1

CHAPTER I

LITERATURE STUDY: PROCESS BACKGROUND AND SELECTION

1.1

INTRODUCTION OF ACRYLONITRILE

Acrylonitrile is liquid at normal temperatures and pressure and has a faint

characteristic odour. It is one of the most important intermediates in processing of
basic hydrocarbon products to polymer end-products, as illustrated in Figure 1.3.
The chemical formula for acrylonitrile is CH2 = CH C = N. Acrylonitrile has several
synonyms and tradenames including propenenitrile, vinyl cyanide, cyanoethylene,
Acrylon, Carbacryl, Fumigrain, and Ventox. Lewis structure of acrylonitrile is
shown in Figure 1.1 below.

Figure 1.1: Lewis Structure of Acrylonitrile (Source: Wikipedia Foundation Inc.,

2010).

Figure 1.2: Chemical Structure of Acrylonitrile (Source: Wikipedia Foundation Inc.,

2010).

2
1.1.1

PHYSICAL AND CHEMICAL PROPERTIES OF ACRYLONITRILE

Selected physical and chemical properties of acrylonitrile are presented in Table 1.1.
Acrylonitrile is relatively volatile with a vapour pressure of 13.3 kPa (1.9 psi) at 25C
(77F) and a boiling point of 77.3C (171.1F). It readily ignites and can form
explosive mixtures with air. In addition, acrylonitrile polymerizes explosively in the
presence of strong alkalinity. Acrylonitrile is photochemically reactive and has an
estimated atmospheric residence time 5.6 days. Atmospheric residence time
represents the time required for a quantity of an individual chemical to be reduced to
1/e (37 percent) of its original value.

Table 1.1: Physical and Chemical Properties of Acrylonitrile

Property

Value

Molecular weight

53.06

Boiling point, C

77.3

Freezing point, C

- 83.55 + 0.05

Critical pressure, kPa

3536

Critical temperature, C

246

Density at 20 C, g/cm3

0.806

Viscosity, mPa s (or cP)

0.34

Vapour density (theoretical)

1.83 (air = 1.0)

Dielectric constant at 33.5 MHz

38

Dipole moment, cm
(liquid phase)

1.171 x 10-29

(vapour phase)

1.294 x 10-29

Vapour pressure, kPa

8.7 C

6.7

23.6 C

13.3

45.5 C

33.3

64.7 C

66.7

77.3 C

101.3

Explosive limits in air, vol 96

3.05 17.0 + 0.5

Heat of formation of vapour, kJ/mol

185.02

Latent heat of fusion, kJ/mol

6635

Source: U.S Environmental Protection Agency (EPA), 1984.

3
Furthermore, the reactions of acrylonitrile which is known as reactive
compound, occurred at its two chemically active sites namely, the nitrile group and
the carbon carbon double bond. Since, acrylonitrile is one of the most important
chemicals in polymer industries, it is readily polymerizes in the absence of
hydroquinone inhibitor, strictly when exposed to light. Theoretically, polymerization
reaction is initiated by free radicals, redox catalysts, or bases and can be carried out
in the liquid, solid, or gas phase. For example, there are two types of products
formed particularly in liquid phase polymerization, which are known as
homopolymers as well as copolymers. Table 1.2 below shows various types of
acrylonitrile reactions by nitrile and carbon carbon double bond categories.

Table 1.2: Various Types of Acrylonitrile Reactions.

Reaction of Carbon Carbon Double
Bond Group

Reaction of Nitrile Group

Hydration with sulphuric acid to

form
acrylamide
sulphate
(C3H5NO.H2SO4),
which can
further
be
converted
to
acrylamide
(C3H5NO)
by
neutralization with base.
Complete hydrolysis
acrylic acid.

to

form

Partial
hydrolysis
to
form
acrylamide (qv) by using copper
based catalysts.

Diels Alder addition to dienes

to form cyclic products.

Hydrogenation
over
metal
catalysts to give propionitrile
(C3H5N)
and
propylamine
(C3H9N).

Hydrodimerization to
adiponitrile (C6H8N2).

Addition of halogens to produce

dihalopropionitrile.

