CHAPTER ONE

INTRODUCTION

1.1 Introduction to maleic anhydride

Maleic anhydride (butenedioic anhydride, toxilic anhydride,
2,5-dioxofuran), an organic compound with the formula C2H2(CO)2O
is the acid anhydride of maleic acid. In its pure state it is a
colourless or white solid with an acrid odour. Maleic anhydride is a
solid at room temperature. Above 52.9 C it becomes a clear,
colourless, low viscosity liquid. Maleic anhydride is soluble in water
forming maleic acid. In the United States, one plant uses only nbutane and another uses n-butane for 20 %of its feedstock, but the
primary raw material used in the production of Maleic Anhydride is
benzene. The Maleic Anhydride industry is converting old benzene
plants and building new plants to use n-butane. Maleic Anhydride
also is a by-product of the production of phthalic anhydride. It is a
solid at room temperature but is a liquid or gas during production. It
is a strong irritant to skin, eyes, and mucous membranes of the
upper respiratory system Table 1.1 further explains some physical
and chemical properties of industrial maleic anhydride. (McKetta, J.
J.1985)

Table 1.1 Physical and Chemical Properties for Industrial Maleic

Anhydride
Property

Maleic Anhydride

Formula

C4H2O3

Formula weight, g

98.06

Melting point, oC

52.85

Boiling point, oC

202

Heat of formation, kJ/mold

-470.41

Heat of combustion, kJ/ mold

-1389.5

Heat capacity,kJ/(K mol)d

Solid

0.1199

Liquid

0.164

Heat of sublimation, kJ/ mold

71.5

Heat of vaporization, kJ/ mold

54.8

Heat of fusion, kJ/ mold

13.55

Heat of hydrolysis, kJ/ mold

-34.9

1.2 Production of maleic anhydride

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
2

anhydride or fumaric acid. Benzene, although easily oxidized to

maleic anhydride with high selectivity, is an inherently inefficient
feedstock since two excess 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 C 4 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.
In 1983, Monsanto started up the world's first butane-toMaleic anhydride plant, incorporating an energy efficient solventbased product collection and refining system. This plant was the
world's largest Maleic anhydride production facility in 1983 at
59,000t/year capacity, and through rapid advances in catalyst
technology has been debottlenecked to a current capacity of
105,000t/year in 1999. Advances in catalyst technology, increased
regulatory pressures, and continuing cost advantages of butane
over benzene have led to a rapid conversion of benzene- to butanebased plants. By the mid-1980s in the United States 100% of maleic
3

anhydride production used butane as the feedstock. (Chem Systems

PERP Program 2009)
Coincident with the rapid development of the butane-based
fixed-bed process, several companies have developed fluidized-bed
processes. Two companies, Badger and Denka, collaborated on the
development of an early fluid-bed reaction system which was
developed

through

the

pilot-plant

stage

but

was

never

commercialized. Three fluid-bed, butane-based technologies were

commercialized during the latter half of the 1980s by Mitsubishi
Kasei, Sohio (British Petroleum). Europe has largely converted from
benzene-based to butane-based Maleic anhydride technology with
the construction of several new butane based facilities by CONDEAHuntsman, Pantochim and Lonza. Growth in the worldwide maleic
anhydride

industry

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 fixedbed butane process indicates that the largest companies in fixedbed 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)
1.3

Usage of maleic anhydride.

4

Maleic anhydride is truly a remarkable molecule in that it possesses

two types of chemical functionality making it uniquely useful in
chemical synthesis and applications. Maleic anhydride itself has few
consumer uses but in derivative form,it is extremely versatile in the
consumer uses in which it is found. The majority of the maleic
anhydride

produced

is

used

in

unsaturated

polyester

resin.

Unsaturated polyester resin is then used in both glass-reinforced

applications and in unreinforced applications. Another significant
use of maleic anhydride is in the manufacture of alkyd resins, which
are in turn used in paints and coatings. Other applications where
maleic anhydride is used include the production of agricultural
chemicals,

maleic

acid,

copolymers,

fumaric

acid,

lubricant

additives, surfactants and plasticizers. It is also used as a comonomer for unsaturated polyester resins, an ingredient in bonding
agents used to manufacture plywood, a corrosion inhibitor, and a
preservative in oils and fats (Greiner, E., et al. 2002).

