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The use of ASPEN Plus for the Optimization of

the Production of Acrylo Nitrile by
Ammoxidation Process

Conference Paper December 2013

DOI: 10.13140/2.1.2733.1362

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 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

The use of ASPEN Plus for the Optimization of the Production of Acrylo Nitrile by
Ammoxidation Process
Avinash Narayan1, Bhuvanesh M1 and Utkarsh Maheshwari2
1
Post Graduate Student, Department of Chemical Engineering, Birla Institute of Technology and Science, Pilani, Rajasthan-
333031, India.
2
Lecturer, Department of Chemical Engineering, Birla Institute of Technology and Science, Pilani, Rajasthan-333031, India.
E-mail addresses: bhuvi1150@yahoo.com,eranarayan@gmail.com, utkarshmaheshwari13@gmail.com

Abstract: Acrylic acid nitrile, usually referred to acrylonitrile (CH_2=CH-CN) today, became industrially important around
1930 in Germany and then in the USA. It was copolymerized with butadiene to form the synthetic rubber buna N. Since that
time, it has found numerous other applications as monomer, comonomer, and intermediate for fibers, resins, thermoplastics, and
elastomers. This wide range of applications and the successful improvements in production techniques were the key reasons for
the dramatic expansion in acrylonitrile production. The primary method for the Acrylo nitrile production is through the
ammoxidation process. In the present study, The amoxidation process is modeled and simulated on the ASPEN Plus plateform.
The process is also optimized for increasing the purity of acrylonitrile. The number of stages and the reflux ratio of the process
is optimized to increase the purity of acrylonitrile from 74 to 77 %.

Keywords: Acrylonitriles, Ammoxidation , Acrylic fiber, Polyacrylonitrile, ASPEN, Simulation.

1. Introduction: acetonitrile (ACN) and heavy nitriles. Their removal from

Acrylonitrile (AN) is one of the leading chemicals with a
worldwide production. The most important applications are
acrylic fibers, thermoplastics (SAN, ABS), technical
rubbers, adiponitrile, as well as speciality polymers. About
90% of the worldwide acrylonitrile (AN) is manufactured
today by the ammoxidation of propene. The reaction is
highly exothermal ( H = -123 kcal/mol) and takes place in
gaseous phase over a suitable catalyst at temperatures of
300 500 C and pressures of 1.5 3 bar in fluid - bed or
fixed bed reactors with efficient cooling. The catalyst
employed makes the difference in technologies. The first
commercial plant built by Sohio (now BP International)
used a catalyst based on Bi2O3, MoO3. Since then,
numerous chemical formulations have been patented. The
catalyst should be multifunctional and possess redox
properties. The most commonly employed contain
molybdenum or antimonium oxides mixed with transition
metals, such as Fe, Ni, Co and V, activated by alkali and
rare - earth elements. The reaction rate is high enough to
achieve almost total per - pass conversion at ratios of
reactants close to stoichiometry. High selectivity in
acrylonitrile remains a challenge. Today the best catalysts
can give a yield in acrylonitrile of 70 72%, mainly
because of losses in propene by combustion. Significant
amounts of highly toxic species form, such as HCN,
1
aqueous mixtures is difficult, as reflected in elevated water
treatment and energy costs [1]. Acrylonitrile (AN) is
commercially produced by a reaction of propylene and
ammonia in the presence of a catalyst. The commercial
product is a clear colourless to pale yellow flammable
liquid. Having both olefinic (C=C) and nitrile (CN)
groups permits a large variety of reactions and makes AN a
versatile chemical intermediate. The nitrile group can
undergo hydrolysis, hydrogenation, esterification and
reduction. Reactions of the carbon double bond include
polymerization, copolymerization, cyanoethylation,
cyclization and halogenation. In its liquid state,
acrylonitrile has a tendency to polymerize, which is
prevented by the addition of phenolic or amine-based
stabilizers and small quantities of water for preventing
uncontrolled polymerization is a critical issue for the safe
handling of acrylonitrile [2].
2. Properties
Appearance : Clear colorless to pale
yellow liquid
Odour : Pungent odour
Melting Point : -83.5C
Boiling Point : 77.3C
Flammability limits
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

