0.0487 1731187.32
8 35562240 0.0316 1124147.61
9 35562240 0.0205 729965.981
10 35562240 0.0133 474003.884

∑PV = $64,978,215
NPV = $64,978,215 - $63,836,060

46
NPV = $1,142,155.
Note that $1,142,155 is positive and still far away from zero. So we will take 2 steps further i =
56%.
Discounting again with 56% interest rate.
Table 5.8: Discounted cash inflow at 56% rate.

period cash
(n) inflow PVIF PV
1 35562240 0.641 22796307.7
2 35562240 0.4109 14613017.8
3 35562240 0.2634 9367319.07
4 35562240 0.1689 6004691.71
5 35562240 0.1082 3849161.35
6 35562240 0.0694 2467411.12
7 35562240 0.0445 1581673.8
8 35562240 0.0285 1013893.46
9 35562240 0.0183 649931.705
10 35562240 0.0117 416622.888

∑PV = $62,760,030.6
NPV = $62,760,030.6 - $63,836,060
NPV = -$1,076,029.4
Interpolating between i = 54% and i = 56% on PVIF,
54 $1,142,155.
X 0
56 -$1,076,029.4
Where x is unknown IRR.

X = 56 – 0.97

47
X = 55.03% which is approx. 55%. Therefore, the internal rate of return is 55%.

EQUIVALENT ANNUAL OPERATING COST (EAOC)

EAOC = − (product value – feed cost – other operating costs – capital cost annuity)

Capital cost annuity = $570,305.83

Operating costs = $4,645,885

Feed cost = $30,268,500

Product value = $35,562,240

EAOC = - (35562240 – 30268500 – 4645885 - 570305.83)

EAOC = -$77,549.17.

A negative value of EAOC means there is a profit. It is desirable to minimize EAOC.

From the profitability analysis, it can be concluded that it is economically feasible to produce
maleic anhydride using these process conditions.

48
CHAPTER 6

SAFETY ANALYSIS
ENVIRONMENTAL EFFECTS
Releases of maleic anhydride into the environment can result from the manufacture and use of
the chemical. Small amounts can be found in the emissions from this production process. There
are believed to be no natural sources of release to the environment. Besides that, maleic
anhydride is biodegrades in soil and water. When released into soil it can leach into groundwater;
it will not evaporate significantly from water. When released to air, maleic anhydride is expected
to exist in the aerosol phase with a short half-life; it can be broken down by reacting with ozone
and hydroxyl radicals. It is not expected to bio-accumulate. There is no significant global
environmental effects are considered likely.
However, excessive exposure to maleic anhydride may affect the digestive system, eye, kidney,
lung and skin. The Environment Agency aims to ensure that environmental exposures are too
low to cause such effects (Environment-agency.gov.uk 2009).

PLANT RISK ANALYSIS


Risk analysis is an analysis to determine the amount of exposure (Dosage) to a hazard that will
result in a negative effect and the degree of the effect
Risk = Hazard + Exposure (i.e. Dosage).
As such risk analysis is a very wide subject, stretching from financial investment analyses, to
analysis of continuing health hazards, insurance questions, as well as the problems of safety.
Even within the field of safety there is a wide variation in technique, depending on what to be
analysed.
Risk analysis is routinely applied for weapons systems, space systems, communications systems,
aircraft, road and transport, and bridge design as well as to process plant. The techniques
described here cover therefore just a small part of the total field of risk analysis. Apart from that,
accidents in chemical plants can be grouped into a few dominant causes:
a) Mechanical crushing, falls, dropped objects.
b) Traffic accidents.
c) Corrosive burns, from spray and splashes.
d) Leaks of toxic substances, causing poisoning.
49
e) Asphyxiation after tank entry.
f) Fire.
g) Explosions.
h) Major toxic releases.
Of these, the last three can give rise to major hazards with large consequences (Multiple fatalities
and major environmental incidents). Fires and explosions can at the same time be starting points
for major toxic and environmental accidents. While here the leakage and spills can lead to
ground pollution, groundwater pollution and sea area pollution (J.R. Taylor 1994).
Therefore, defining the scope of the analysis is important. It is easy to leave out important
contributors to risk, because of the choice of the method for analysis or because of the
preconceptions about what is most hazardous. A concept hazards analysis initial review
(CHAIR) and detailed concept hazard analysis initial review (CHA) can help to avoid these
problems which will be discussed later. Unfortunately any risk analysis is very dependent on the
assumptions made. If the situation changes, the analysis becomes invalid, and may serve only as
a false assurance. The CHAIR and CHA are based on the preliminary Process Flow Diagram
(PFD) for production of the maleic anhydride from benzene.