CHAPTER TWO

ECONOMY ASPECTS

2.1

Supply and demand of maleic anhydride

5

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. Maleic anhydride consumption
for butanediol will grow primarily in Asia and the Middle East. Maleic
anhydride consumption for butanediol is not included in the United
States since maleic anhydride is not refined. A plant in the Republic
of Korea uses refined maleic anhydride for butanediol production.
Maleic anhydride consumption for butanediol production is included
in Other Asia and the Middle East, in cases where refined maleic
anhydride is believed to be used.
Regionally,

smaller

end-use

applications

will

experience

higher-than-average growth, such as maleic copolymers in the

United States. New product developmentdriven by increasing the
use of renewable or replacing one petroleum-based chemical with a
more environmentally friendly onewill 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).
6

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
worlds 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 worlds 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, Chinas 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 Pacific. Continuous rise in raw
7

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.
Unsaturated polyester resins dominate the maleic anhydride
consumption, accounted for 49.3 percent of the total consumption in
2012 and expected to grow at a CAGR of 5.3 percent from 2012 to
2018. The demand for unsaturated polyester resins was primarily
driven by the increasing demand for general construction, pipes and
ducts, corrosion resistant tanks, paints and coatings, bathroom
fixtures and fibreglass reinforced plastics (Chem Systems PERP
Program 2009).
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.

Figure 1: Global Consumption of Maleic Anhydride for Year 2012.

8

Source: Maleic Anhydride (MA): 2013 World Market Outlook and

Forecast up to 2017.

3000
2500
2000

Capacity of malic anhydride (kilo tonnes)

1500
Supply

1000

Demand

500
0

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.
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.

Demand of maleic anhydride:

=2200000 tonnes/year

Supply of maleic anhydride:

=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
10

tonnes/year. This is due to the competitions in the market from

various companies.
Production capacity:
=(10/100) x 400000 tonnes/year
=40000 tonnes/year

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 $1,6001,650/tonne, which is
approximately RM8256-8514/tonne (ICIS 2013).
2.3

List of Companies in Malaysia That Produce Maleic Anhydride

1) Heller Industries Malaysia Sdn. Bhd. at Bayan Lepas, Pulau

Pinang
2) Teleflex Medical Sdn. Bhd.
3) Gimmill Industrial (M) Sdn. Bhd. at Bukit Mertajam, Pulau
Pinang
4) Orient Co One Cross Island Plaza
2.4

Current issue related to maleic anhydride

2.4.1 Economic issues on maleic anhydride plant

In the end of 2009, BASF company plans to shut down a 115,000metric-ton-per-year maleic anhydride facility in Feluy, Belgium.
About 133 jobs will be affected. The facility closure effectively
marked the end of all BASF activities in Feluy. About four years
11

ago, the firm ended production of phthalic anhydride, plasticizers,

fumaric acid, and butanediol at the Feluy site that it had purchased
in 2001 from the bankrupt Italian firm SISAS.
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.
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
12

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 developmentdriven by increasing the
use of renewable or replacing one petroleum-based chemical with a
more environmentally friendly onewill 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.

CHAPTER THREE

PROCESS DESCRIPTIONS

3.1

Chemical reactions.