Cyanoethylation by acrylonitrile
of alcohols, aldehydes, esters,
amides,
nitriles,
amines,
sulphides, sulfones, and halides.

produce

Source: John J.McKetta and William A.Cunningham, 1982.

On the other hand, Table 1.3 and Table 1.4 show the descriptions of
thermodynamic data and azeotropes of acrylonitrile respectively. Moreover, Table
1.5 shows the solubilities of acrylonitrile in water for different values of temperature.
Last but not least, Table 1.6 shows acrylonitrile vapour pressure over aqueous
solutions at 25 C.

4
Table 1.3: Thermodynamic Data.
Property

Value

Autoignition temperature, C

481

Flash point, C

Flammability limits in air, 25 C vol%

lower

3.0

upper
Free energy of formation,

17.0
Gg ,

25 C, kJ/mol

195

Enthalpy of formation, 25 C, kJ/mol

Hg

180

Hl

147

Heat of combustion of liquid, 25 C, kJ/mol

1761.47

Heat of vaporization, 25 C, kJ/mol

32.65

Molar heat capacity of liquid, kJ/(kg - K)

2.09

Molar heat capacity of vapour of 50 C , kJ/(kg - K)

1.204

Molar heat of fusion, kJ/mol

6.61

Entropy of vapour, kJ/mol

274.06

Source: John J.McKetta and William A.Cunningham, 1982.

Table 1.4: Azeotropes of Acrylonitrile.
Azeotrope

Boiling point, C

Acrylonitrile concentration,
wt%

Water

71.0

88

Isopropyl alcohol

71.6

56

Benzene

73.3

47

Methanol

61.4

39

Carbon tetrachloride

66.2

21

Tetrachlorosilane

51.2

11

Chlorotrimethylsilane

57.0

Source: John J.McKetta and William A.Cunningham, 1982.

5
Table 1.5: Solubilities of Acrylonitrile in Water.
Temperature, C

Acrylonitrile in water, wt%

Water in acrylonitrile, wt%

-50

0.4

-30

1.0

7.1

2.1

10

7.2

2.6

20

7.3

3.1

30

7.5

3.9

40

7.9

4.8

50

8.4

6.3

60

9.1

7.7

70

9.9

9.2

80

11.1

10.9

Source: John J.McKetta and William A.Cunningham, 1982.

Table 1.6: Acrylonitrile Vapour Pressure over Aqueous Solutions at 25 C.

Acrylonitrile, wt%

Vapour pressure, kPa

1.3

2.9

5.3

6.9

8.4

10.0

10.9

Source: John J.McKetta and William A.Cunningham, 1982.

Figure 1.3: Pathways from Basic Hydrocarbons to Polymers (Source: Sami Matar and Lewis F. Hatch, 2000).

7
1.2

PROCESS BACKGROUND

The task is to design and setting a chemical plant for the production of 100 000
matrix tonne acrylonitrile per year in Malaysia.

1.3

SYNTHESIS OF ACRYLONITRILE

The acrylonitrile can be synthesized by three major routes, which are listed as
follows:
1. Propylene route.
2. Acetylene route.
3. Ethylene route.
The general descriptions as well as brief explanation for each route mentioned
above are discussed in the following sub sections.
1.3.1

PROPYLENE ROUTE

Nowadays, most of acrylonitrile produced via the propylene route, specifically

ammoxidation of propylene. Chemically, ammoxidation is a catalytic oxidative
reaction of activated methyl-groups with ammonia, NH3 to form a nitrile group. On
the other hand, the term ammoxidation is also used to describe the oxidative
amination reaction occurred during that particular process. Acrylonitrile is then
produced from propylene ammoxidation, with the following chemical equation:
H2C=CHCH2 + NH3 + 1.5 O2 H2C=CHCN + 3 H2O
In history, there are basically six types of processes in production of
acrylonitrile, which are also discussed briefly in the following sub sections.
1.3.1.1

SOHIO PROCESS

This kind of process is introduced in nearly 1957 and developed by Sohio

researchers (The Standard Oil Company) lead by John D. Rockefeller. The
company is determined to be a specialist petroleum company and it became part of
the British Petroleum Company P.I.C in 1987.

