MANUFACTURE OF MALEIC ANHYDRIDE

Submitted in partial fulfillment for the award of the degree

of

BACHELOR OF TECHNOLOGY
in

CHEMICAL ENGINEERING
by

CHANDRU.V (10704002)
ANURAJ.R (10704022)
under the guidance of

Mrs.E.Poonguzhali, B.Tech.,
(Lecturer, School of Chemical Engineering)

FACULTY OF
ENGINEERING AND TECHNOLOGY
SRM UNIVERSITY
(under section 3 of UGC Act,1956)
SRM Nagar, Kattankulathur 603 203
Kancheepuram Dist.

MAY 2008

BONAFIDE CERTIFICATE
Certified that this project report MANUFACTURE OF MALEIC
ANHYDRIDE is the bonafide work of CHANDRU.V (10704002), ANURAJ.R
(10704022) who carried out the project work under my supervision.

HEAD OF THE DEPARTMENT

INTERNAL GUIDE

Date:

EXTERNAL EXAMINER

INTERNAL EXAMINER

Date :

ACKNOWLEDGEMENT
2

ACKNOWLEDGEMENT
First of all, we thank Dr.C.Muthamizhselvan, Associate Director, S.R.M
University (Engg & Technology) for allowing us to work on this project.
We are extremely thankful to Dr.R.Karthikeyan, B.E., PhD, Professor and
Head,

School of Chemical Engineering, S.R.M University, for permitting us to

venture on this project and providing us with good support and guidance.
We would like to thank Mrs.E.Poonguzhali B.Tech, , Faculty, School of
Chemical Engineering, S.R.M University, for her encouragement and guidance at all
stages of this project.
We would like to thank the management and staff of E.I.D Parry (India)
Limited, Pudukottai, for their valuable assistance.
We extend our sincere thanks to all the staff members of the School of
Chemical Engineering, S.R.M University, for their support and assistance.

CONTENTS

Page no

1. INTRODUCTION

2. PROPERTIES

3. APPLICATIONS

4. PROCESS DESCRIPTION

5. MATERIAL BALANCE

16

6. ENERGY BALANCE

20

7. DESIGN

25

8. PROCESS CONTROL
AND INSTRUMENTATION
9. SAFETY AND LOSS PREVENTION

33
37

10. PLANT LAYOUT

41

11. PROCESS ECONOMICS

46

12. CONCLUSION

55

13. REFERENCE

57

INTRODUCTION

INTRODUCTION
The dominant end use of Maleic anhydride (MA) is in the production of
unsaturated polyester resins. These laminating resins, which have high structural
strength and good dielectric properties, have a variety of applications in automobile
bodies, building panels, molded boats, chemical storage tanks, lightweight pipe,
machinery housings, furniture, radar domes, luggage, and bathtubs. Other end
products are fumaric acid, agricultural chemicals, alkyd resins, lubricants,
copolymers, plastics,succinic acid, surface active agents, and more. In the United
States, one plant uses only n-butane 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 byproduct 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.
The model Maleic Anhydride plant, as described in this section, has a
benzene-to- Maleic Anhydride conversion rate of 97.7 percent. Because of a lack of
data on the n-butane process, this discussion covers only the benzene oxidation
process.

History
In OSHA Method 25 , Maleic anhydride is collected and derivatives on p-anisidinecoated XAD-2 tubes. An untreated XAD-2 tube is connected in series to trap the p-anisidine
that is partly leached from the first tube during sampling. In trying to develop sampling and
analytical methods for a series of anhydrides (acetic, maleic, phthalic, and trimellitic),
derivatizing agents other than p-anisidine were investigated to obviate the use of the second
tube. 1-(2-Pyridyl)piperazine, the agent used in earlier methods for a series of isocyanates was
considered. A sampling method for acetic anhydride was validated using this derivatizing
agent. With maleic and other anhydrides, however, this reagent was found to be unsatisfactory
due to the instability of its derivatives. After a brief survey, veratrylamine was selected
because: (1) it readily forms relatively stable acid-amides with these anhydrides, (2)it does not

leach from the glass fiber filters impregnated with it, even at a flow of 1 liter per minute, and
(3) its cost is reasonable. The sampling device consists of two filters which are separated by a
center support section Samples are collected closed-face to minimize contamination.

SOURCES AND EMISSIONS

Sources
Maleic anhydride is used in the manufacture of alkyl and polyester resins,
surface coatings, agricultural chemicals, copolymers, malic and fumaric acids, and as
an oil additive
The primary stationary sources that have reported emissions of maleic anhydride in
California are sources that manufacture or use plastic materials and synthetics,
manufacturers of soaps, cleaners, and toilet goods, and national security installations
Emissions
The total emissions of Maleic anhydride from stationary sources in California
are estimated to be at least 4,900 pounds per year, based on data reported under the
Air Toxics .

