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INTRODUCTION
1
Table 1.1 Physical and Chemical Properties for Industrial Maleic Anhydride
Formula C4H2O3
Liquid 0.164
In the early 1930s, maleic anhydride was first commercially produced by the
vapour-phase oxidation of benzene. The use of benzene as a feedstock for the
production of Maleic anhydride was dominant in the world market well into the 1980s.
Several processes have been used for the production of Maleic anhydride from benzene
with the most common one from Scientific Design. Small amounts of maleic acid are
produced as a by-product in production of Phthalic anhydride. This can be converted to
either Maleic anhydride or fumaric acid. Benzene, although easily oxidized to maleic
anhydride with high selectivity, is an inherently inefficient feedstock since two excess
2
carbon atoms are present in the raw material. Various C4 compounds have been
evaluated as raw material substitutes for benzene in the production of maleic anhydride.
Fixed- and fluid-bed processes for production of maleic anhydride from the butene
present in mixed C4 streams have been practiced commercially. None of these processes
is currently in operation because of rapid increases in the price of benzene and the
recognition of benzene as a hazardous material intensified the search for alternative
process technology in the United States. These factors led to the first commercial
production of maleic anhydride from butane at Monsanto's J. F. Queenly plant in 1974
(McKetta, J. J.1985).
By the early 1980s, the conversion of the U.S. maleic anhydride manufacturing
capacity from benzene to butane feedstock was well under way using catalysts
developed by Monsanto, Denka, and Halcon. One factor that inhibited the conversion
of the installed benzene-based capacity was that early butane-based catalysts were not
active and selective enough to allow the conversion of benzene-based plant without
significant loss of nameplate capacity.
3
construction of several new butane based facilities by CONDEA-Huntsman, Pantochim
and Lonza. Growth in the worldwide maleic anhydride industry I predominantly in the
butane-to-maleic anhydride route, often at the expense of benzene-based production.
Only a few newer benzene-based fixed-bed processes have been built since the
early 1980s and these were built where the availability of butane was limited. The
fluidized-bed butane-based process is experiencing some growth, but based on growth
rates from it does not appear destined to challenge fixed-bed technology. The
announcement from Huntsman Specialty Chemicals Corp., formerly Monsanto, and
DWE that they intend to cooperate in the development of catalyst and reactor
technology to permit operation at 50% higher productivity than the standard non-
flammable fixed-bed butane process indicates that the largest companies in fixed-bed
technology are confident that further advances are possible. Three fixed-bed processes,
from Huntsman Pantochim, and Scientific Design and two fluidized-bed processes,
from Alusiusse-Lummus (ALMA) and BP Chemicals, are currently offered for license
(Kirk, et al. 2005)
4
CHAPTER TWO
ECONOMY ASPECTS
5
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 last five years growing rapidly,
world demand for maleic anhydride rapid growth, annual growth rate of 7.3%, of which
the average annual growth in North American demand for maleic anhydride rate of 4%,
while demand in Western Europe and Japan, the growth rate of maleic anhydride,
respectively, 12% and 6.5% . Maleic anhydride in 2000 global production capacity has
reached 137 million tons. A few years ago the production capacity of maleic anhydride
in Asia only the world’s total production capacity of 24% in recent years as China,
Malaysia, South Korea and China Taiwan maleic anhydride production capacity of
rapid growth, the current production capacity of maleic anhydride in Asia already
accounts for the world’s total production capacity of 44%, the Asian region into the
world the largest production base of maleic anhydride at the same time, Asia has
become the maleic anhydride production than to be pure output region of Asia maleic
anhydride capacity growth, changed the world production of maleic anhydride regional
capacity allocation pattern present, China’s annual production capacity of maleic
anhydride has been close to 20 million tons, production capacity of maleic anhydride
in Asia about 35% of the current market is very mature maleic anhydride, maleic
anhydride downstream while new products are constantly land developed, such as
Germany, Bayer has developed a biodegradable chelating agent, poly aspartic acid and
biodegradable dispersant addition, without the use of refined or refined maleic
anhydride, maleic or direct use acid as raw materials to produce 1,4 – butanediol.