8
It is a single step, direct and heterogeneously - catalyzed process, namely
propylene ammoxidation. The raw materials are refinery grade of propylene with
more than 90% purity, refrigerant grade of ammonia with more than 99.5% purity, as
well as air as the source of oxygen. The raw materials are introduced near
stoichiometric ratio which is 1 / 1.06 / 8.4 for propylene / ammonia / air respectively
(U.S Pat. No: 4 296 046). The vapour - space ammoxidation reaction takes place in
a fluidized bed reactor at approximately 2 atm and 400 - 510C (750 - 950C) in the
presence of catalyst developed by Sohio. The catalyst developments for Sohio
process:
1. Catalyst A (1960): Bi2O3.MoO3.
2. Catalyst 21(1967): UO2.Sb2O3.
3. Catalyst 41(1972): Bi2O3.MoO3 with additives including Fe compounds.
4. Catalyst 49 (1977): Co62Ni22Fe33Bi3(MoO4)12O12.

The composition of this catalyst is described in the patent literature as 70

percent by weight P2O5:Bi2O3:MoO3 in a molar ratio of 1:9:24. The conversion of
propylene in the reactor is essentially complete. The reactions involve in this reactor
are shown below (U.S Pat. No: 4 296 046):

C 3 H 6 NH3

3
O 2 CH 2 CHCN 3H 2 O
2

(Main reaction)

2
C 3 H 6 NH 3 O2 CH 3 CN 2 H 2 O
3
3 1 C3 H 6 NH 3 O2 HCN 2 H 2 O
3
1
3
(4)
C 3 H 6 O2 CO2 H 2 O
3
2
1
(5)
C 3 H 6 O2 CO H 2 O
3

The main reaction is highly exothermic with H =

(Side reaction)

760 kJ/mol, so an

efficient heat removal system is essential by using a set of immersed tubes with
internal boiler feed water circulation which is placed within the catalyst bed reactor.
The selectivity of the main reaction is roughly 86%, while the rest will be the
selectivity of all the side reaction, where propylene is the basis component for both
reactions. The conversion of propylene in both reactions is 98%.

9
Generally, unreacted ammonia is then separated from the product stream
using sulphuric acid, H2SO4, resulting in an ammonium sulphate, (NH4)2SO4
solution. Waste gas is incinerated in a power plant. Acrylonitrile, acetonitrile, as well
as hydrogen cyanide (HCN) is separated by a series of separation processes from
the product stream before further being purified. The purified acrylonitrile is then
sent to storage tanks after stabilization.

1.3.1.2

BP (DISTILLERS) UGINE ROUTE

Propylene is oxidized on a Se/CuO catalyst to acrolein, which is then converted into

acrylonitrile in a second stage with NH3 and air over a MoO3 fixed-bed catalyst. This
two-step conversion leads to higher acrylonitrile selectivity of about 90% (based on
H2C=CHCHO). However, it had never been important commercially.
1.3.1.3

MONTEDISON UOP ROUTE

It is a single-step propylene conversion with Te-, Ce-, Mo-oxides catalyst on SiO2.

Propylene is then ammoxidized in a fluidized-bed at 420-460oC. As a result, one
thousand kilograms of acrylonitrile, 50 kg HCN, 25 kg Acetonitrile, and 425 kg
(NH4)2SO4 are obtained from 1200 kg propylene and 560 kg NH3. Further
development by UOP improved the acrylonitrile yield to over 80% at a propylene
conversion of about 95%.
1.3.1.4

SNAMPROGETTI / ANIC ROUTE

The process occurred in a fixed-bed catalyst based on Mo/V or Bi. An amount of

1260 kg of propylene is converted into 1000 kg acrylonitrile, 240 kg HCN, and 25 kg
acetonitrile at 440-470oC and 2 bars.

1.3.1.5

PROPANE ROUTE

This particular route required higher temperatures of 485-520oC, in which propane is

initially dehydrogenated to propene. It is developed by Monsanto, Power Gas, BP,
and ICI. The selectivity is 30%, markedly lower than with direct use of propene.