PROPERTIES

PROPERTIES
Chronic Toxicity Summary
Inhalation reference exposure level

l 0.7 g/m3 (2.5 ppb)

Critical effect(s) Neutrophilic infiltration of the nasal epithelium;

Irritation of the respiratory system in rats,
Hamsters and monkeys
Hazard index target(s) Respiratory system
Chemical Property Summary
Description Colorless or white solid
Molecular formula

C4H2O3

Molecular weight

98.06 g/mol

Boiling point

202C

Melting point

52.8C

Vapor pressure 0.1 torr @ 25C (AIHA, 1970)

Solubility Soluble in water, ether, acetate, chloroform,
Dioxane;

25C , 227 g/100 g acetone,

112 g/100 g ethyl acetate,

52.5 g/100 g

Chloroform,

50 g/100 g benzene,

23.4 g/100 g toluene, 19.4 g/100 g o-xylene,

0.6 g/100 g CCl4, 0.25 g/100 g ligroin
Conversion factor

4.0 g/m3 per ppb at 25C

APPLICATIONS

10

Applications

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.

It is also used as a co-monomer for unsaturated polyester resins, an ingredient

in bonding agents used to manufacture plywood, a corrosion inhibitor, and a
preservative in oils and fats.

The annual statewide industrial emissions from facilities reporting under the
Air Toxics Hot Spots Act in California based on the most recent inventory
were estimated to be 7366 pounds of Maleic anhydride.

11

PROCESS DESCRIPTION

12

PROCESS DESCRIPTION
Maleic anhydride was first commercially produced in the early 1930s by the
Vapor-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 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 butenes present in mixed C4 streams have been practiced
commercially. None of these processes is currently in operation. 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. 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-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, and through rapid advances in catalyst technology has
been debottlenecked to a current capacity of 105,000t/yr (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 butane-based plants.

13

By the mid-1980s in the United States 100% of maleic anhydride production

used butane as the feedstock. Coincident with the rapid development of the butanebased 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
CONDEA-Huntsman, Pantochim and Lonza. Growth in the worldwide Maleic
anhydride industry is predominantly in the butane-to-maleic anhydride route, often at
the expense of benzene-based production. Table 4 shows 1993 and 2000 worldwide
Maleic anhydride production capacity broken down in categories of fixed-bed
benzene, fixed-bed butane, fluidized-bed butane, and phthalic anhydride coproduct.
As can be seen from this table, both fixed- and fluidized-bed butane routes have
grown dramatically with the fixed-bed route adding 336,000t/yr capacity compared to
90,000t/yr for the fluid-bed process. 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 nonflammable 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.
The catalyst used for the conversion of benzene to maleic anhydride consists
of supported vanadium oxide. The support is an inert oxide such as kieselguhr,

14

alumina, or silica, and is of low surface area . Supports with higher surface area
adversely affect conversion of benzene to Maleic anhydride. The conversion of
benzene to Maleic anhydride is a less complex oxidation than the conversion of
butane, so higher catalyst selectivitys are obtained. The vanadium oxide on the
surface of the support is often modified with molybdenum oxides. There is
approximately 70% vanadium oxide and 30% molybdenum oxide in the active phase
for these fixed-bed catalysts. The molybdenum oxide is thought to form either a solid
solution or compound oxide with the vanadium oxide and result in a more active
catalyst.

Maleic anhydride is produced by the controlled air oxidation of benzene,

illustrated by the following chemical reaction:
C6H6 +

4.5O2

Benzene

Oxygen

C4H2O3 +
Maleicanhydride

2H2O + 2CO2
Water

Carbon- dioxide

Air-79 mol%N2, 21mol%O2 at 200% excess based on Maleic anhydride

formation reaction (note: 100% excess is double the stoichiometric amount).
Vaporized 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), forming
a vapor of, water, and carbon dioxide. The exothermic heat of reaction is removed, by
circulating molten salt, or by generating steam, in the shell side of the reactor.
The vapor, which may also contain oxygen, nitrogen, carbon monoxide,
benzene, maleic acid, formaldehyde, formic acid, and other compounds from side
reactions, Maleic Anhydride leaves the reactor and is cooled and partially condensed
so that about 40 percent of the Maleic Anhydride is recovered in a crude liquid state.
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 %maleic acid. Dibutyl phthalate solvent is
used in absorption column,where 99% of the maleic anhydride is absorbed into

15

dibutyl phthalate. Some processes may use a double-effect vacuum evaporator at this
point.Waste gas from the absorber contains unreacted benzene and O2, N2, CO2, and
H2O, plus some dibutyl phthalate . This Maleic Anhydride is then combined in
storage with that from the separator. The molten product is aged to allow colorforming impurities to polymerize. These are then removed in a distillation column,
leaving the finished product.In the distillation column separation of maleic anhydride
and dibutyl phthalate 99 mol % of maleic anhydride separates and send to storage
tank. MA product is usually stored in liquid form, although it is sometimes flaked and
palletized into briquettes and bagged.[Reference : 2]
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. The refining
vacuum system vent,the only other exit for process emissions. Benzene oxidation
process emissions can be controlled at the main vent by means of carbon adsorption,
thermal incineration, or catalytic incineration. Benzene emissions can be eliminated
by conversion to the n-butane process. Catalytic incineration and conversion from the
benzene process to the n-butane process are not discussed for lack of data. The vent
from the refining vacuum system is combined with that of the main process as a
control for refining vacuum system emissions. A carbon adsorption system or an
incineration system can be designed and operated at a 99.5 %removal efficiency for
benzene and volatile organic compounds.
The entire Maleic anhydride process should be optimized using decision
variables of your choosing. Decision variables should be chosen as the design
variables most strongly affecting the objective function. There are topological
optimization and parametric optimization. In topological optimization, which is
usually done first, the best process configuration is chosen. Parametric optimization
involves varying operating variables and should be done after topological
optimization is complete. Some examples of parameters that can be used as decision
variables are reactor temperature, pressure, and conversion; absorber temperature and
pressure; and distillation column reflux ratio.