Concept Hazard Analysis Initial Review (CHAIR)


Concept Hazard Analysis Initial Review (CHAIR) is an early safety in wide use in the process
industries. It is often known as pre-HAZOP STUDY. In it is simplest form this merely involves
gathering a simple record of one or more meetings between appropriate specialists at which
various aspects of design and operation are discusses in a structured way. This record might
consist of a simple system description identifying the plant, plant items and process description.
Various keywords can then be used to stimulate an appropriate discussion topic which is
recorded together with actions and notes (Geoff Wells 1997).
The main reaction in the plug flow reactor involves the reaction of benzene and oxygen to
produce maleic anhydride:
Benzene + Oxygen → Maleic Anhydride + Carbon Dioxide + Water

C 6 H 6(g) + 4.5O 2(g) 


K1
 C 4 H 2 O 3(g) + 2CO 2(g) + 2 H 2 O(g)
The process is quite simple, so hazard analysis will be performed on the whole production plant.

50
Table 5.9: Concept Hazard Analysis Initial Review for MAN production plant (Sajjad, 2015)
Keyword Discussion Action/Recommendation
Flammable Benzene is extremely flammable Consider fire-fighting
and tends to self-ignite on release requirements
as a leak through flanges and
joints.
Fire Loss of integrity on reactor i) Evaluate length of flame
circuit likely to give rise to torch from pipe at various
fire. Escalation probable if torch locations.
fire impacts on other equipment ii) Action to de-pressure
or pipe rack. needs evaluation.
iii) Maintain oxygen-free
atmosphere at start-up and
shutdown.
Explosion An internal explosion could Nitrogen purge required at
occur if plant is not thoroughly start-up and shutdown.
purged at start-up.
Discharge The emission of material on Check if carbon monoxide
overpressure can be to and carbon dioxide are
atmosphere or to flare. environmentally friendly.
Reaction and over temperature The reaction of MAN production A temperature controller
is exothermic. As the production and cold water flow is
process for MAN continued will needed to maintain the
result in increased temperature temperature of reactor.
inside the reactor and also the Check mechanical design to
outlet temperature will be withstand maximum
increased. feasible temperature.
Overpressure Overpressure can occur due to Check relief requirements if
lack of demand for product or product off-spec or lack of

51
downstream blockage. Upstream demand. Consider venting
plant has slow response to reduce to atmosphere or fuel gas.
capacity. Hence need for venting Report back on relief valve
as well as process relief. decision.
Start-up of reactor It is necessary to provide heat to An extra heat exchanger
warm up the reactor during start- circuit is needed as start-up
up. Consider heat exchanger line for the reactor.
circuit for this purpose.
Toxics Chronic and acute effect for Delayed adverse effects
exposure of materials such as possible. Obtain medical
butane and carbon dioxide which assistance
are toxic by inhalation.
Utility problems: i) Process is disturbed and cause i) Open the bypass on air
i) Loss of air production capacity MAN to failure.
ii) Loss of cooling decrease. ii) Install back-up of the
iii) Loss of electricity ii) Process is disturbed and might utility if necessary.
cause failure. iii) Open the bypass on
iii) All flows to stop. electricity failure.
External Threats i) A local fire would necessitate i) Check plot plans of rest
the immediate pressure drop of of complex.
the plant. Segregate plant items ii) Check packing operation
by distance or barriers. to ensure no impact danger.
ii) Space required around reactor
for packing the reactor and
bringing in the columns.