10
1.3.1.6

LUMMUS ROUTE

The manufacturing process is based on propane or propene, NH3 and O2 in a salt

melt such as KCl-CuCl-CuCl2. This process has not been practiced commercially
but the starting of a demonstration plant in 1994 has been announced by BP.
Propane is of particular interest because of a low advantage over propene. But, this
price difference is not likely to be great enough in the near future to dictate change.
1.3.2

ACETYLENE ROUTE

It is a homogeneously-catalyzed hydrocyanation in liquid phase or also known as

Nieuwland system. The catalyst used in this particular reaction is cuprous chloride in
hydrochloric acid (CuCl-NH4Cl). Commercially, the addition of HCN to acetylene
occurred at 80-90oC with a large excess of acetylene, slightly above atmospheric
pressure. The unreacted acetylene was recycled.

The chemical equation is as

follows:
HCCH + HCN H2C=CHCN
The reactor effluent is allowed to be cooled and passed into water, whereby
the acrylonitrile is extracted. The acrylonitrile solution is stripped with steam and the
acrylonitrile is purified by passage through a series of columns, the last of which
operates under reduced pressure.
This kind of pathway was developed by Bayer and practiced commercially by
Cyanamid, duPont, Goodrich, Knapsack, and Monsanto.

1.3.3

ETHYLENE ROUTE

In this type of route, ethylene is first converted to ethylene oxide. Then, the process
of base catalyzed addition of HCN to ethylene oxide are occurred to form
intermediate compound of ethylene cyanohydrins, which was then hydrated either in
the liquid phase at 200 oC in the presence of alkali metal or alkaline earth salts. The
alternative condition is such that it also can occur in gas phase at 250 oC - 300 oC
over Al2O3. The route to acrylonitrile is illustrated in Figure 1.4. This kind of route
was developed by IG Farben and operated by UCC from 1952 and by Cyanamid
from 1970.

11

H2C=CH2

O2

HCN

CH2-CH2
ethylene oxide

ethylene

-H2O

OH CN
CH2-CH2
ethylene cyanohydrin

H2C=CH-CN
acrylonitrile

Figure 1.4: Ethylene Route to Acrylonitrile (Source: John J.McKetta and William
A.Cunningham, 1982.).
1.4

PROCESS SELECTION

The methodologies to select the best available technique among three routes
discussed in the previous section are by analyzing and comparing the processes
based on several main factors considered in designing a chemical plant. Note that,
for the propylene route method, our concern is towards the Sohio process
(ammoxidation of propylene). The factors are listed as follows:
1. Economical (price for raw material).
2. Environmental and Safety.
3. Nature of Process.

Table 1.7 shows the descriptions of comparison factors for process selection to
produce acrylonitrile. After analyzing and comparing the main factors above, we
decide to select the Sohio process as our route to produce acrylonitrile. This is
because of its substantial advantage in overall production costs, primarily due to
lower raw material costs. Although the catalyst is quite expensive as it is specially
developed by Sohio researchers, but then the beneficial will counter act the higher
cost of catalyst as it catalyzed the ammoxidation reaction with propylene conversion
of 98 % as well as acrylonitrile selectivity of 86 %. Besides that, all raw materials
could also be supplied by many chemical producers in Malaysia. Furthermore,
although it produces significant amounts of highly toxic species form, such as HCN,
acetonitrile and heavy nitrile, but the implementation of efficient treatments will
prevent issues regarding to environment, safety, and health problems. Last but not

12
least, this particular process is also the latest process in acrylonitrile industry,
compared to others kind of route, in which the acetylene route is no longer practised
nowadays. On the other hand, although ethylene route able to produce high yield of
acrylonitrile, but the process has been abandoned after 1970 due to hazardous
properties of intermediate products and difficulties to remove its by products as
shown in Table 1.7.
Thus, in view of that situation, and with the factors, advantages, and reasons
discussed above, the Sohio process is selected as our route to produce our high
purities and quality of acrylonitrile.

13

Table 1.7: Descriptions of Comparison Factors for Process Selection.