16

17

EQUIPMENTS
Compressor
The compressor increases the pressure of the feed air to approximately 12 atm. The
compressor may be assumed to be adiabatic with an efficiency of 75%. It may be
necessary to use staged compressors with inter cooling.
Heat Exchanger
This heat exchanger vaporizes the benzene feed to saturated vapor at the stream
pressure, which you must choose based on the optimization in mini-design #1.

Fired Heater
This heats reactor feed vapor to reaction temperature. Natural gas is used as the
fuel, and the amount needed is based on the LHV of natural gas and the process heat
load. The cost of natural gas is a utility cost, and you should assume that the fired
heater is 85% efficient.

Reactor Information
The reaction conditions are limited to temperatures between 450C and 650C.
Table 1 gives conversion and selectivity information for the reactor. It should be
observed that CO2, the undesired product, is also formed in the desired reaction.
Therefore, the maximum possible selectivity, defined as maleic anhydride
formed/total CO2 formed, is 0.5.

18

Reactor Conversions and Selectivities

X
selectivity
T (C)
conversion of
lbmoles maleic
benzene
anhydride/lbmoles
CO2
450
17.5
0.257
460
21.6
0.252
480
31.8
0.238
500
44.5
0.229
520
58.8
0.219
540
63.0
0.208
560
85.0
0.197
580
93.3
0.185
600
97.7
0.175
620
99.47
0.163
640
99.92
0.152
650
99.97
0.147

Thermodynamics of components
The separations section of this process involves dibutyl phthalate, maleic
anhydride, maleic acid, and quinone. It is necessary to understand the vapor-liquid
equilibrium between different pairs of these components. Specifically, you are to
investigate the vapor-liquid equilibrium between maleic anhydride and quinone,
maleic anhydride and maleic acid, and maleic acid and dibutyl phthalate. First of all,
check different thermodynamics packages in Chemcad to see if there are differences
between the predictions of the packages. The term thermodynamics package means
the choice of K-value and enthalpy calculation methods. At a minimum, you should
investigate ideal, SRK, Peng-Robinson, UNIQAC, UNIFAC, UNIFAC/UNIQAC,
plus the recommendation of the expert system if it differs from those listed above.
Specifically, examine the T-xy diagrams of the pairs of components using the same
thermodynamics packages at a variety of possible operating pressures (1-10 atm) for
the separation section. The presence of azeotropes strongly affects the ability to do
separations.

What do you observe?

Compare the predictions of the different

packages. Explain and discuss reasons for any differences observed.

Additionally, there appears to be a discrepancy in the reported physical
properties for some of the components involved in this design. Specifically, the

19

properties in the Chemcad data base do not match those in other published data bases.
Please investigate this problem in depth and determine which information is correct.
If the Chemcad data base is in error, discuss how the vapor-liquid equilibrium results
would be affected.

MATERIAL BALANCE

20

MATERIAL BALANCE
Molecular weight of C6H6

=78

Molecular weight of O2

=32

Molecular weight of C4H2O3

=98

Molecular weight of CO2

=44

Molecular weight of H2O

=18

REACTOR
C6H6+4.5O2C4H2O3+2CO2+2H2O
Basis: Produce 3000tons maleic anhydride per year
We take 1000kg of benzene
Its a batch process. Working days is 250days/yr

Feed
C6H6

1000kg

Theo. O2

(144/78)*1000

1846.15kg

1846.15+(1846.15*200/100)

5538.45kg

5538*(79/21)

20835.12kg

(144/78)*977

1803.6923kg

=
=

(98/78)*977
1227.512kg

Exp. O2
N2 in the air

97.7% conversion
Reacted O2

Product
C4H2O3 formed

21

Unreacted C6H6

=
=

1000-977
23kg

Unreacted O2

5538.45-1803.69

3734.755kg

(88/78)*977

1102.25kg

(36/78)*977

450.92kg

20835.12kg

CO2 formed

H2O formed

Unreacted N2

Air
O2-5538.45Kg
N2-20835.12Kg

REACTOR
C6H6-1000kg

C4H2O3-1227.512Kg/hr
CO2-1102.25Kg
H2O-450.92Kg
O2-3734.75Kg

ABSORBER
99% of the Maleic anhydride is absorbed into Dibutyl phthalate

22

Dibutyl phthalate -900Kg

ABSORBER

C4H2O3-1227.51Kg/hr
CO2-1102.25Kg
O2-3734.75Kg
C6H6-23Kg

C4H2O31215.23Kg
Dibutyl
phthalate896 Kg

Dibutyl phthalate-4Kg
CO2-1102.25Kg
O2-3734.75Kg
C6H6-23Kg

DISTILLATION COLUMN
Separation of maleic anhydride and dibutyl phthalate

C4H2O3-1215.23Kg
Dibutyl phthalate896Kg

DISTILLATION COLUMN
C4H2O3-1202Kg

99%

Dibuty phthalate-6Kg

Recycle
Dibuty phthalate-890Kg
C4H2O3 -13.23Kg

Maleic anhydride produced from distillation column=1202kg/hr

=12.02tons/day
=3000tons/yr

23

ENERGY BALANCE

24

ENERGY BALANCE
VAPORISER
Q C6H6

10000.240910 (283-273)