52
CHAPTER 7

CONCLUSION
The overall design project for the production of Maleic Anhydride meets the desired
requirements and objectives. The production of 40,000 metric tonne per year of Maleic
Anhydride has a bright future from the feasibility study carried out. 93.4% conversion of
benzene was achieved in the plug flow reactor. The benzene feed requirement to produce 40,000
tons/year maleic anhydride was determined at 57.4 kmol/hr. The maleic anhydride produced had
99% purity. The future growth of Maleic Anhydride demand in Africa however is improving, a
4.5 % per year growth on Maleic Anhydride consumption is forecasted until year 2019.

The process chosen for the production of Maleic Anhydride is the catalytic oxidization of
benzene. Heuristics approach has been applied in identifying the appropriate design. For the
process synthesis and flow sheeting, base case material and energy balance together with process
simulation has been performed both by manual calculation and Aspen Hysys simulator.

Equipment process design and mechanical engineering design of all major equipment has been
performed by the Hysys simulator with standard input referred from literatures.

The economic evaluation of the production process was carried out using the Aspen Process
Economic Analyzer (APEA). From the result, the calculated payback period (PBP) was
approximately 2 years, the internal rate of returns (IRR) for the project was 55%. The equivalent
annual operating cost (EAOC) was also evaluated to be -$77,549.17. The large negative value
indicates that the project has a high profit return. From the profitability analysis, it was
concluded that the production of maleic anhydride using the process conditions simulated is very
feasible.

53
REFERENCE
B. Dmuchovsky and J. E. Franz, "Maleic Anhydride", Kirk-Othmer Encyclopedia of Chemical
Technology, Volume 12, John Wiley and Sons, Inc., New York, NY, 1967, pp. 819-837.

For Italy: Decreto Ministeriale n°60, 2nd April 2002.


Guliants, V.V. & Benziger, J.B. 1999. Effect of promoters for n-butane oxidation to maleic
anhydride over vanadium–phosphorus-oxide catalysts: comparison with supported vanadium
catalysts. Catalysis Letters 62(1999): 87–91.
Tecnon Orbichem, London SW11 3TN, UK.
Huntsman. S. C, (2001) Catalysis for the production of maleic anhydride containing vanadium-
phosphorus oxide with selected promoter elements147.

J. F. Lawson, (1978), Maleic Anhydride Product Report, EPA Contract No. 68-02-2577,
Hydroscience, Inc., Knoxville, TN, March.

N. F. Dummer, J. K. Bartley, G. J. Hutchings (2011), Advanced Catalysis. Volume 54, page 189.
Samuel Danishefsky, Takeshi Kitahara, and Paul F. Schuda (1983) "Preparation and Diels-Alder
Reaction of a Highly Nucleophilic Diene: trans-1-Methoxyl-3-Trimethylsiloxy-1,3-Butadiene
and 5β-Methoxycyclohexan-1-one-3β,4β-Dicarboxylic acid Andhydride" Organic Synthesis,
page 61.
Sajjad Khudhur Abbas, Production of Maleic Anhydride from Oxidation of n-Butane, Research
Gate; Technical Report no 303075230· December 2015

Timothy, R. Felthouse, Joseph, C. Burnett, Ben Horrell, Michael J.M. & Yeong- Jen Kuo. 2001.
Maleic Anhydride, Maleic Acid, and Fumaric Acid. Huntsman Petrochemical Corporation.

Trivedi. B. and M. Culbertson (2009) Maleic Anhydride.

www.polynt.com, assessed 15th June, 2017.

54
APPENDIX
Appendix 1: Reactor Feed Calculations

Benzene Feed Calculation

ASSUMPTIONS MADE:

 Reactor (R501) – No Maleic Anhydride is lost before it enters the absorber


 Absorber (T501) – 19% Maleic Anhydride is lost at the absorber
 Distillation Column (T-502) - 1% Maleic Anhydride is lost to the bottom (which is the
recycle stream).