Types of Routes

Sohio process

Acetylene route

Ethylene route

Comparison Factors
Economical
(price for raw material)
Propylene: RM 3960 per
tonne Cost and Freight
(CFR)
Ammonia: RM 993.19 /
tonne
Oxygen: from air source

Environmental and
Safety
Air
and
water
emissions.
Hazardous by
products.
Solids
or
liquid
wastes.

Usually HCN is not

selling
due
to
its
hazardous properties.
Ethylene: RM 3271.69 /
tonne

HCN is hazardous Old production process.

compound.
No longer practised.
Ethylene oxide is
hazardous
compound as it is
extremely
flammable,
explosive, toxic, and
carcinogen.

Nature of Process
Propylene conversion
of 98 %.
Single step reaction.
Acrylonitrile selectivity
of 86 %.
Major by-product: HCN,
Acetonitrile which
beneficial for sale.

After 1970, the process

had been abandoned.
High yield.
Major
by-product:
Divinylacetylene
and
methyl vinyl ketone,
which
difficult
to
remove.

Source: ICIS, 2010 and John J.McKetta and William A.Cunningham, 1982.

14
1.5

DETAILS OF THE SOHIO PROCESS: PROCESS DESCRIPTION

In this particular section, the details of the Sohio process are discussed, which
covers process descriptions of acrylonitrile production and also a sketch of
designing plant in Process Flow Diagram (PFD).

The raw materials in this process are determined to be propylene as well as

ammonia, in which we decide to purchase them due to the fact that they are widely
available in local market with reasonable prices. On the other hand, the oxygen
supply for the ammoxidation reaction will be also purchased purely from the market
rather than retrieve from the surrounding air. A reasonable benefit of using pure
oxygen is that it can increase reaction rates thus will improve and reduce feedstock
consumption as well as lowering operating cost which thereafter reduce capital
costs especially for new plants. The reasons of not utilize the air surrounding for
reaction process is that the outside air is contaminated with pollutant such as dust or
particulate matter, in which leading to the requirement of purifying the air by filter
equipment. As a result, the operating cost will be sufficiently increased. If the air
filter is not used, then the particulate types of pollutant might give problems to
equipments such as heat exchanger and compressor. Apart from that, there is also
another problem to encounter in terms of environmental consideration by using
surrounding air. Most of air composition consists of nitrogen (79 vol%). The reaction
of nitrogen and oxygen in combustion process later (incineration) will produce
enormous nitrogen dioxide gas (NOx) which is considered as one of major air
pollution. Nitrogen oxides can cause a wide range of environmental and health
problem. This pollutant contributes to the formation of acid rain which therefore can
cause damage to the earth surface. For that reasons, the most preferable approach
is to choose purchased pure oxygen.

Table 1.8 shows more descriptions regarding to the feedstock of the

process.

15
Table 1.8: Descriptions of Feedstock.
Feedstock

Descriptions

Propylene

The Chemical Grade propylene is available at 1 atm. The

component of the propylene will be as follows:

Ammonia
Oxygen

Propylene: 95.0 mol%

Propane: 4.7 mol%

Ethane: 0.3 mol%

Ammonia with 99.5 wt% is available as a liquid at 25 psig.

Pure oxygen will be purchased.

The catalyst used in order to enhance the rate of ammoxidation reaction in

heterogenous fluidized bed reactor is catalyst 41 which is contains molybdenum or
antimonium oxides mixed with transition metals such as Fe, Ni, Co, and V activated
by alkali and rare earth elements.

The feed of propylene and ammonia are in form of liquid phase whereas
oxygen is in vapour phase. Propylene must be in liquid phase due to the fact that, it
is a double bond and thus unstable and reactive compound, and hence it should be
stored under low pressure and temperature. Propylene (Stream 1) and ammonia
(Stream 2) is mixed by using a mixer (I - 4) together to reduce propylene reactivity
and then increasing the temperature by using a heater (E - 31). Then, the mixture of
propylene and ammonia is compressed (E - 35) before being introduced to reactor
for pressure regulation. On the other hand, oxygen (Stream 3) is heated by a heater
(E-5) and thus compressed by a compressor (E - 36). The reason for not feeding
propylene and ammonia together with stream containing oxygen is that if they were
introduced together the formation of an explosive composition could exist due to the
flammability properties of propylene and ammonia.