240910 cal

2.40910 k cal

HEATER
Reference Temperature = 0C
Heat associated with reactants
Q C6H6

Qair

10000.240910(283-273)

240910 cal

2.40910 k cal

26373.57140.240810(313-273)

254030.2310 cal

254.0310 k cal

Heat associated with products

QC6H6 =

QN2

QO2

10000.605710(873-273)

36342010 cal

363.4210 k cal

20835.121410/14 273.15 873.15 (6.5+0.00100T)dT

3157927.2610 cal

3157.927310 k cal

5538.4510/32273.15873.15(8.27+0.000258T-187700/T)dT

792435.2310 cal

792.435210 k cal
Heat change

= Qpdt Hreac

25

(3157.9273+792.4352+363.42-2.409-254.03) 10

4057.3510 k cal

REACTOR
Reference Temperature = 25C
C6H6 + 4.5 O2 C4H2O3+ CO2 + H2O
Standard heat of reaction
HR = Hf Pdt Hf reac
= [-94.052+2 (-68.3164)+(-4062)]-

[0+6.9152]

= -4299.602 k cal
Heat associated with reactants
QC6H6

10000.605710(873.15-298.15)

348277.510 cal

348.277510 k cal

Q O2

5538.4510/32298.15873.15 (8.27+0.000258T-187700/T)dT

4427557.210 cal

4427.557210 k cal
Heat associated with products

Q C4H2O3
=

1227.512810/98298.15873.15 (93760+188.9T)d

35124.9610 cal

351.524910 k cal
= 1102.2510/44298.15873.15(10.34+0.00274T-195500/T)dT

Q CO2
=

161238.761410 cal

161.238710 k

cal
26

Q H 2O

450.9210/18298.15873.15(8.22+0.22015T+0.00000134T)dT

1982726.22410 cal

1982.72610 k cal

Heat Required =

Qpdt hreac + HR

(2495.4898-4775.8347- 4299.602)10

-6579.946910 k cal

6579.946910 k cal of heat it released

COOLER
Maleic Anhydride
mCpT

Water

mCpT

(1227.512810/98)10373.15873.15 (93670+188.9T)dT = m10/18

303.15

318.15

(8.22+0.22015T+0.00000134T)dT
m

=
=

3974730 kg
3974.730 tonnes

REBOILER
INPUT
Q DBP

896/278 100.192
616.04T+2.2101T)dT

8753982.39410 cal

27

475.15
(461790373.15

8753.98210 k cal

OUTPUT
Q DBP

896/278 100.192 373.15 613.15(461790-

616.04T+2.2101T)dT
= 36350930.310 cal
= 36350.930310 k cal

HEAT CHANGE

OUTPUT INPUT

27596.9510 k cal

CONDENSER

MALEIC ANHYDRIDE

WATER

1202/98100.192303.15 318.15 (93760+188.9T)dT = m/1810

303.15

475.15

(8.22+0.22015T+0.00000134T)dT

m = 1058909 kg
= 1058.91 tonnes

28

DESIGN

29

Design
Reactor
Spherical catalyst particle diameter =

0.03m

Catalyst paryticle density ,

1600khg/m3

0.0873kg/m3

As/Ap

(6Vp/)2/3

Vp

1.41310-5m3

-fluidization, mf

(0.071/)1/3

mf

0.414

Sphericity,

Void fraction at minimum-

Remf

dphmfg/

(33.722+0.0408Ar)1/2-33.72

Archimedes number
Ar

dp3g(s-g)/ 2

0.033.0879(1600-.0879)9.81/8.52

5.1510-4

Minimum fluidization velocity

Umf

5.40610-7m/s

Volumetric flow rate

Residence time

mass flow rate/density

1000/.0879

3.16m/sec

V/v0

3.476/3016

1.1sec

Volume of the reactor

V

r2H

6D3/4

3.476

6D3/4

13.904

6D3

30

D3

13.904 / 6

0.9m

6D

60.9

5.4m

Design datas:
Diameter of reactor

0.9m

Height of reactor

5.4m

Minimum fluidization velocity

[Reference:9]

31

5.40610-7m/s

FLUIDIZED BED REACTOR

32

Distillation column
Maleic anhydride

1251-23/98

12.4 moles

896/278

3.22moles

3.22+12.4

15.262moles

0.793

1202/98

12.265moles

6/278

0.0216moles

xD

0.998

xB

0.04

xF

0.793

xD

0.998

xB

0.04

Dibutyl phthalate
Total moles
xF
Distillate
Maleic anhydride
Dibutyl phthalate

33

VLE data maleic anhydride and dibutyl phthalate system

X

0
.019
.0721
.0966
.1661
.2337
.2608
.3273
.3965
.5079
.5189
.5732
.6763
.7472
.8943

0
.17
.3891
.4375
.5089
.5445
.558
.5826
.6122
.6584
.6599
.6856
.7485
.7815
.8951

Assuming gas velocity, uc

= 1.3675m/s

Bubbling area

v/uc

Vapor flow rate

1404kg/sec

To fond volumetric flow rate

v

mass flow rate /Density

1.404/2.1227

3
0.5372m /sec

0.5372/1.3675

2
0.3928m

Bubbling area

0.3928/0.7

0.5611m2

D2/4

0.5611

[(40.5611)/ ]1/2

0.8453m

85cm

Bubbling area

C.S.A of column

/0.7

34

0.998/(R+1)