Unsaturated polyester resin was the largest end use market for maleic anhydride
in 2012. However, the demand is strongest in BDO market due to the growing use in
the production of elastic fibers, plant protection, thermoplastic polyurethanes, coatings,
solvents, pharmaceuticals, and electronic chemicals. Increasing demand for maleic
anhydride has triggered capacity expansion by companies mainly in Europe and Asia
6
Pacific. Continuous rise in raw material prices has increased the production cost thus
bringing maleic anhydride prices under pressure. However, continuous efforts on
research and development are expected to provide huge market opportunities such as
bio-based maleic anhydride to the industry participants.
Asia Pacific dominated the global market for maleic anhydride in 2012.With
over 52 percent global market shares in terms of both volume and revenue, Asia
Pacific is the leading consumer of maleic anhydride. North
America and Europe together accounted for over 30 percent of total volume share in
2012. The global maleic anhydride market has witnessed significant capacity addition
during the recent past. Asia Pacific is lucrative market for new plant establishments and
capacity expansions. The following pie chart shows global production of maleic
anhydride in 2012.
7
3000
2000
1500
Supply
Demand
1000
500
0
2000 2005 2010 2015 2020
Year
Figure 2.1: Comparison of Demand and Supply of Maleic Anhydride for Global
Market
Figure 2.1 indicates the graph of demand and supply of malic anhydride (tonnes)
against years from year 2000 to 2020. According to the chemical business, the demand
of maleic anhydride was increased by 15% from year 2000 to 2005, and 15.38% from
year 2005 to 2010. It is estimated that the demand will grow at a rate of 7.8% from year
2010 to 2015 due to the high demand of production of elastic fibers, plant protection,
thermoplastic polyurethanes, coatings, solvents, pharmaceuticals and electronic
chemicals. Its demand predicted to increase by 13.6% from 2015 to 2020.
The supply of maleic anhydride was increased by 18.22% from year 2000-2005,
and 18.18% from year 2005-2010. Its supply is predicted to rise by 35.74% from year
2010-2015, and increased by 11.11% from year 2015-2020.
Based on the market analysis that our group has been made, we can conclude
that the demand and supply of maleic anhydride will keep increasing in the coming
years due to the multi usages of maleic anhydride.
As we know, the demand is always greater than the supply of maleic anhydride
for every five year. Thus, to make a target for the production capacity, the shortage
must be first calculated.
8
Shortage = Average demand of maleic anhydride - Average supply of maleic
anhydride
To calculate the average demand and supply of maleic anhydride, we take the
data from the line graph of Figure 2.1 in year 2015.
=2200000 tonnes/year
=1800000 tonnes/year
Shortage:
= (2200000-1800000) tonnes/year
= 400000 tonnes/year
Based on the value of the shortage that is 300000 tonnes/year, we had decided
to produce maleic anhydride in industrial only 10% from the shortage which is about
40000 tonnes/year. This is due to the competitions in the market from various
companies.
Production capacity:
=40000 tonnes/year
9
2.2 Price of Maleic Anhydride per Tonne
Based on Asian market price for the end of August 2013, the price of maleic anhydride
was assessed at $1,600–1,650/tonne, which is approximately RM8256-8514/tonne
(ICIS 2013).
The maleic anhydride facility survived the 2005 cutbacks. But now, because
of industry overcapacity, profit margins for maleic anhydride, a building block for
unsaturated polyester resins, are unacceptably low, BASF says. Efforts to make the
plant more efficient haven't succeeded in making the plant sustainably cost
competitive, the firm adds.
10
Tom Witzel, BASF group vice president of European diols and polyalcohols,
says, "A withdrawal from maleic anhydride production in Feluy would help us to focus
on our core intermediates business," in vertically integrated value chains such as
butanediol and its derivatives, and polyalcohols. BASF adds, it will work with union
representatives to find "socially acceptable solutions" for employees affected by the
plant shutdown (Reisch, M. S. 2009).