After the feed meet with the specification requirement of reaction to occur,
only then the permitted directly into heterogeneous fluidized bed reactor by a ratio
as stated in the literature study of Sohio process. A slight excess of ammonia forces

16
the reaction closer to completion and also a slight excess of oxygen continually
regenerates the bed catalyst used in the reaction.

The selection of this type of reactor is based on the excellent uniformity of

temperatures. This is the achievable throughout the bed because of the motion of
the solid and the good heat exchange between solid and gas. The ease of adding
and removing solid is an additional advantage. Hence a fluidized bed reactor is of
value for a very exothermic reaction that cannot be adequately controlled with a
multi-tube reactor, or when catalyst must be removed and replaced frequently. For
a partial oxidation reaction, this kind of reactor also permits a method of readily
introducing oxygen and reactant at different locations in the reactor. A fluid-bed
reactor may be less expensive to construct than multi-tube reactor the same the
capacity, and heat exchange may be simpler than with the adiabatic multi-bed
reactor. However, the hydrodynamics of fluidized beds are complex, scale-up
procedures are still relatively empirical, solids-separation equipment must be
provided, and the catalyst must be attrition-resistant and not agglomerate.
The vapor-phase ammoxidation reaction takes place in a fluidized bed
reactor at approximately 200 kPa (2 atm) and 400-510C (750-950F) in the
presence of Catalyst 41. The conversion of propylene in the reactor is essentially
complete. The reactions involve in this reactor are also discussed in the literature
study of Sohio process.

The main reaction is highly exothermic with H = 760 kJ/mol, so an efficient

heat removal system is essential by using a set of immersed tubes with internal
boiler feed water circulation which is placed within the catalyst bed reactor. The
selectivity of the main reaction is roughly 86%, while the rest will be the selectivity of
all the side reaction, where propylene is the basis component for both reactions. The
conversion of propylene in both reactions is 98%.

As a result, the reactor effluent (Stream 6) consist of acrylonitrile, unreacted

compounds such as propylene and ammonia as well as other by products from
side reactions such as acetonitrile, hydrogen cyanide, water, carbon dioxide and
carbon monoxide. Before the reactor effluent stream is introduced into an absorber,
it is first cooled by a cooler (E - 7). The cooling process is beneficial in order to
prevent water from boiling and vaporizing. Water is used as a solvent in a counter -

17
current absorber for removal of inert gases and vents them to the incinerator prior to
release to the atmosphere.

The scrub bottom stream which contains acrylonitrile, unreacted propylene

and ammonia, acetonitrile, hydrogen cyanide, carbon dioxide, carbon monoxide,
and some water is then introduced to an in line acid base mixer (I - 5). Sulphuric
acid is also introduced into the in line mixer to permit neutralization of unreacted
ammonia to produce ammonium sulphate. This is due to the fact that ammonia is
hazardous, unstable, as well as gives toxic effects to the respiratory system, senses,
liver, kidneys and bladder observed in mammalian species from prolonged
inhalation exposures at above 100 ppm. Ammonium sulphate will be discharged
with wastewater rather than crystallizing and selling them for fertilizers industries.
This is because the equipment cost will be sufficiently increased by installing the
crystallizers unit. In addition, it is also consumed large amount of energy.

The neutralized crude (Stream 11) undergoes a series of separation to

obtain products and by product of the desired purity, as described below.

Separator 1 (E - 24) is used to separate the acrylonitrile crude from

acetonitrile and water where the crude is removed from the top of the separator
while the acetonitrile and water goes into the bottom recovery. The recovery bottom
(Stream 12) which comprises of acetonitrile and water are then entered into the
Distillation Column 1(E-17) for further purification process where the water is
removed from acetonitrile. The heavy bottom (Stream 13) from the Distillation
Column 1 is discharged to waste water treatment whereas the acetonitrile byproduct (Stream 14) will then pass to the incinerator. The acrylonitrile crude (Stream
15) exiting the first separator is allow to condensed by using a cooler (E-18) so that
it can be feed into distillation column 2 (E-19) as it is one of the requirement of
distillation column. The hydrogen cyanide and the light components are separated
from acrylonitrile at the top of the distillation column 2 based on the volatility
differences. For environmental purpose, stream 7, 16 and 14 are introduced into the
incinerator where the combustion process occurs.