0.998/(3+1)

0.2495

Reflux ratio is taken as 3

Slope = 1-/
Where = Fraction vaporized
Assuming =1
Slope = 0
From graph,
Number if theoretical stages = 13
Excluding reboiler the number of trays

13-1

12

Assuming efficiency

70%

Actual number of trays

12/0.7

17

Assuming trays spacing

40cm = 0.4m

Height of the distillation column

(17 0.4) + (20.4)

7.6m

Design Data:
Diameter of distillation column

0 .85m

Height of the distillation column

7.6m

Actual number of trays

17

[Reference:7]

35

DISTILLATION COLUMN

VAPOUR

LQUID
WATER OUT
WATER IN

OVERHEAD
PUMP
PRODUCT
FEED

LIQUID

REBOILER
STEAM
CONDENSATE
VAPOUR
BOTTOM PRODUCT

36

PROCESS CONTROL AND

INSTRUMENTATION

37

PROCESS CONTROL AND INSTRUMENTATION

The primary objectives of the designer when specifying instrumentation and

Control schemes are

SAFE PLANT OPERTION

a) To keep the process variables within known safe operating limit.
b) To detect dangerous situations as they develop and provide alarms and automatic
shutdown systems.
c) To provide inter locks and alarms to prevent dangerous operating procedures.
1. Production rate:
To achieve the desired product output.
2. Product Quality:
To maintain the product composition within specified quality standards.
3. Cost:
To operate at the lowest production cost , commensurate with the other objectives.
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 design of the equipment, the control value should be
placed on the discharge line from the pump.

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.
FLOW CONTROL

38

Flow control is usually with inventory control in a storage tank or othe r 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.
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 stream s whose flows are fixed, bypass control will have to be used.
CONDENSOR CONTROL
Temperature control is unlikely to be effective, unless the liquid stream is subcooled. Pressure control is often used, or control can be based on the outlet coolant
temperature.

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 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 unreacted materials from the reactor .

DISTILATION COLUMN CONTROL

39

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.
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.
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 preheater is used.

40

SAFETY AND LOSS PREVENTION

41

SAFETY AND LOSS PREVENTION

Any organization has a legal and moral obligation to safeguard the health and welfare
of its employees and the general public. The term loss prevention is an insurance
term, the loss being the financial loss caused by an accident. These losses will not
only be the cost of replacing damaged plant and third party claims ,but also the loss of
earnings from lost sales opportunities.
All manufacturing processes are to some extent hazardous, but in chemical process
are additional, special , hazards associated with the chemicals used and the process
condition. the designer must be aware of these hazards, and ensure , through the
application of sound engineering practice that the risks are reduced to acceptable
levels.
Safety and loss prevention in process design can be considered under the broad
headings
1)

Identification and assessment of the hazards.

2)

Control of the hazards.

3)

Control of the process.

4)

Limitation of the loss.

The duty of designer to select a process that is inherently safe whenever it is practical
and economical, to do so. However, most chemical manufacturing processes are, to
greater or lesser extent, inherently safe and dangerous situations can develop if the
process deviates from the design values.
The term engineered safety covers the provision in the design of control systems ,
alarms trips , pressure relief devices , automatic shutdown systems, duplication of key
equipment services , fire fighting equipment, sprinkler systems and blast wall to
contain any fire or explosion.

HEALTH EFFECTS
Probable rout The ACGIH threshold limit value in air for maleic anhydride is 0.25
ppm and the OSHA permissible exposure level (PEL) is also 0.25 ppm. Maleic

42

anhydride is a corrosive irritant to eyes, skin, and mucous membranes. Pulmonary

edema (collection of fluid in the lungs) can result from air born exposure. Skin
contact should be avoided by the use of rubber gloves. Dust respirators should be used
when maleic anhydride dust is present. Maleic anhydride is combustible when
exposed to heat or flame and can react vigorously on contact with oxidizers. The
material reacts exothermically with water or steam. Violent decompositions of maleic
anhydride can be catalyzed at high temperature by strong bases (sodium hydroxide,
potassium hydroxide, calcium hydroxide, alkali metals, amines, etc.). Precaution
should be taken during the manufacture and use of maleic anhydride to minimize the
presence of basic materials in maleic anhydride.
Non-Cancer: Maleic anhydride is both a skin and respiratory sensitizer. Inhalation
exposure to maleic anhydride may cause irritation to the respiratory tract, eyes, and
skin. Long-term inhalation exposure to maleic anhydride may cause chronic
bronchitis, asthma, pulmonary edema, upper respiratory tract irritation, eye irritation,
and dermatitis. Rats exposed to maleic anhydride via gavages developed renal lesions.
An acute non-cancer Reference Exposure Level (REL) of 10 micrograms per cubic
meter (g/m3) and a chronic REL of 2.4 g/m3 are listed for maleic anhydride in the
California Air Pollution Control Officers Association Air Toxics "Hot Spots"
Program, Revised 1992 Risk Assessment Guidelines. The toxicological endpoint
considered for chronic toxicity is the respiratory system, and the endpoint for acute
toxicity is respiratory irritation .The United States Environmental Protection Agency
has established an oral Reference Dose of 0.1 milligrams per kilogram per day for
maleic anhydride based on renal lesions in rats. The U.S. EPA estimates that
consumption of this dose or less, over a lifetime, would not result in the occurrence of
chronic, non-cancer effects. The U.S. EPA has not established a Reference
Concentration (RFC) for maleic anhydride
No information is available on adverse reproductive or developmental effects of
maleic anhydride in humans. In one study, abnormalities were reported in the
offspring of mice exposed by injection. No teratogenic or phototoxic effects were
observed in the offspring of rats exposed via gavages or diet