2.5 Conclusion
The demand for maleic anhydride is growing rapidly every year with an annual growth
of 7.3% where the highest demand is a Western Europe followed by Japan. Of the total
demand Asia produces about 44% of maleic anhydride for the global market. The
maleic anhydride producing countries in Asia are China, Malaysia, South Korea, China
and Taiwan. The economic crisis of 2007 through most of 2009 contributed to a large
drop in consumption of maleic anhydride in most regions. Chinese consumption of
maleic anhydride slowed, but did not decline during the same period. The unsaturated
polyester resin market, maleic anhydride's largest consuming market, took a large hit
from the weak housing, construction, automotive and boating industries. At the end of
2009, several markets started to improve and there was a significant increase in demand
in 2010. Unsaturated polyester resins 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 since 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. In
future, 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.
11
CHAPTER THREE
PROCESS DESCRIPTIONS
The following reactions occur during the reaction of butane with oxygen:
The conversion of butane is assumed to be 82.2 percent. The selectivity for maleic
anhydride reaction is 70.0 percent, for carbon dioxide is 1.0 percent, for acrylic acid is
1.0 percent, and for formic acid is 1.0 percent (Preparation of Maleic Anhydride Using
Fluidized Catalysts US 4317778).
12
3.2 Process Flow Diagram
13
Figure 3 shows a PFD for the overall process. Pure butane, Stream 2, and
compressed air, Stream 3, are mixed and fed to R-101, an adiabatic reactor, where
butane reacts with oxygen to form maleic anhydride. The reaction is exothermic.
Therefore, one could consider either a fluidized bed reactor or a packed bed reactor
with heat removal to stay close to isothermal. The reactor effluent is cooled and sent to
T-101, a packed bed absorber, where it is contacted with water, Stream 7, to remove
the light gases and all of the maleic anhydride reacts to form maleic acid. The vapor
effluent, which consists of non-condensable, Stream 8, must be sent to an after-burner
to remove any carbon monoxide prior to venting to the atmosphere. This is not shown
here. The liquid effluent, Stream 9, is then cooled and flashed at 101 kPa and 120°C in
V-101. The vapor effluent from V-101, Stream 11, is sent to waste treatment. Stream
12, the liquid effluent, is sent to R-102 where maleic acid is broken down to maleic
anhydride and water. The reactor effluent is then sent to distillation column, T-102,
where maleic anhydride and water are separated. The distillate, Stream 14, is sent to
waste treatment. Stream 15, the bottoms, consists of 99-wt percent maleic anhydride.
Equipment Summary
C-101 Air Compressor
E-101 Heat Exchanger
E-102 Heat Exchanger
E-103 Condenser
E-104 Reboiler
P-101A/B Reflux Pump
R-101 Packed Bed Reactor
R-102 Maleic Acid Reactor
T-101 Absorbtion Tower
T-102 Distillation Column
V-101 Flash Vessel
V-102 Reflux Vessel
This maleic anhydride plant use butane, water and air as the raw materials.
14
3.4 Material Safety Data Sheet (MSDS) for the production of product
15
CHAPTER FOUR
4.1.1 Long term effects because of environmental issues related to the maleic
anhydride plant.
Exposure to maleic anhydride may occur from accidental release to the environment or
in a workplace where it is produce or used and also from the contact with spills, fugitive
emission, or vent gases. Chronic exposure to maleic anhydride has been observed to
cause chronic bronchitis, asthma-like attacks, pulmonary oedema, upper respiratory
tract irritation, eye irritation, and dermatitis in workers. In some people, allergies have
developed so that lower concentrations can no longer be tolerated. However mostly
exposure to maleic anhydride have cause irritation to several part of bodies.
A number of reports indicate that maleic anhydride is irritating to skin. First to second
degree skin burns and itching, which became more severe on showering, were reported
in two workers exposed by contact with contaminated clothing. (The Danish
Environmental Protection Agency. 2013).
16
4.1.1.2 Eye irritation
17
Table 4 : Sensory response of volunteers exposed to maleic anhydride
18
4.1.4 Current Issue Related to Maleic Anhydride.
4.1.4.1 Food Safety Issue Regarding Starch Containing Maleic Anhydride in Taiwan.
May 2013, the issue of toxic starch in Taiwanese food had spread all over the world.