@ 25C ( vol % in air ) : 3 17 %
Density @ 20C : 806 kg/m3
Molecular weight : 53.1
Vapour Pressure @ 20C : 0.12 bar
Viscosity @ 20C : 0.4 cP
Heat of combustion @ 25C : -33173 kJ/kg
Heat of polymerisation : -1412 kJ/kg
Solubility : miscible with many organic
solvents such as alcohols, ethers,
acetone, carbon tetrachloride,
ethyl acetate and aliphatic
hydrocarbon solvents, and
partially miscible in water.
3. Uses
Acrylonitrile is used as a monomer in the production of
acrylic fibers, which accounts for approximately 50% of its
global use. Acrylic fiber is used for clothing, carpeting and
other fabrics and in the production of rugged plastics for
automotive components, computers, appliances [1]. Acrylic
fiber is also used in the manufacture of polyacrylonitrile
(PAN)-base carbon fibers; which are increasingly
important materials for lightweight, high-strength
applications in aeronautics, automotive, engineering, etc
[2]. Acrylonitrile is used as a co-monomer the production
of acrylonitrile, butadiene, styrene (ABS) and styrene
acrylonitrile (SAN) polymers, which accounts for an
additional 31% of use [3]. These polymers are used in a
wide range of oil- and chemical-resistant nitrile rubber for
industrial hoses, gaskets and seals. Acrylonitrile is also
used as an intermediate in the production of other industrial
chemicals, such as adiponitrile and acrylamide [4].
4. Production process
The older processes for manufacturing acrylonitrile used
the relatively expensive C2 building units ethylene oxide,
acetylene, and acetaldehyde, which were reacted with HCN
to form acrylonitrile or its precursors. Traditional AN
manufacture by three synthetic routes HCN and C2
feedstocks such as:[3]
I. H2COCH2
II. C2H2
III. CH3CHO
This earlier process has been replaced by the propylene
based route, because of its advantages of a higher
conversion rate, no recycling of unreacted raw materials
and resultant lower production cost [1].
4.1.Ammoxidation Process
4.1.1.The First Separation Step:
2
Before separation, the reactor off - gas must be quenched
quickly to prevent thermal degradation and secondary
reactions. At the same time, this operation removes the
excess of ammonia. Two methods can be employed: (1)
one step quench and acidic treatment (acidic quench), (2)
two step separate quench and ammonia removal (basic
quench). In the acidic quench the gas is brought into
contact with a solution of sulfuric acid of 30 40%.
Recycled water is added to compensate the losses by
evaporation. Precooling down to the dew point could be
employed for maximum energy recovery. The entrained
catalyst fines are recovered by filtration. Ammonium
sulfate is separated, purified by crystallization and finally
obtained as a saleable byproduct [2].
By a basic quench the removal of catalyst fines and
ammonia take place separately. After quench, the cleaned
gas is submitted to acrylonitrile absorption in cold water.
The vent gas containing mainly carbon oxides, nitrogen and
unreacted propylene, as well as light organics, is sent to
catalytic oxidation. The liquid mixture is sent to
acrylonitrile recovery in a stripping column [3]. The top
product is raw acrylonitrile, while the water separated in
bottoms is recycled to quench and absorption, eventually
with some pretreatment. The gas is cooled in HX1 from
420C to the 220C. This operation delivers a heat duty
QHX1 = 7.8 MW that can be used for raising steam of 12
bar. Furthermore, the gas is treated in a quench tower with
H2SO4 solution, where both cooling and neutralization of
the excess ammonia take place. The residual gas leaving,
containing unconverted propene, CO2 and other VOC is
usually sent directly to flare after catalytic combustion.
The raw acrylonitrile stream contains approximately 85%
acrylonitrile and 5% water, the rest being organic
impurities namely HCN, acrolein and acetonitrile. A
reasonable number of stages were assumed and the energy
consumptions were adapted to meet the target performance
in terms of component recovery and product purity.
Column C-1 has the target of removing the heads
including light impurities as HCN and acrolein. HCN
separates easily in top, although over 99% recovery
demands tall columns and a high reflux ratio. The removal
of acrolein is much more difficult. A solution of this
problem is chemical conversion to a heavier species by
reaction with HCN, as given by reaction. The reaction may
take place in a pretreatment vessel, or directly on the stages
of the distillation column. Since a sharp HCN split cannot
be done without some acrylonitrile loss, the separation is
done in two columns, HCN removal C-1A and acrylonitrile
recovery C-1B, respectively. The next column C-2 handles
the separation of acrylonitrile/acetonitrile binary by
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013
extractive distillation. A large amount of water is necessary
to modify the volatility of components. After condensation,
the top vapor is separated in a decanter, the water phase
being refluxed to extractive distillation, while the organic
phase goes to the next purification. The simulation
indicates a high sensitivity of acetonitrile recovery with the
temperature of the water feed, which should be about 10
C below the top temperature. Because a large amount of
water is entrained in the side stream, this is removed in the
column C - 3. Raw acetonitrile, namely a binary azeotrope
with 20% water, separates in top. The bottom stream
contains water with heavy impurities[1]. Vacuum
distillation at 0.5 bar is adequate to limit the bottom
temperature. In the next step pure acetonitrile can be
obtained by using pressure - swing distillation. The water -
free acrylonitrile is obtained as bottoms in the column C-4.
Water leaves in top as a binary azeotrope, followed by
decantation and reflux of organic phase.
The separation of acrylonitrile involves a large amount of
water. This is obtained as bottom stream of the distillation
columns, with heavy impurities and traces of HCN, ACN
and AN.
4.1.2.Purification step[1]
Figure 3 presents the process - simulation diagram, which
reflects the separation scheme developed before in Figure
2. A reasonable number of stages were assumed and the
energy consumptions were adapted to meet the target
performance in terms of component recovery and product
purity. In addition, the diameter of trays and packing
columns are compared.
Column C-1 has the target of removing the heads
including light impurities as HCN and acrolein. HCN
separates easily in top, although over 99% recovery
demands tall columns and a high reflux ratio. The removal
of acrolein is much more difficult. A solution of this
problem is chemical conversion to a heavier species by
reaction with HCN, as given by reaction. The reaction may
take place in a pretreatment vessel, or directly on the stages
of the distillation column. Since a sharp HCN split cannot
be done without some acrylonitrile loss, the separation is
done in two columns, HCN removal C-1A and acrylonitrile
recovery C-1B, respectively.
The next column C-2 handles the separation of
acrylonitrile/acetonitrile binary by extractive distillation. A
large amount of water is necessary to modify the volatility
of components. After condensation, the top vapor is
3
separated in a decanter, the water phase being refluxed to
extractive distillation, while the organic phase goes to the
next purification. The simulation indicates a high
sensitivity of acetonitrile recovery with the temperature of
the water feed, which should be about 10 C below the top
temperature. Because a large amount of water is entrained
in the side stream, this is removed in the column C-3. Raw
acetonitrile, namely a binary azeotrope with 20% water,
separates in top. The bottom stream contains water with
heavy impurities. Vacuum distillation at 0.5 bar is adequate
to limit the bottom temperature. In the next step pure
acetonitrile can be obtained by using pressure - swing
distillation. The water - free acrylonitrile is obtained as
bottoms in the column C-4. Water leaves in top as a binary
azeotrope, followed by decantation and reflux of organic
phase. The water phase also removes some light impurities.
Since heavy impurities inevitably appear, a final vacuum
distillation of acrylonitrile is performed in practice before
shipping. An interesting aspect is the relation between the
design of units and the quality specifications. The path of
each impurity can be traced by paying attention to
generation, exit points and accumulation in recycles. In this
respect the component split matrix available in Aspen
Plus gives very useful information and is highly
recommended.
The separation of acrylonitrile involves a large amount of
water. This is obtained as bottom stream of the distillation
columns, with heavy impurities and traces of HCN, ACN
and AN. Before reuse, the wastewater is cleaned by multi-
effect evaporation. The concentrated residual in organics is
burned. The water amount produced by reaction is sent to
advanced purification in a biological unit.
4.1.3. Reactions at ammoxidation of propene in the reactor
1) CH = CH CH + NH + 3/2 O