43

Cancer: No information is available regarding the carcinogenic effects of maleic

anhydride in humans, and there is limited evidence in animals. The U.S. EPA has not
classified maleic anhydride because it has not been adequately tested for potential
carcinogenicity). The International Agency for Research on Cancer has not classified
maleic anhydride with respect to potential carcinogenicity.

44

PLANT LOCATION AND

SITE LAYOUT
45

PLANT LOCATION AND SITE LAYOUT

The location of the plant has a crucial effect on the profitability of a project, and the
scope for future expansion. The principal factors to be considered are:

1. Location, with respect to the marketing area

For a plant that produces a product at a high cost it is better to locate the plant close to
the marketing area. This will help us to reduce our transportation cost.

2. Raw materials supply

Te availability and price of the raw materials will often determine the site location. It
is better to locate the plant in such a way that there is easy access both to the raw
materials and also to the market.

3. Transport
Transport of raw materials, finished products and labor to and from the plant also
plays a key role in selecting the plant site.

4. Availability of labor
Labor will be need for the construction and operation of any plant. Skilled
construction will usually be brought in from outside the site area, but there should be
an adequate pool of unskilled labors available locally; and labors suitable to operate
the plant.

5. Utilities
Chemical processes invariably require large quantities of water for cooling and
general process use, and the plant must be located near a source of water of suitable
quality and quantity. Rivers, wells, lakes, sea etc can be used as sources of water .

46

6. Environmental impact
All industrial processes produce waste products, and full consideration must be
given to the difficulties and cost of their disposal. The disposal of toxic and harmful
effluents will be covered by local regulations and it is essential that these regulations
must be met.
7. Climate
Adverse climatic conditions at a site will increase costs. Buildings should be provide
with the necessary facilities.
8. Political and strategic considerations
Capital grants, tax concessions and other inducements are often given by
governments to direct new investment to preferred locations; such areas of high
unemployment. The availability of such grants can be overriding consideration in site
selection.
PROCESSING AREA
Processing area also known as plant area is the main part of the plant where the actual
production takes place. There are two ways of laying out the processing area
1) Grouped layout
2) Flow line layout
GROUPED LAYOUT
Grouped layout places all similar pieces of equipment adjacent. This provides for ease
of operation and switching from one unit to another. This is suitable for large plants.

FLOW LINE LAYOUT

Flow line layout uses the line system, which locates all the equipment in the
order in which it occurs on the flow sheet. This minimizes the length of transfer lines
and therefore reduces the energy needed to transport materials. This is used mainly for
small volume products.

STORAGE HOUSE

47

The main stage areas placed between the loading and unloading facilities and
the process they serve. The amount of space required for storage is determined from
how much is to be stored in what size containers. In raw material storage, liquids are
stored in bulk containers. Solids on the other hand are frequently stored in smaller
containers or in a pile on the ground.
UTILITIES
The word Utilities is now generally used for ancillary services needed in
the operation of any production process. These services will normally be supplied
from central site facilities and will include:
1. Electricity
2. Steam for process heating
3. Cooling water
4. Water for general uses
5. Inert gas supplies
FIRE STATION
Fire station should be located adjacent to the plant area, so that in case of
fire or emergency, the service can be put into action.
MEDICAL FACILITIES
Medical facilities should be provided with at least basic facilities giving
first aid to the injured workers. Provision must be made for the environmentally
acceptable disposal of effluent.

48

49

PROCESS ECONOMICS

50

ECONOMIC DATA

Equipment Costs
The numbers following the attribute are the minimum and maximum values for
that attribute. For a piece of equipment with a lower attribute value, use the minimum
attribute value to compute the cost. For a piece of equipment with a larger attribute
value, extrapolation is possible, but inaccurate. To err on the side of caution, you
should use the price for multiple, identical smaller pieces of equipment.
Pumps

log10(purchased cost)=3.4+0.05log10W+0.15[log10 W]2

W = power (kW, 1, 300)
assume 80% efficiency

Heat Exchangers

log 10 ( purchased cost ) = 4 .6 0 .8 log 10 A + 0 .3[log 10 A ]2

A = heat exchange area (m2, 10, 1000)

Compressors

log10 (purchased cost ) = 2.3 + 1.4 log10 W 0.1[log10 W ]2

W = power (kW, 450, no limit)
assume 70% efficiency

Compressor Drive

log10 (purchased cost ) = 2.5 + 1.4 log10 W 0.18[log10 W ]2

W = power (kW, 75, 2600)