Department of Health of China had announced that it had found maleic acid in food
such as tapioca balls (the balls in bubble tea), rice noodles and oolian a Taiwanese night
market staple inspired by Japanese tempura. Pointing out that the acid is formed after
maleic anhydride comes into contact with water, the Food and Drug Administration
(FDA) raised the possibility of maleic anhydride-grafted starch being used in food
products to make them chewier (The Straits Times 2013).
To cut synthesization costs and to reduce the water absorbency of the polymer,
maleic anhydride-grafted starch which is an industrial compound was added to polymer
plastics in part. The industrial starch is also used in polymeric films in the non-food
contact layer of food packaging. The FDA bans the compound's use as a food additive,
pointing out that the industrial substance maleic anhydride, which imparts chewiness,
can cause kidney failure if taken in sufficient doses (The China Post 2013).
However, as the solution, the Department of Health of China has demanded that
all tainted food products be promptly removed from shelves and destroyed, and that a
risk alert mechanism be established to enhance food safety inspections and management
nationwide. The government will also implement border control measures whereby any
company that is found to have manufactured products containing unapproved additives
or industrial starch will have to present safety certificated before it can export products
to other countries (Department of Health of Hong Kong 2013).
19
4.1.5 Pollution made by the maleic anhydride plant.
Maleic anhydride in soils is readily broken down. It does not bind particularly
strongly to soil particles, so can leach to groundwater where it will be broken down
naturally. In air, it reacts fairly quickly and so has a short life. Maleic anhydride does
not accumulate in the environment. It is not considered likely that Maleic anhydride
pollution has any effects on the global environment.
In general, industries and industrial operations should be encouraged that are more
efficient in terms of resource use, that generate less pollution and waste, that are based
on the use of renewable rather than non-renewable resources, and that minimize
irreversible adverse impacts on human health and the environment. The WARR Act
sets out eight objectives which are to encourage the most efficient use of resources and
to reduce environmental harm in accordance with the principles of ecologically
sustainable development and ensure that resource management options are considered
against a hierarchy of the following order:
Next is to provide for the continual reduction in waste generation, minimise the
consumption of natural resources and the final disposal of waste by encouraging the
avoidance of waste and the reuse and recycling of waste and to ensure that industry
shares with the community the responsibility for reducing and dealing with waste.
20
Furthermore, this act also ensure the efficient funding of waste and resource
management planning, programs and service delivery .Lastly, to achieve integrated
waste and resource management planning, programs and service delivery on a State-
wide basis and to assist in the achievement of the objectives of the Protection of the
Environment Operations Act 1997.
Malaysia has had environmentally-related legislation since the early 1920s.But the
legislation is limited in scope and inadequate for handling complex emerging
environmental problems. So through EQA, 1974, a more comprehensive form of
legislation and an agency to control pollution was established.
EQA is an enabling piece of legislation for preventing, abating and controlling
pollution, and enhancing the environment, or for other related purposes. Pollution, as
declared in EQA, includes the direct or indirect alteration of any quality of the
environment or any part of it by means of a positive act or act of omission.
Pollution is ‘controlled’ through the mechanism of licences issued by the
Department of Environment. The mode of control is by prescribing, by means of a
ministerial regulation, that licences are mandatory for:
The use and occupation of prescribed premises;
Discharging or emitting wastes exceeding acceptable conditions into the
atmosphere, as well as noise pollution, polluting or causing the pollution of any
soil or surface of any land;
Emitting, discharging or depositing any wastes or oil, in excess of acceptable
conditions, into inland waters or Malaysian waters.
The provision of "acceptable conditions" is controversial because the polluter is
not liable for prosecution if the discharge is within those acceptable conditions, even if
the effluents are sufficient to severely damage the environment. Most people adversely
affected by pollution do not want to seek legal remedy through common law because
of the prolonged nature of such hearings and the costs incurred.