13

The following reactions occur during the reaction of butane with

oxygen:
C4H10+3.5O2

C4H2O3+4H2O

(1)

C4H10+5.5O2

2CO+2CO2+5H2O

C4H10+3.502

C3H4O2+CO2+3H20

(3)

C4H10+6O2

CH2O2+3CO2+4H2O

(4)

(2)

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).
The

process

thermodynamic

was

package

simulated
for

using

Kvalues

the

and

Peng-Robinson

Peng-Robinson

for

enthalpy. UNIFAC thermodynamic suggested an azeotrope between

maleic anhydride and water, which would not allow purification of
the maleic anhydride to the purity obtained here. This should be
considered when designing the separation units.
3.2

Process Flow Diagram

14

Figure 3 shows a PFD for the overall process. Pure butane,

Stream 2, and compressed air, Stream 3, are mixed and fed to R101, 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
15

then cooled and flashed at 101 kPa and 120C 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
3.3

Raw materials

This maleic anhydride plant use butane, water and air as the raw
materials.
3.4

Material Safety Data Sheet (MSDS) for the production of

product
-Attached in the appendix.

16

CHAPTER FOUR
17

ENVIRONMENTAL OF SAFETY ISSUES

4.1

Environmental issues faced by operating the maleic anhydride

plant.
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,

concentrations

allergies

can no

have

longer

developed

so

that

be tolerated. However

lower
mostly

exposure to maleic anhydride have cause irritation to several part of

bodies.
4.1.1.1 Skin irritation
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).

4.1.1.2 Eye irritation

18

Maleic anhydride as dust or vapour has been reported to cause

conjunctivitis, inflammation and swelling of the eyelids, severe
lachrymation and photophobia (HSE, 1996). According to data
presented in IUCLID (2000), exposure to a concentration of 6-8
mg/m3(form of test material not described) resulted in eye irritation
within 15 minutes (IUCLID 2000).
4.1.1.3 Respiratory irritation
Two cases of respiratory irritation following exposure to maleic
anhydride dust or vapour have been reported (HSE 1996). A
threshold of 5.48 mg/m3for irritative effects has been reported in a
review by Ruth (1986).According to data presented in IUCLID (2000),
exposure to a concentration of 6-8 mg/m 3(form of test material not
described) resulted in nasal irritation within 1 minute; among
workers repeatedly exposed to 5-10 mg/m 3, ulceration of nasal
mucous membrane, chronic bronchitis and in some cases asthma
occurred (IUCLID 2000).An exposure chamber study in male
volunteers (age 22-27 years) has been performed. Maleic anhydride
vapour was produced by melting the solid; exposure concentrations
were

determined

by

atmospheric

analysis.

Three

sets

of

investigations were performed (HSE, 1996). In the first set of trials

(6 trials, twice/week), groups of 2-7 volunteers were exposed for 5
minutes to concentrations ranging from 22 to 270 mg/m 3. In the
second set, 6 volunteers were exposed to a concentration of 54
mg/m3for 1 hour. In the third set, 5 volunteers were exposed to 45
mg/m3for 1 hour.

Table 4 shows the description made by the

volunteers regarding their sensory responses on a standard form at

regular intervals throughout the exposure periods:

19

Table 4 : Sensory response of volunteers exposed to maleic

anhydride
Concentration (mg/m3)

Description of sensory response

270

Nasal

irritation,

impairment

of

smell, eye irritation, greater than

moderate pulmonary discomfort in
3/5 subjects.
179

Eye irritation, moderate pulmonary

discomfort in 1/5 subjects.

54

Very

occasional

pulmonary

discomfort and impairment of smell.

45

Very

occasional

pulmonary

discomfort and impairment of smell

22

Response not described in HSE

1996.

4.1.2 Waste relevant to maleic anhydride plant.

Maleic anhydride plant is operated to produce maleic anhydride as
the product. However, some waste products such as un-reacted
butane, carbon monoxide gas, acetic, acrylic acids, water and
carbon dioxide are obtained in this plant, as the plant is operated.
4.1.3 Waste treatment of maleic anhydride plant.
A small slipstream of the circulating solvent is purified to remove
solvent degradation products in order to prevent the build up of
impurities in the solvent recycle loop. The absorber offgas is
20

combined with the light ends column distillate and vacuum system
exhausts and fed to the incinerator, where unreacted butanes and
reaction by-products (carbon monoxide, acetic and acrylic acids) are
combusted. The waste heat is recovered as high pressure steam,
which is combined with the steam from the reactor and
superheated. A portion of this steam can be used to drive the air
compressor, with the excess exported or used to generate electric
power.
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 anhydridegrafted 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).
Singapore's Agri-Food and Veterinary Authority (AVA) reported
that it had detected maleic anhydride in eleven products imported
21

from Taiwan out of sixty six tested. Besides, AVA said all products
had been withdrawn from stores and consumers who bought the
products were asked to return them to the retailers or discard them
(Asia News Network 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

manufactured

any

products

company
containing

that

is

found

unapproved

to

have

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).