CALCULATIONS
 From the Distillation Column,

Maleic Anhydride produced = 5000kg/hr

1% is lost before it come s out

i.e 99% is produced

5000/total output = 0.99

Total output = 5050.50 Kg/hr

Amount lost = 5050.50 – 5000 = 50.50Kg/hr

Total input of Maleic Anhydride to the distillation Column is 5050.50 Kg/hr

 To the Absorber
Output Maleic Anhydride = 5050.50Kg/hr
i.e total output from the reactor since it is assumed no Maleic Anhydride is lost.
Total input M.A to the absorber = Output M.A from reactor + Recycle M.A
Recycle M.A = M.A lost at the distillation column
Recycle M.A = 50.50 kg/hr
Therefore, total input M.A to the Absorber = 5050.50 + 5050 = 5101Kg/hr

55
 To the Reactor
Output M.A from the reactor = 5050.50kKg/hr
Assuming a 95% conversion of Benzene
From stoichiometry;
1 Kmol of Benzene yields 1kmol of M.A
Molecular weight of Maleic Anhydride = 98Kg/kmol,
M.A output from reactor = 5101/98 =52.03kmol/hr
Kmol of Benzene required (yield) = 52.05/0.63 = 82.62Kmol/hr
Therefore Benzene fed into the reactor = 82.62 Kmol/hr
Benzene fed = Amount in Kmol/hr × Molecular weight of Benzene
= (12 × 6) + (1 × 6) = 78Kg/kmol
Benzene fed in = 82.62 × 78 = 4231.3518 Kg/hr
i.e Benzene fed to the reactor = 4231.352 kg/hr
% Conversion = Benzene fed in – Unreacted Benzene × 100
Benzene fed in
0.95 = 82.62 – Benzene unreacted
Benzene fed in
Therefore, Unreacted benzene = 4.131 Kmol/hr.

Air Feed Calculation

Given from stoichiometry of equation 1,


4.5 moles of O2 = 1 kmol Maleic Anhydride
Amount of Maleic Anhydride ttt be produced:
40000 tonnes/ year = 5000kh/hr
Molecular weight of Maleic Anhydride = (12 × 4) + (2 × 1) + (3 × 16) = 98 Kg/Kmol
Amount of Maleic Anhydride in Kmol = 5000/98 = 51.02 Kmol/hr
Therefore,
4.5 = 1

56
X = 51.02
X = 51.02 × 4.5 = 229.59Kmol/hr
Amount of O2 required is 229.59kmol/hr
Amount of air required = Amount of O2 required = 229.59 =1093.2857 Kmol/hr
Percentage O2 in air 0.21
Theoretical amount of air required = 1093.2857 Kmol/hr
For 200% excess air;
Actual air amount required becomes
200 + 100 × theoretical = Actual air required
100
Amount of air required = 300 × 1093.2857 = 3279.8511Kmol/hr
100
Molecular Weight of Air = 28.84 kg/kmol
Mass of Air required = 3279.8511Kmol/hr × 28.84 kg/kmol
Thus mass of Air required = 94591.07876 Kg/hr

57
Appendix 2: Process simulation flowsheet.

Figure A1: Hysys simulation of the maleic anhydride production process using benzene as feed stock.