21
enhanced to ensure the full compliance with laws and regulations. With regard to
monitoring and enforcement, surveillance capability will be strengthened. The penalty
structure related to environment offences will be revised to ensure a more effective
deterrent, especially in the case of repeat offenders. The enforcement function of
agencies such as the Department of Environment, Health Department, Pesticide Board
and local authorities will be rationalized and streamlined, and adequate training will be
provided for their enforcement staff.
Motor Vehicles (Control of Smoke and Gas Emission) Rules, 1977 (made under
the Road Traffic Ordinance of 1958)
Environmental Quality (Control of Lead Concentration in Motor Gasoline)
Regulations, 1985
22
Environmental Quality (Motor Vehicle Noise) Regulations, 1987
In any equipment where an interface exits between two phases (eg. Liquid vapor), some
means of maintaining the interface at the required level must be provided. This may be
incorporated in the design of the equipment, the control value should be placed on the
discharge line from the pump.
Pressure control will be necessary for most systems handling vapor or gas. The method
of control depends on the nature of the process.
Flow control is usually with inventory control in a storage tank or other equipment.
There must be a reservoir to take up the changes in flow –rate. To provide flow control
on a compression or pump running at a fixed speed and supplying a near constant
volume output, a by-pass would be used.
Here, the temperature can be controlled by varying the flow of the cooling or heating
medium. If the exchange is between two process streams whose flows are fixed, by-
pass control will have to be used.
23
4.2.5 Condenser Control
The schemes used for reactor control depend on the process and type of reactor. If a
on–line analyzer is available and the reactor dynamics are suitable, the product
composition can be monitored continuously and the reactor conditions and feed flows
controlled automatically to maintain the desired product composition and yield. More
often, the operation is the final link in the control loop, adjusting the controller set points
to maintain the product within specification, based on periodic laboratory analyzer.
Regulating the flow of the heating or cooling medium will normally control reactor
temperature. Pressure is usually held constant. Material balance control will be
necessary to maintain the correct flow of reactants to the reactor and the flow of product
and un-reacted materials from the reactor.
24
4.3 First aid measures
4.3.1 Swallowed
For advice, contact a Poisons Information Centre or a doctor at once. Urgent hospital
treatment is likely to be needed.
4.3.2 Eye
If this product comes in contact with the eyes: Immediately hold eyelids apart and flush
the eye continuously with running water. Ensure complete irrigation of the eye by
keeping eyelids apart and away from eye and moving the eyelids by occasionally lifting
the upper and lower lids. For thermal burns: “Do not remove contact lens”. Lay victim
down, on stretcher if available and pad both eyes, make sure dressing does not press on
the injured eye by placing thick pads under dressing, above and below the eye. Seek
urgent medical assistance, or transport to hospital.
4.3.3 Skin
If skin or hair contact occurs: Immediately flush body and clothes with large amounts
of water, using safety shower if available. Quickly remove all contaminated clothing,
including footwear. In case of burns: Immediately apply cold water to burn either by
immersion or wrapping with saturated clean cloth. Do not remove or cut away clothing
over burnt areas. Do not pull away clothing which has adhered to the skin as this can
cause further injury. Do not break blister or remove solidified material. Quickly cover
wound with dressing or clean cloth to help prevent infection and to ease pain. For large
burns, sheets, towels or pillow slips are ideal; leave holes for eyes, nose and mouth. Do
not apply ointments, oils, butter, etc. to a burn under any circumstances. Water may be
given in small quantities if the person is conscious. Alcohol is not to be given under
any circumstances. Reassure. Treat for shock by keeping the person warm and in a lying
position. Seek medical aid and advise medical personnel in advance of the cause and
extent of the injury and the estimated time of arrival of the patient.
4.3.4 Inhaled
If fumes or combustion products are inhaled remove from contaminated area. Lay
patient down. Keep warm and rested. Inhalation of vapors or aerosols (mists, fumes)
25
may cause lung oedema. Corrosive substances may cause lung damage. To extinguish
the media, do not apply direct a solid stream of water or foam into burning molten
material; this may cause spattering and spread the fire. Dry chemicals are not
recommended to be used because they contain alkalis which may cause rapid
exothermic reactions.