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.
4.1.6 Environmental acts.
Releases of Maleic anhydride are controlled through the UK
Pollution, Prevention and Control (PPC) Regulations. An upper limit
for safe long term exposure to Maleic anhydride has been
designated in amendments to the 1994 UK Control of Substances
Hazardous to Health (COSSH) Regulations (SI 1996/3138)
22

4.1.7 The latest act on environmental quality.

4.1.7.1
In

Waste Avoidance and Resource Recovery Act 2001.

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:
(i) Avoidance of unnecessary resource consumption.
(ii) Resource recovery (including reuse, reprocessing, recycling
and energy
recovery).
(iii) Disposal.
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. 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 Statewide basis and to assist in the achievement of the objectives of
the Protection of the Environment Operations Act 1997.
4.1.7.2 Environmental Quality Act, 1974

23

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.
Currently, 16 sets of regulations and orders are enforced by
the Department of Environment under EQA. Despite government
24

efforts to implement environmental laws and regulations, it has

been found that enforcement measures need to be further
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.
4.1.7.3 Control of agro-based water pollution

Environmental Quality (Licensing) Regulations, 1977

Environmental Quality (Prescribed Premises) (Crude Palm Oil)

Order, 1977

Environmental Quality (Prescribed Premises) (Crude Palm Oil)

Regulations, 1977, and (Amendment) 1982

Environmental Quality (Prescribed Premises) (Raw Natural

Rubber) Order, 1978

Environmental Quality (Prescribed Premises) (Raw Natural

Rubber) Regulations, 1978

4.1.7.4

Control of municipal and industrial waste water pollution

Environmental

Quality

(Sewage

and

Industrial

Effluents)

Regulations, 1979

Environmental Quality (Prohibition on the Use of Controlled

Substance in Soap, Synthetic Detergent and Other Cleaning
Agents) Order, 1995
25

4.1.7.5

Control of industrial emissions

Environmental Quality (Clean Air) Regulations, 1978

Environmental Quality (Compounding of Offenses) Rules, 1978

4.1.7.6

Control of motor vehicle emissions

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

Environmental Quality (Motor Vehicle Noise) Regulations, 1987

4.1.7.7

Control of toxic and hazardous waste management

Environmental Quality (Scheduled Wastes) Regulations, 1989

Environmental

Quality

(Prescribed

Premises)

(Scheduled

Wastes Treatment) and Disposal Facilities) Order, 1989

Environmental

Quality

(Prescribed

Premises)

(Scheduled

Wastes Treatment and Disposal Facilities) Regulations, 1989

Promotion of Investments (Promoted Activities and Products)

(Amendment)

(No.

10)

Order,

1990

(made

under

the Promotion of Investments Act, 1986

4.2 Safety issues of the maleic anhydride plant.
4.2.1 Level Control
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
26

design of the equipment, the control value should be placed on the

discharge line from the pump.
4.2.2 Pressure Control
Pressure control will be necessary for most systems handling vapor
or gas. The method of control depends on the nature of the process.
4.2.3 Flow Control
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.
4.2.4 Heat Exchangers
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.
4.2.5 Condenser Control
Temperature control is unlikely to be effective, unless the liquid
stream is sub-cooled. Pressure control is often used, or control can
be based on the outlet coolant temperature.
4.2.6 Reactor Control
The schemes used for reactor control depend on the process and
type of reactor. If a online 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
27