Turbine

log10 (purchased cost ) = 2.5 + 1.45 log10 W 0.17[log10 W ]2

W = power (kW, 100, 4000)
Assume 65% efficiency

Fired Heater

log10 (purchased cost ) = 3.0 + 0.66 log10 Q + 0.02[log10 Q ]2

Q = duty (kW, 3000, 100,000)
Assume 80% thermal efficiency

51

Vertical Vessel

log10 (purchased cost ) = 3.5 + 0.45 log10 V + 0.11[log10 V ]2

V = volume of vessel (m3, 0.3, 520)

Horizontal Vessel

log10 (purchased cost ) = 3.5 + 0.38 log10 V + 0.09[log10 V ]2

V = volume of vessel (m3, 0.1, 628)

ADDITONAL COST INFORMATIONS

Piping
straight pipe

Rs/m =5.0 (nominal pipe

diameter, in) (1+(sch #)/20)0.25

sch = schedule number for pipe

Rs/fitting = 50.0 (nominal pipe diameter, in)(1+(sch #)/20)0.25
for gate (isolation) valves

Rs100 (nominal pipe diameter, in)0.8 (1+(sch

#)/20)0.25
for control valve use Rs1000 (nominal pipe diameter, in)0.8(1+(sch #)/20)0.25

UTILITY COSTS
Low-Pressure Steam (618 kPa saturated)
Rs272.3/1000 kg
Medium-Pressure Steam (1135 kPa saturated)
Rs287.7/1000 kg
High-Pressure Steam (4237 kPa saturated)
Rs344.05/1000 kg
Natural Gas (446 kPa, 25C)

Rs210/GJ

52

Fuel Gas Credit

Rs175/GJ

Electricity

Rs2.1/kWh

Boiler Feed Water (at 549 kPa, 90C)

Rs85.75/1000 kg

Cooling Water
Rs12.39/GJ
Available at 516 kPa and 30C
Return pressure 308 kPa
Return temperature is no more than 15C above the inlet temperature
Rs155.05/GJ

Refrigerated Water
Available at 516 kPa and 10C
Return pressure 308 kPa
Return temperature is no higher than 20C

Rs35/1000 kg

Deionized Water
Available at 5 bar and 30C
Waste Treatment of Off-Gas

incinerated - take fuel

credit
Refrigeration

Rs276.15/GJ

Wastewater Treatment

Rs1960/1000 m3

53

EQUIPMENT COST FACTORS

Total Installed Cost = Purchased Cost (4 + material factor (MF) + pressure factor
(PF))
Pressure

< 10 atm, PF = 0.0

does not apply to turbines,

compressors, vessels,
(absolute) 10 - 20 atm, PF = 0.6

packing, trays, or catalyst, since their

cost
20 - 40 atm, PF = 3.0

equations include pressure effects

40 - 50 atm, PR = 5.0
50 - 100 atm, PF = 10
Carbon Steel MF = 0.0
Stainless SteelMF = 4.0
Chemical

Price/Cost, Rs/kg

Dibutyl phthalate

60.2

Benzene

15.75

Maleic Anhydride

32.55

ECONOMIC ANALYSIS
When evaluating alternative cases, the equivalent annual operating cost
(EAOC) objective function should be used. The EAOC is defined as
EAOC = -(product value - feed cost utility costs waste treatment cost - capital cost
annuity)
A negative EAOC means there is a profit. It is desirable to minimize the EAOC; i.e.,
a large negative EAOC is very desirable.
The capital cost annuity is an annual cost (like a car payment) associated with
the one-time, fixed cost of plant construction.
The capital cost annuity is defined as follows:

54

S.No

Equipment

1
2
3
4

Reactor
Compressor
Heat Exchangers
Distillation
column
Absorber
Condenser
Storage tanks
Vessel

5
6
7
8

capital cost annuity = FCI

Cost of single
Equipment(in lakhs)
20
10
15
15

Number
1
1
2
1

Overall cost(In
lakhs)
20
10
30
15

15
10
12
10

1
1
4
1

15
10
48
10

i (1 + i ) n
(1 + i ) n 1

where FCI is the installed cost of all equipment; i is the interest rate (take i = 0.15)
and n is the plant life for accounting purposes (take n = 10).
When evaluating alternative cases, the following relationship should be used:
gross profit = value of products cost of raw materials

TEC

Physical plant cost(ppc)

EXPENSES
Erection(f1)
Piping(f2)
Control equipments(f3)
Instrumentation(f4)
Electrical fittings(f5)
Buildings(f6)
Ancillary buildings(f7)
Site development(f8)
Utilities(f9)
PPC

158lakhs

TEC[1+f1+f2+..f9]
Cost factor(c.f)
.4
.6
.15
.2
.1
.15
.1
.05
.4

158[1+.4+.6+.+.4]

497.7lakhs

55

Design and engineering(f10)

Contractorsfee(f11)
Contingency(f12)
Fixed capital cost

.2
.05
.1

= PPC [1+f10+f11+f12]
= 497.7[1+.2+.05+.1]
= 671.895lakhs

Working capital (WC)

This is the capital tied up in the interest of the system in the form of ready cash to
meet operating expenses, inventories of raw materials and products .The working
capital may conveniently, to be assumed as 5% of the fixed capital cost.
Working capital (WC)

= 671.895.05
= 33.59lakhs

Total investment required

= FCC+WC
= 705.4898lakhs

Operating labor
POSITION
Managing Director
General Manager
Deputy General
Manager
Senior Engineer
Junior Manager
R&D Staff
Lab Staff
Maintenance Staff
Formen
Operators
Unskilled Workers