26
CHAPTER FIVE
Mass balance is used to compare the inputs and the output of the processes. It is an
application of the law of conservation of mass to analyze the physical system. Law of
the conservation of mass states that the mass of a closed system will remain constant,
regardless the processes occur in the system. This mean that the mass enter the system
must equal to the mass leave the system. By accounting for material entering or leaving
a system, mass flows can be identified which might have been unknown, or difficult to
measure without this technique. The purpose for using the mass balance is to ensure
that there is no mass loss during the entire reaction.
Molecular weight of CO = 28
27
COMPRESSOR
Figure 3 shows the raw materials, butane in stream 1 and compressed air in stream 2
are mixed. The components in the stream 2 are the same as in the stream 3 which
contains oxygen, nitrogen and water. There is a mixer before the components in
stream 1 and 3 flow into stream 4.
Butane
1
2 3
Air
C-101
Compressor
Figure 3
For stream 1
REACTOR
Figure 4 shows the butane and air enter the reactor to form maleic anhydride. The
material mass balance that needs to be considered is at the reactor. Based on the
Principle of Conservation Of Mass, it shows that the amount of mass entering a system
must be equivalent to the amount exiting the system. Hence, the mass at the inlet and
outlet have to be determined to confirm the accuracy of the data,
28
4
R-101
Packed XC4H10=0.822
bed
reactor
5
E-3
Figure 4
r1
r2
r3
r4
0.822= -[(-1)r1+(-1)r2+(-1)r3+(-1)r4]/(5131.71÷58)
Selectivity of C4H203=0.7
0.7= r1/(5131.71÷58)
r1= 61.9339
29
Selectivity of CO2=∑αco2r/N4C4H10= 1.5320
2r1+r2+3r3/(5131.71÷58)=1.5320
r2=9.02526
SC3H4O2=∑αC3H4O2 r /N4C4H10
0.01=r3/(5131.71÷58)
r3=0.88477
SCH2O2=∑αCH2O2 r /N4C4H10
0.01=r4/(5131.71÷58)
r4=0.88477
For stream 4
F4=100260.04kg/h
F4N2= 75152.02kg/h
F4O2= 18074.54kg/h
F4C4H10=5130.9kg/h
F4H2O=1902.58kg/h
For stream 5
Component balance
F4=Fi,F5=Fo
30
C4H10:
NoC4H10 = 15.7491 X 58
FoC4H10 = 913.4478kg/h
O2 :
NoO2 = 290 X 32
FOO2= 9280.34kg/h
C4H203:
NoC4H203 = 0 + 61.9339X 98
FoC4H203 = 6069.5222kg/h
H2O:
No H2O = 404.75829 X 18
FOH2O = 7285.64922kg/h
31
CO :
NICO +α CO r = NoCO
O + 2 r2 = NoCO
NoCO = 2(9.02526) X 28
FOCO = 505.41456kg/h
CO2 :
0 + 2 r2 + r3+ 3 r4 = NoCO2
NoCO2=21.5896X 44
=949.9424 kg/h
C3H4O2:
O + r3 = No C3H4O2
No C3H4O2 = 0.88477X 72
FOC3H4O2 = 63.70344kg/h
CH202 :
0 + r4 = No CH202
0.88477 = No CH202
No CH2O2 = 0.88477
FoCH2O2=0.88477 X 46
FOCH2O2 = 40.69942kg/h
32
N2:
FoN2= 75150.92kg/h
F4=F5
75152.02+18074.54+5130.9+1902.58=913.4478+9280.34+6069.5222+7285.64922+5
05.41456+949.9424+63.70344+40.69942+75150.92
100260.04=100260.04(proven)
HEAT EXCHANGER
Figure 5 shows stream 5 and stream 6. The components in both streams are the same
as the purpose of having it is to lower the temperature of the reaction from 410°C to
95°C.