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.
4.2.7 Distillation Column Control
The primary objective of distillation column control is to
maintain the specified composition of the top and bottom
products, and any side streams; correcting the effect of
disturbances in:
1) Feed flow rate, composition and temperature.
2) Steam supply pressure.
3) Cooling water pressure and header temperature.
4) Ambient conditions, which cause changes in internal
reflux.
5)

Regulating

reflux

flow

and

boil-ups

control

the

compositions. The column

overall material balance should also be controlled;
distillation columns
have little surge capacity and the flow of distillate and
bottom product
must match the feed flows.
6)Column pressure is normally controlled at a constant value.
The level of
controller on a preceding column often sets the feed flow
rate. It can be
independently controlled if the column is fed from a
storage tank. Feed
temperature is not controlled unless a pre-heater is used.
4.3

First aid measures

4.3.1 Swallowed
28

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
29

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) 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.
4.4

Accidental release measures

4.4.1 Minor spills

1) Remove all ignition sources and clean up all spills immediately.
2) Avoid contact with skin and eyes.
3) Control personal contact by using protective equipment.
4) Use dry clean up procedures and avoid generating dust.
5) Place in a suitable, labelled container for waste disposal.
4.4.2 Major spills
1) Clear area of personnel and move upwind.
2) Alert Emergency Responders and tell them location and nature
of hazard.

30

CHAPTER FIVE

MASS AND ENERGY BALANCE

5.1

Mass Balance

5.1.1

Introduction of mass balance

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.
5.2

Calculation of Mass Balance for Reactor

Molecular weight of C4H10 =58

Molecular weight of O2 =32
Molecular weight of C4H2O3 =98
Molecular weight of CO2 =44
Molecular weight of CO = 28
Molecular weight of H2O =18
Molecular weight of N2=28
31

Molecular weight of CH2O2 =46

Molecular weight of C3H4O2=72

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.

Figure 3

For stream 1
F1= 5130.9 kg/h
F1C4H10= 5130.9 kg/h
For stream 2 & stream 3
F2=F3= 95129.14 kg/h
F2o2 =F3o2=18074.54 kg/h
F2n2 = F3n3= 75152.02 kg/h
F2H20 = F3H20=1902.58 kg/h

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
32

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,

XC4H10=0.822

Figure 4

r1
r2
r3
r4

Conversion of C4H10=0.822 ( Preparation of maleic anhydride using fluidized

catalysts US 4317778)
XC4H10= - C4H10 rr / N4C4H10
0.822= -[(-1)r1+(-1)r2+(-1)r3+(-1)r4]/(5131.7158)
72.7287= r1+ r2 + r3+ r4

Selectivity of C4H203=0.7
( Preparation of maleic anhydride using fluidized catalysts US 4317778)
SC4H2O3 =C4H203 r / N4C4H10
0.7= r1/(5131.7158)
r1= 61.9339
33

Selectivity of CO2=co2r/N4C4H10= 1.5320

2r1+r2+3r3/(5131.7158)=1.5320
r2=9.02526
Selectivity of C3H4O2= 0.01
(Preparation of maleic anhydride using fluidized catalysts US 4317778)
SC3H4O2=C3H4O2 r /N4C4H10
0.01=r3/(5131.7158)
r3=0.88477

Selectivity of CH2O2 =0.01

( Preparation of maleic anhydride using fluidized catalysts US 4317778)
SCH2O2=CH2O2 r /N4C4H10
0.01=r4/(5131.7158)
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
34

C4H10:
NiC4H10 +C4H10 r = NoC4H10
5131.71/58 + (-r1) + (-r2) + (-r3) + (-r4) = NoC4H10
88.4778 61.9339 9.02526 0.88477- 0.88477 = NoC4H10
NoC4H10 = 15.7491 X 58
FoC4H10 = 913.4478kg/h

O2 :
NIo2 +O210 r= NoO2
18074.36/32 +( -3.5 r1) +( -5.5 r2) + (-3.5 r3) + (-6 r4)
NoO2 = 564.82375 - 216.76865 49.63893 3.096695 5.30862
NoO2 = 290 X 32
FOO2= 9280.34kg/h