CH = CH CN ( AN ) + 3 HO
2) 2CH = CH CH+ 3 NH + 3/2 O

3 CH CN ( ACT ) + 3 H O
3) CH = CH CH+ 3 NH + 3 O

3HCN + 6 HO
4) CH = CH CH+ 3/2 O
3 CO + 3 H O
5) CH = CH CH+ 1/2 O

CH = CH CHO (ACR) + H O
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

Figure 1 : Reactor section and first separation step by acrylonitrile manufacturing.

Figure 2 :Separation and purification of acrylonitrile.

Figure 3: Simulation flowsheet of acrylonitrile production using ASPEN PLUS

4
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

5. Simulation and Optimisation
The simulation of the separation and purification process is
done using ASPEN PLUS and the model is validated. The
purity was 74% initially before any optimization had been
done. To increase the purity of the acrylonitrile product
produced, optimization is done in the process by changing
the reflux ratio and in the number of stages in the column.
When the reflux ratio is increased from 5 to 20 and the
number of stages is reduced from 65 to 30, there is slight
increase in purity which is about 77% is observed in the
production of acrylonitrile.
6.Conclusion
From the optimization done using ASPEN PLUS for the
simulated process flow sheet for the acrylonitrile
production, we conclude that there is increase in the
product purity from 74 to 77 % and thereby the quality and
the effectiveness of the acrylonitrile product is increased.
References
[1] Pep Process Module, Acrylonitrile by the Ammoxidation of
Propane, Aspen Model Documentation, November 2000.
[2] An Group, Acrylonitrile Safe Handling Guide, February 2012.
[3] K. Weissermel, H. J. Arpe, Industrial Organic Chemistry, 1997.
[4] A. C. Dimian, C. S. Bildea, Chemical Process Design: Computer-
aided Case Studies ,2008.

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