5 6
Heat exchanger
Figure 5
F5=F6
ABSORPTION TOWER
8 To atmosphere
Water
Absorption tower
6
E-4
9
33
For stream 6
F6=100260.04kg/h
F6N2=75150.92kg/h
F6CO=505.41456kg/h
F6O2=9280.34kg/h
F6CO2=949.9424kg/h
F6C4H10=913.4478kg/h
F6H2O=7285.64922kg/h
F6CH2O2=40.69942kg/h
F6C3H4O2=63.70344kg/h
F6C4H2O3=6069.5222kg/h
For stream 7
F7=1902.58kg/h
F7H2O=1902.58kg/h
For stream 8
F8=85886.623kg/h
F8N2=75150.9266kg/h
F8CO=505.41456kg/h
F8O2=9280.34kg/h
F8CO2=949.9424kg/h
For stream 9
F9=16275.60186kg/h
F9C4H10=913.4478kg/h
F9H2O=9188.229kg/h
34
F9CH2O2=40.69942kg/h
F9C3H4O2=63.70344kg/h
F9C4H2O3=6069.5222kg/h
F6+F7=F8+F9
100260.04+1902.58=85886.623+16275.60186
102162=102162 (proven)
HEAT EXCHANGER
Figure 7 shows stream 9 and stream 10. The components in both streams are the same
as the purpose of having it is to lower the temperature of the reaction from 60 °C to
40°C.
9 10
Heat exchanger
For stream 10
F9=F10 =16275.60186kg/h
F10C4H10=913.4478kg/h
F10H2O=9188.229kg/h
F10CH2O2=40.69942kg/h
F10C3H4O2=63.70344kg/h
F10C4H2O3=6069.5222kg/h
35
11
To waste treatment
10
Flash vessel
12
E-5
Distillation
Column
F10=F11+F12
For stream 11
F11=8428.085kg/h
F11C4H10=913.4478kg/h
F11H2O=7350.5832kg/h(80% selecrivity)
F11CH2O2= 40.2924kg/h
F11C3H4O2=63.0664kg/h
F11C4H4O3=60.6952kg/h
For stream 12
F12=7847.5166kg/h
F12H2O=1837.6458kg/h
36
F10=F11+F12
16275.60186=8428.085+7847.5166
16275.601=16275.601 (proven)
Condenser
Reflux
vessel
To waste
treatment
13
12
Reflux Pump
Distillation
column
Reboiler
Maleic Anhydride
14
F12=F13+F14
Assume top product contains 0.1% maleic anhydride, 0.8% water, 0.7% of acrylic
acid and formic acid
For stream 13
F13=2071.730kg/h
F13H2O=1470.11664g/h
F13CH2O2=0.284893 kg/h
F13C3H4O2=0.4459 kg/h
F13C4H2O3=600.882678 kg/h
37
For stream 14
F14=5775.595257kg/h
F14H2O=367.52916kg/h
F14CH2O2=0.122097kg/h
F14C3H4O2=0.19111kg/h
F14C4H2O3=5407.944kg/h
F12=F13+F14
(1837.6458+0.40699+0.637034+6008.82678=(1470.11664+0.284893+0.4459+600.8
82678)+( 367.52916+0.122097+0.19111+5407.9440)
7847.516=2071.730+5775.95257(proven)
F1+F2+F7=F8+F11+F13+F14
5130.9+95129.14+1902.58=85886.623+8428.085+2071.730+5775.595257
102162=102162 (proven)
38
Stream 1 2 3 4 5 6 7 8
Temp. (°C) 20 20 147.9 121 410 95 45 59.9
Vapor 0 1 1 1 1 1 0 1
Fraction
Total Flow 5130.9 95129.14 95129.14 100260.04 100260.04 100260.04 85886.623
(kg/h) 1902.58
Component 0 0 0 0 0 0 0 0
Flow(kg/h)
39
5.2 Energy Balance
The energy balance is the arithmetic balancing of energy inputs versus outputs for an
object, reactor, or other unit processing. It determine the heat released or absorbed
during the reaction. The reaction is exothermic if the heat is released and is endothermic
if heat is absorbed. The concept of energy balance is generally the same for all process
but only with different approach. The energy balances are used to quantify the energy
used or produced by a system. This can be used to build complex differential equation
models to design and analyze real systems. To make an energy balance for a system is
very similar to making a mass balance but there are a few differences.