C4H203:
NIc4h2o3 + C4H203 r = No C4H203
NoC4H203 = 0 + 61.9339X 98
FoC4H203 = 6069.5222kg/h

H2O:
NIH2O + H2O r = No H2O
1902.65/18 + 4 r1 + 5 r2 + 3 r3+ 4 r4= No H2O
No H2O = 105.7028 + 247.7358+ 45.1263+ 2.65431+3.53908
No H2O = 404.75829 X 18
FOH2O = 7285.64922kg/h

35

CO :
NICO + CO r = NoCO
O + 2 r2 = NoCO
NoCO = 2(9.02526) X 28
FOCO = 505.41456kg/h

CO2 :
NICO2 + CO2 r = NoCO2
0 + 2 r2 + r3+ 3 r4 = NoCO2
NoCO2 = 2(9.02526) + 0.88477 + 3(0.88477)
NoCO2=21.5896X 44
=949.9424 kg/h

C3H4O2:
NIC3H402+ C3H4O2 r = No C3H4O2
O + r3 = No C3H4O2
No C3H4O2 = 0.88477X 72
FOC3H4O2 = 63.70344kg/h

CH202 :
NICH2O2+ CH202 r = No CH202
0 + r4 = No CH202
0.88477 = No CH202
No CH2O2 = 0.88477
FoCH2O2=0.88477 X 46
FOCH2O2 = 40.69942kg/h
N2:
36

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 410C to
95C.

Figure 5
F5=F6

ABSORPTION TOWER

For stream 6
F6=100260.04kg/h
37

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
F9CH2O2=40.69942kg/h
F9C3H4O2=63.70344kg/h
F9C4H2O3=6069.5222kg/h
38

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
40C.

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

39

F10=F11+F12
Make assumption all butane goes to waste treatment

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
F12CH2O2=0.40699kg/h (1% selectivity)
F12C3H4O2=0.637034kg/h (1% selectivity)
F12C4H4O3=6008.82678kg/h (99% selectivity)
F10=F11+F12
40

16275.60186=8428.085+7847.5166
16275.601=16275.601 (proven)

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

For stream 14
F14=5775.595257kg/h
41

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+600.88
2678)+( 367.52916+0.122097+0.19111+5407.9440)
7847.516=2071.730+5775.95257(proven)

Total mass flow rate in = Total mass flow rate out

F1+F2+F7=F8+F11+F13+F14
5130.9+95129.14+1902.58=85886.623+8428.085+2071.730+5775.595257
102162=102162 (proven)

42

Stream
Temp. (C)

1
20

2
20

3
147.9

4
121

5
410

6
95

7
45

8
59.9

Press(kPa)

275

101

275

275

275

200

170

170

Vapor
0
1
1
1
1
Fraction
Total Flow 5130.9 95129.14 95129.14 100260.0 100260.04
(kg/h)
4
Componen
t
Flow(kg/h)

Nitrogen
Carbon
Monoxide

0
0

100260.04

75152.02 75152.02 75152.02 75150.92066 75150.92066

0
0
0
505.41456 505.41456

1902.58

85886.623

0
0

75150.9266
505.41456

Oxygen
0
18074.54 18074.54 18074.54 9280.34
9280.34
0
9280.34
Carbon
0
0
0
0
949.9424
949.9424
0
949.9424
Dioxide
Butane 5130.9
0
0
5130.9
913.4478
913.4478
0
0
Water
0
1902.58 1902.58 1902.58 7285.64922 7285.64922 1902.58
0
Formic
0
0
0
0
40.69942
40.69942
0
0
Acid
Arcylic
0
0
0
0
63.70344
63.70344
0
0
Acid
Maleic
0
0
0
0
6069.5222 6069.5222
0
0
Anhydride

5.2

Energy Balance

5.2.1 Introduction of energy balance

43

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.
5.2.2 Calculation of energy balance of the reactor
Stream
4

121oC

Nitrogen gas
Oxygen gas
Water
n-butane
Reactor 1

Stream
5
410oC

44

Nitrogen gas
Oxygen gas
Water
n-butane
Carbon monoxide gas
Carbon dioxide gas
Formic acid
Acrylic acid
Maleic anhydride