NUMBER
1
2
4

SALARY(lakhs)
4.5
3.2
2.75

OVERALLSALARY(lakhs)
4.5
6.4
11.0

10
15
8
8
20
8
30
20

2.5
1.75
1.0
0.5
0.4
0.5
0.4
0.2

25.0
26.25
8.0
4.0
8.0
4.0
12.0
4.0

Total operating labor

=
113.15lakhs
EXPENSES
COST(lakhs)
Plant overheads(50% of operating labor)
56.575
Maintenance(5% of FCC)
33.59
Operating labor
113.15
Capital charges(15% of FCC)
100.78
Insurance(1% of FCC)
6.72
Local taxes(2% of FCC)
13.44
Royalties(1% of FCC)
6.72
Total fixed cost

330.96lakhs

56

Variable cost(VC)
Raw material:
Benzene requirement/yr

10000250

2500000kg

Cost/kg of benzene

Rs15.75

Annual cost of benzene

393. 75000 lakhs

Units of electricity

4500uits/day

Charges per unit

Rs2.1

Annual electricity charges

4500 2.1 250

23. 62500 lakhs

Utility per annum:

Steam requirement
(5% of raw materials)

19.68750lakhs

4.331250lakhs

1134+4.331250

117.48lakhs

FC+VC

330.96+1219.05

448.441lakhs

1.1 times of PC

1.1448.441

493.2851lakhs

Rs32.55

12020250

3005000Kg

maleic anhydride

Rs32.55

Total annual sales

978.1275lakhs

Gross profit

Net income from annual sales- Annual

Total variable cost

Production cost(PC)

Annual production cost

Production cost /kg

Annual production of
maleic anhydride
Sales price/kg of

production cost
=

978.1275-493.2851

57

484.8424lakhs

Depreciation(R)
Using Sinking Fund Method for calculating depreciation,
=

(V-Vs) (i/(1+i)n-1)

uniform annual payments made at the end of each year

Installed cost of plant (Total investment)

Vs

Salvage value of plant after n years

Annual interest rate

Life period of plant

(705.4898-0) (.15/(1+.15)15 -1)

14.82lakhs

R
Where

Net profit
Net profit is defined as the expected annual return on investment after deducting
depreciation and taxes. Tax rate is assumed to be 45%
Net profit

Gross profit- depreciation-(gross profit tax rate)

251.84332lakhs

[Reference :6]

58

CONCLUSIONS

59

CONCLUSIONS
The Maleic Anhydride technology, through benzene route, which Indian
entrepreneurs opted for, in 70's, was appropriate, till early 80's. Because of the health
hazards associated with untreated benzene vapors, rising cost of benzene and its
demand in detergent alkylate, caprolactum, etc., attention, in developed countries, was
focused on alternate feed stock. Butane emerged the winner, because of, low cost and
easy availability, besides, being less hazardous to health. India has vast reserves of
natural gas, the utilization of which is poor, because of lack of infrastructural
development, so far C3/C4 fraction has-been earmarked for domestic fuel only, which
is a less profitable use, vis--vis, raw material for Maleic Anhydride.The demand of
Maleic Anhydride has been sluggish due to high cost of raw material and various
taxes on different end products. Installations of benzene recovery system, in the
existing manufacturing units, are lacking. Development of further applications of MA,
or, value added product growth, specially, with respect to usage of polyester resin
based products, appears insignificant, in India, going by the usage, of Maleic
Anhydride , in developed countries. Some research, on benzene oxidation, and, also,
for development of catalyst, on a limited scale, was undertaken by two National
Institutes, without much fruitful result. Enough capabilities exist, within the country,
with respect to fabrication of critical equipments, e.g., reactor, submersible pumps,
distillation column internals, etc., for Maleic Anhydride Plants. There is no evidence
to show that, on-line optimization, was done, for the existing plants. None of units is
having any benzene recovery system. Maleic Anhydride units in India are working,
outside the explosive range, with low benzene/O2 (air) ratio, with, consequent, higher
utilities cost, bigger reactor size for a, comparatively, less through-put. No attempt has
been made to manufacture Maleic Anhydride catalyst, though V2O5 based catalyst has
been developed and successfully used for other chemical processes.

60

REFERENCES

61

REFERENCES
1. Robert H.Perry:
Perrys Chemical Engineers Hand Book 5th and 6th edition.
2. Kirk and Othmer,
Encyclopedia of Chemical Technology Vol.13.2nd edition.
3. Robert Ewald Treybal
Mass Transfer operations
Mc Graw Hill Publications 2000
4.

M V Joshi, V V Mahajani
Process Equipment Design
Mac Millan Publications 2003

5. David Mautner Himmelblau

Basic principles & Calculations in chemical engineering
Prentice Hall PTR Publications 1996
6.

John Metcalfe Coulson, John Francis Richardson

Plant Design & Economics for Chemical Engineers
Butterworth and Heinemann Publications 2002

7. Warren L. McCabe, Julian C. Smith, Peter Harriot

Unit Operations of Chemical Engineering
Mc Graw Hill Publications 2004
8. Hollman.J.P:
Heat Transfer, 1989, Mc Graw Hill international editions.
9. Octave Levenspiel,
Chemical Reaction Engineering ,Wiley publications,3rd edition.

62