The recovery of these by-products depends on several factors such as

market conditions, plant location and energy costs however we prefer to incinerate
by-product rather than purify or sell it off to the market as the hydrogen cyanide and
acetonitrile has low demand in the market. Besides that, it also can minimize the

18
amount and duration of hydrogen cyanide (very hazardous compound) by
incineration.

In addition, the beauty side of the process is such that major of all those
compounds are highly combustible. The incinerator is equipped with the energy
recovery facilities as the exhausted flue gas from the combustion process can be
utilized as fuel boilers to produce high pressure steam. Then, the high pressure
steam can be used to drive the steam turbine and hence the electrical generator
which supplies onsite power particularly for mechanical devices such as pump and
compressor. If the power is surplus, then it can be sold off and thus boost our profit
as well. In addition, the low pressure steam from the turbine can be used for heating
process in the plant, condensed and recycled back to the boiler feed water.

The bottom product of Distillation Column 2 is introduced to the Distillation

Column 3 (E-20) whereby the heavy ends stream (stream 18) from the product
column contains essentially no acrylonitrile. The acrylonitrile product (stream 19)
obtained from this separation process has a purity of 99%. Besides that, stream 13
and 18 are mixed together and then goes to the deep well pond prior to treatment
process. The wastewater treatment has it benefit as the treated water from the
treatment facilities can be recycled back to the plant and used as solvent for
absorption process.

19

Incinerator
P-11

P-8

E-25

P-9

Cooler
E-7

P-19

Cooler

P-20

Vent Gases

P-23

E-18

16

15

Hydrogen
Cyanide (HCN)

Catalysed Fluidized
Bed Reactor

P-25

19

8
E-4

Acrylonitrile

Heater

Water

E-26

Separator

DC 2

Cooler

P-10

E-27

Absorber

E-35

E-24

11

E-19
P-24

I-5

17

E-37

Ammonia

P-16

E-31

E-20

In-line
Acid Base Mixer

I-4

P-38

DC 3

12
P-15

P-49

P-21

Acetonitrile
14

Heater
1

Mixer

10

P-18

18

DC 1
P-22

Propylene
E-17
P-31
P-29
P-13
P-3

P-3
P-22

3
P-32

Oxygen

E-5

Heater

Sulphuric Acid

E-36

Compressor

Figure 1.5: Process Flow Diagram of Acrylonitrile Production.

13
Waste water
treatment

20

Table 1.9: Estimated Composition Stream Table.

Stream 1
Component
C3H6 (propylene)
NH3 (ammonia)
O2 (oxygen)
C3H3N (acrylonitrile)
HCN (hydrogen cyanide)
C2H3N (acetonitrile)
H2O (water)
CO (carbon monoxide)
CO2 (carbon dioxide)
H2SO4 (sulphuric acid)
(NH4)2SO4 (ammonium
sulphate)

Propylene
feed

Stream 2
Ammonia
feed

Stream 3

Stream 4

O2 feed

Reactor
effluent

Stream 5

Stream 6

Stream 7

Stream 8

Vent
gases

Scrub
water

Scrub
bottom

Sulfuric
acid

Stream 9
Neutralized
crude

Stream 10
Acrylonitrile
crude

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Component

Stream 11

Stream 12

Stream 13

Stream 14

Stream 15

Stream 16

Stream 17

Recovery
bottoms

Crude
acetonitrile

Aqueous

HCN
byproduct

Interim
acrylonitrile

Acrylonitrile
product

Heavy
impurities

residues
C3H6 (propylene)
NH3 (ammonia)
O2 (oxygen)
C3H3N (acrylonitrile)
HCN (hydrogen cyanide)
C2H3N (acetonitrile)
H2O (water)
CO (carbon monoxide)
CO2 (carbon dioxide)
H2SO4 (sulphuric acid)
(NH4)2SO4 (ammonium
sulphate)

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