Table 5.3 Properties data of each component

Liquid-Phase Heat Capacity: Cp = A + BT + CT2 + DT3 + ET4
Liquid-Phase Heat Capacity (J/kmol.K)
Component

Water

92.0
53

-3.9953e-2

-2.1103e-4

Maleic
anhydride

3.12
3

0.08323

n-butane

3.96

Oxygen

25.4
8

-5.217X105

5.3469e-7

1.156X10-7

37.15X10-

-18.34X10-

35X10-9

1.520X10-

0.7155X10

1.312X10-9

-5

0.1571X1
0-2

Nitrogen

28.9
0

0.8081X10

Carbon dioxide

22.2
6

5.981X10-

-3.501X10-

Carbon
monoxide

28.1
6

0.1675X1
0-2

0.5372X10

-5

-5

-2.873X10-9

7.469X10-9
-2.222X10-9

Cp acrylic acid = 2050 J/kmol.K

Cp formic acid = 101.3 J/kmol.K
Stream 4
394

394

i Oxygen

Cp dT =
298

298.

A + BT + CT2 + DT3 dT

298

298.

= AT + BT2/2 + CT3/3 + DT4/4

45

= 25.48(394-298)+(1/2)(1.52X10-2)(3942-2982)+(1/3)(0.7155X10-5)
(3943-2983)+(1/4)(1.312X10-9)(3944-2984)
= 2873.52 J/kmol.K

394

i Nitrogen

394

Cp dT = A + BT + CT2 + DT3 dT

=
298

298

298.

298.

= AT + BT2/2 + CT3/3 + DT4/4

=28.90(394-298)+(1/2)(-0.1571X10-2)(3942-

2982)+(1/3)(0.8081X10-5)
(3943-2983)+(1/4)(-2.873X10-9)(3944-2984)
= 2804.05 J/kmol.K
394

i Water

394

= Cp dT = A + BT + CT2 + DT3 dT
298

298

298.

298.

= AT + BT2/2 + CT3/3 + DT4/4

=92.053 (394-298)+(1/2)( -3.9953e-2)(3942-

2982)+(1/3)( -2.1103e-4)
(3943-2983)+(1/4)( 5.3469e-7)(3944-2984)
= 19302287.84 J/kmol.K
394

i n-butane

394

Cp dT
298

298.

298

A + BT + CT2 + DT3 dT

298.

= AT + BT2/2 + CT3/3 + DT4/4

=3.96 (394-298)+(1/2)( 37.15X10-2)(3942-2982)+(1/3)(

-18.34X10-5)
46

(3943-2983)+(1/4)( 35X10-9)(3944-2984)
= 10740.43 J/kmol.K
Stream 5
683

o Oxygen

683

Cp dT
298

A + BT + CT2 + DT3 dT

298

298.

298.

= AT + BT2/2 + CT3/3 + DT4/4

= 25.48(683-298)+(1/2)(1.52X10-2)(6832-2982)+(1/3)(-

0.7155X10-5)
(6833-2983)+(1/4)(1.312X10-9)(6834-2984)
= 12052.23 J/kmol.K

683

o Nitrogen

683

Cp dT
298

A + BT + CT2 + DT3 dT

298

298.

298.

= AT + BT2/2 + CT3/3 + DT4/4

= 28.90 (683-298)+(1/2)( -0.1571X10-2)(68322982)
+(1/3)( 0.8081X10-5)(6833-2983)+(1/4)( -2.873X10-

)(6834-2984)
= 11466.33 J/kmol.K
683

683

o water

Cp dT = A + BT + CT2 + DT3 dT

=
298

298

298.

298.

= AT + BT2/2 + CT3/3 + DT4/4

= 92.053(683-298)+(1/2)( -3.9953e-2)(6832-

2982)+(1/3)( -2.1103e-4)
(6833-2983)+(1/4)( 5.3469e-7)(6834-2984)
= 251811.59 J/kmol.K
683

o n-butane

683

= Cp dT = A + BT + CT2 + DT3 dT
298

298.