58
Appendix 3: Material Safety Data Sheet – MSDS

1. IDENTIFICATION OF THE SUBSTANCE


 Product name (label): Maleic Anhydride
 Name in English: Maleic Anhydride
2. COMPOSITION AND INFORMATION ON INGREDIENTS
 Commom chemical name of the substance: Maleic Anhydride
 Synonyms: Anhydride Cis-butenodioic Anhydride; 2,5-Furanedione; Toxylic
Anhydride; 2,5- Dioxihydrofurane; Anhydride of Acid Maleic
 Register in Chemical Abstract Service (nº C.A.S): [108-31-6]
 Ingredients that contribute to risk: Maleic Anhydride > 99,5%, corrosive, Nº C.A.S.:
[108-31-6]
3. HAZARD IDENTIFICATION
 Hazards and most important effects of the product: Corrosive substance, irritant to
skin and mucous membranes. Can cause chemical burns, and when there is contact
with the molten product, it causes thermic burns.
4. FIRST-AID MEASURES
 Inhalation: Remove the exposed person to non-contaminated area and apply artificial
respiration.
 Contact with skin: Wash immediately the skin with plenty of water and soap.
Contaminated clothing and shoes should be removed.
 Contact with eyes: Wash the eyes with plenty of water during, at least, 15 minutes.
 Ingestion: NO Induce vomiting. Keep the victim lying and warm. Do not give
anything to drink if the person is unconscious.
 Observation: in any situation, the victim should be sent to emergency medical
treatment.
 Information to physician: If there is contact of molten maleic anhydride with the skin,
it will cause severe thermic burn. The product will solidify and form a crust over the
affected area. This crust should be removed manually, and it should be administered
treatment for thermic burns of same size and depth. Intubation, if necessary. Signs
and symptoms of mucous membranes irritation can occur in cases of acute exposure

59
to the product. Doubling vision, photofobia or sensation of seeing rings around lights
can come from repeated moderate exposures or brief acute exposure. Inhalation for
prolonged periods can cause bronchospasms in individuals with predisposition.
Ingestion: induce to vomit and, later, administer two soup spoons of activated carbon
diluted in water. In case of aggression to other apparatuses or systems, call an expert.
5. FIRE-FIGHTING MEASURES
 Proper extinguishing media: Light fire: dry powder, CO2, and water fog or
mechanical foam. Intense fire: water fog or mechanical foam. Dry powder cannot be
used, because it contains Sodium.
 Specific hazards: Combustible product, but does not ignite easily. Flammable and
toxic gases can accumulate indoors. Fire can cause emission of irritant and toxic
gases. Water resulting from firefighting and dilution waters cannot be released
directly to bodies of water.
 Specific methods and firemen protection: Remove containers from the fire area, if
this can be done without risk. Cool with water the side parts of the containers exposed
to flames, long time after the fire is extinguished. Evacuate personnel in the affected
area. People involved in firefighting should wear self-contained apparatus and full
protection clothing.
6. ACCIDENTAL RELEASE MEASURES •
 Special precautions: Keep away bystanders, isolate the risk area, remove sources of
ignition and forbid the entrance of persons. Avoid dust formation (solid product).
Keep on the wind and keep away from low areas. Do not touch the spilled material.
Contain the spill, if this can be done without risks. Avoid contact of the product with
skin, eyes and respiratory system, wearing personal protective equipment, mentioned
in item 8.
 Environment precautions: - Solid product spills: collect with a clean shovel, put in
clean, dry vessels and close them. Remove them from the spill area.
 Cleaning methods: Follow the recommendations above mentioned.
7. HANDLING AND STORAGE

60
 Handling (technical measures) Wear safety equipment, according to item 8. Avoid
dust formation and buildup. Do not smoke or take meals in the area. At the slightest
sign of contact with the product, proceed according to item 4, first aid measures.
 Storage (technical measures) Solid: Keep the product in well closed packages, in a
dry and ventilated area. Do not reuse empty packages. Because the product is
hygroscopic, it is not advisable its storage for long periods, in order to avoid acidity
increasing and aggregation due to crystallization bridges. Put the product in
polypropilene packages. Molten: Store in 316 stainless steel tanks, grounded with
inert atmosphere by using nitrogen and keep temperature between 60 and 65ºC, but
not higher than 80ºC.

General Recommendations: Protect the area against physical damages and isolate from
incompatible substances (see item 10). Empty containers/tanks of the product can be hazardous
since they keep residues (dusts/particulates). Protect the area and tanks against static electricity.
Empty containers, only under inert or non-flammable atmosphere, due to the risk of fire or
explosion caused by static electricity. Storage area should have adequate ventilation.

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