The law of conservation of energy states that energy can neither be created nor
destroyed; it can only be changed from one form to another or transferred from one
body to another. Therefore the sum of all the energies in the system remains constant.
The purpose is to carry out the calculation of energy balance is to determine the heat
change of the unit processing which being analyzed.
Stream 4 121oC
Nitrogen gas
Oxygen gas
Water
n-butane
Reactor 1
Nitrogen gas
Oxygen gas
Water
Stream 5 n-butane
Carbon monoxide gas
410oC Carbon dioxide gas
Formic acid
Acrylic acid
Maleic anhydride
40
Table 5.3 Properties data of each component
Stream 4
394 394
(3943-2983)+(1/4)(1.312X10-9)(3944-2984)
= 2873.52 J/kmol.K
41
394 394
(3943-2983)+(1/4)(-2.873X10-9)(3944-2984)
= 2804.05 J/kmol.K
394 394
(3943-2983)+(1/4)( 5.3469e-7)(3944-2984)
= 19302287.84 J/kmol.K
394 394
(3943-2983)+(1/4)( 35X10-9)(3944-2984)
= 10740.43 J/kmol.K
Stream 5
683 683
(6833-2983)+(1/4)(1.312X10-9)(6834-2984)
= 12052.23 J/kmol.K
42
683 683
= 11466.33 J/kmol.K
683 683
(6833-2983)+(1/4)( 5.3469e-7)(6834-2984)
= 251811.59 J/kmol.K
683 683
(6833-2983)+(1/4)( 35X10-9)(6834-2984)
= 55654.68 J/kmol.K
683 683
= 11564.55 J/kmol.K
43
683 683
(6833-2983)+(1/4)( 7.469X10-9)(6834-2984)
= 16847.01 J/kmol.K
683 683
(6833-2983)+(1/4)( 1.156X10-7)(6834-2984)
= 15495.6 J/kmol.K
683 683
(kmol/h) (kJ/kmol.K)
Nitrogen gas 2684 2.804
44
Nnitrogen Ĥinitrogen = 7525.94
∑Ĥ4 = 2050349.39
Stream 5
(kJ/kmol.K)
Nitrogen gas 2683.96 11.47
45
Nn-butane Ĥon-butane = 874.82
∑H5 = 139309.53
Q= Ĥout-Ĥin+r(∆Hof)
=-559.08 kJ/mol
= - 34626 kJ/mol
Q = 139309.85-2050349-34626
Therefore, the reactor need to release 1945665.15 kJ/hour of heat in order for the
process to occur.
46
CONCLUSION
Maleic anhydride has been use a lot in industry to produce various kind of product.
However majority of it is use in unsaturated polyester resin which is then used in both
glass reinforced applications and in unreinforced applications. Other than that it also
use in manufacture of alkyd resins, production of agricultural chemicals ,maliec acid,
copolymers and etc.
Even though unsaturated polyester resin was the largest end use market for maleic
anhydride in 2012 but, the demand is strongest in the BDO market due to the growing
use in the production of elastic fibers, plant protection, thermoplastic polyurethanes,
coatings, solvents, pharmaceuticals, and electronic chemicals. Increasing demand for
maleic anhydride has triggered capacity expansion by companies mainly in Europe and
Asia Pacific. Continuous rise in raw material prices has increased the production cost
thus bringing maleic anhydride prices under pressure. However, continuous efforts on
research and development are expected to provide huge market opportunities such as
bio-based maleic anhydride to the industry participants.
Mass and energy balance of maleic anhydride can be calculated either using manual
or iCON software. Although it might be a difference between these two values, but the
changes is too small.
Exposure to maleic anhydride can effect someone health if he/she expose to maleic
anhydride exceed the warning concentration. Thus, there’s a lot of precaution need to
be carried out during working with maleic anhydride.
In conclusion, maleic anhydride is one of the products that has been use widely all
over the world to produce another kind of product. Market of maleic anhydride also
increase from year to years.
47
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48
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49
APPENDIX
50