298

298.

47

= AT + BT2/2 + CT3/3 + DT4/4

= 3.96 (683-298)+(1/2)( 37.15X10-2)(6832-2982)+(1/3)
( -18.34X10-5)
(6833-2983)+(1/4)( 35X10-9)(6834-2984)
= 55654.68 J/kmol.K
683

o carbon monoxide

683

Cp dT

298

A + BT + CT2 + DT3 dT

298

298.

298.

= AT + BT2/2 + CT3/3 + DT4/4

= 28.16(683-298)+(1/2)( 0.1675X10-2)(6832-2982)
+(1/3)( 0.5372X10-5) (6833-2983)+(1/4)(

-2.222X10-9)(6834-2984)
= 11564.55 J/kmol.K

683

683

o carbon dionoxide

=
298

Cp dT =

A + BT + CT2 + DT3 dT

298

298.

298.

= AT + BT2/2 + CT3/3 + DT4/4

= 22.26 (683-298)+(1/2)( 5.981X10-2)(6832-

2982)+(1/3)( -3.501X10-5)
(6833-2983)+(1/4)( 7.469X10-9)(6834-2984)
= 16847.01 J/kmol.K
683

o maleic anhydride

=
298

298.

683

Cp dT =

A + BT + CT2 + DT3 dT

298

298.

= AT + BT2/2 + CT3/3 + DT4/4

= -3.123 (683-298)+(1/2)( 0.08323)(6832-2982)+(1/3)(

-5.217X10-5)
(6833-2983)+(1/4)( 1.156X10-7)(6834-2984)
48

= 15495.6 J/kmol.K
683

o formic acid

683

Cp dT
298

101.3 dT

298

298.

298.

=39000.5 J/kmol.K

683

o acrylic acid

683

=
298

298.

Cp dT

2050 dT

298

298.

=789250 J/kmol.K

Stream 4
Component

Molar flow
rate, N

Enthalpy, i
(kJ/kmol.K)

Nitrogen gas

(kmol/h)
2684

2.804

Oxygen gas

564.83

2.874

n-butane

88.28

10.74

Water

105.70

19302.29

Molar flow
rate, N

Enthalpy, o

Nnitrogen initrogen = 7525.94

NOxygen iOxygen = 1623.32
Nn-butane in-butane = 948.13
Nwater iwater = 2040252
4 = 2050349.39

Stream 5

Component

49

(kJ/kmol.K)

Nitrogen gas

2683.96

11.47

Carbon
monoxide

18.05

11.56

Oxygen

290.01

12.05

Carbon dioxide

21.59

16.85

n-butane

15.72

55.65

Water

404.76

251.81

Formic acid

0.8842

39.00

Acrylic acid

0.8840

789.25

Maleic
anhydride

61.896

15.5

Nnitrogen onitrogen= 30785.02

NCarbon monoxide oCarbon monoxide = 208.66
Noxygen ooxygen = 3494.62
NCarbon dioxide ocarbon dioxide = 363.79
Nn-butane on-butane = 874.82
Nwater owater = 101922.62
Nformic acid oformic acid = 34.48
N

Acrylic acid

Maleic anhydride

Acrylic acid =

666.13

Maleic anhydride =

959.39

H5 = 139309.53

Q= out-in+r(Hof)
(Hof) = -a(Hofn-butane) b(HofO2) +c(Hofmaleic anhydride) +d(Hofwater)
= -1(-125kJ/mol) -3.5(0) +1(-398.076) +1(-286kJ/mol)
50

=-559.08 kJ/mol
r(Hof) = 61.9339 (-559.08 kJ/mol)
= - 34626 kJ/mol
Q

= 139309.85-2050349-34626
-1945665.15 kJ/hour (exothermic reaction)

Therefore, the reactor need to release 1945665.15 kJ/hour of heat in

order for the process to occur.

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
51

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, theres 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.

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52

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54

APPENDIX

55