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Ministry of Higher Education and Scientific Research

College of Chemical Engineering

Fourth stage, Project: Part 1

Production of Acrylonitrile
By
Alseddiq Oday

Supervisor
Marwa N. Muhammad
List of Contents
Chapter 1 / INTRODUCTION .......................................................................................................................... 2
1.1 History of Acrylonitrile............................................................................................................................... 2
1.2 Physical Properties ...................................................................................................................................... 3
1.3 Chemical Properties .................................................................................................................................... 3
1.4 Uses of Acrylonitrile ................................................................................................................................... 4
1.5 Production of Acrylonitrile ......................................................................................................................... 5
1.5.1 Sohio Process ....................................................................................................................................... 5

1.5.2 Production from ethylene cyanohydrin ............................................................................................... 6

1.5.3 Production from Acetylene & Hydrocyanic acid .................................................................................. 6

1.5.4 Production from Hydrogen Cyanide Process ....................................................................................... 7

1.6 Process Description..................................................................................................................................... 9

1.6.1 Used Equipment................................................................................................................................. 10

1.6.2 Raw Martials ...................................................................................................................................... 13

Chapter 2 / MATERAIL BALANCE .............................................................................................................. 14
2.1 Material Balance on Reactor ..................................................................................................................... 15
2.2 Material Balance on Absorber .................................................................................................................. 19
2.3 Material Balance on Distillation 1 ............................................................................................................ 20
2.4 Material Balance on Distillation 2 ............................................................................................................ 21
Streams Material Balance : ............................................................................................................................. 22

List of Figures
Figure 1-1 Stricture of Acrylonitrile ..................................................................................................................... 2
Figure 1-2 Block Flow Diagram Sohio Process.................................................................................................. 10
Figure 1-3 Physical Properties of propylene ....................................................................................................... 13
Figure 1-4 Physical Properties of ........................................................................................................................ 13

List of Tables
Table 1-1 Physical Properties of Acrylonitrile ..................................................................................................... 4

Page | 1
Chapter 1 / INTRODUCTION
1.1 History of Acrylonitrile
Acrylonitrile (also called acrylic acid nitrile, propylene nitrile, vinylamine,
propanoic acid nitrile) is a multidirectional and reactive monomer which can be
polymerized under a wide variety of conditions and copolymerized with wide range
of other vinyl monomers. It was first prepared in 1893 by the French chemist
Charles. These processes were based on the catalytic dehydration of ethylene
cyanohydrin [1]. It is one of the most widely used monomers in the chemical
industry, with more than 14 billion pounds produced annually for use in plastics,
rubbers, resins, acrylic fibers, and polyacrylonitrile (PAN) – based carbon fibers .
Acrylonitrile of 99.5–99.7% purity is available commercially with the Structural
formulae as shown in (Figure 1-1)

Figure 1-1 Stricture of Acrylonitrile

Acrylonitrile did not become important until the 1930s, when industry began using
it in new applications such as acrylic fibers for textiles and synthetic rubber [2].
Although by the late 1940s the utility of Acrylonitrile was unquestioned, existing
manufacturing methods were expensive, multistep processes. They seemed reserved
for the world’s largest and wealthiest principal manufacturers. At such high

Page | 2
production cost Acrylonitrile could well have remained little more than an
interesting, low-volume specialty chemical with limited applications. However, in
the late 1950 s, SoHo’s research into selective catalytic oxidation led to a
breakthrough in Acrylonitrile manufacture. The people who invented, developed,
and commercialized the process showed as much skill in marketing as in chemistry.
The result was a dramatic lowering of process costs. Acrylonitrile is a clear, colorless
liquid with a slightly sharp odor. Considering that acrylonitrile is produced in such
huge amounts due to its varied uses and that it is a toxic chemical with stringent
regulations on its environmental impact.

1.2 Physical Properties

Physical Properties Acrylonitrile ( C3HN.mol - 53.064 ) is an unsaturated molecule
having a carbon - carbon double bond combinate with a nitrile group [3] . It is an
uncolored liquid. With the faintly pungent odor of peach pits. Its properties are
summarized in Table 1. Acrylonitrile is miscible with most organic solvents ,
including acetone , benzene , carbon tetrachloride , ether , ethanol , ethyl acetate ,
ethylene , cyanohydrin , liquid carbon dioxide , methanol , petroleum ether , toluene
xylene , and some kerosene . The water solubility of acrylonitrile at a number of
temperatures is shown in Table [1-1]

1.3 Chemical Properties

Properties The presence of both the olefinic (carbon - carbon double bond) group
and the nitrile group int acrylonitrile gives the molecule its matchless and varied
reactivity [4]. This reactivity leads to the great versatility of acrylonitrile as a raw
material. The olefinic group can undergo polymerization and co -polymerization,
hydrogenation, oxidation, addition and cyclization. The nitrile group can undergo
hydrogenation, hydrolysis, hydration, esterification, cyclization and reduction [3]

Page | 3
 Table 1-1 Physical Properties of Acrylonitrile

1.4 Uses of Acrylonitrile

1) A pure material used in the manufacture of synthetic fibers, plastics, and rubber.
One of the reasons for acrylonitrile's versatility is that it may create copolymers
with other unsaturated compounds such as styrene and butadiene [5].
2) Acrylonitrile is commercially produced by propylene ammoxidation, in which
propylene, ammonia and air react with the catalyst in the fluidized bed.
Acrylonitrile is primarily used as a co-monomer in the production of acrylic and
modacrylic fibers. It includes plastic, surface coatings, nitrile elastomers, barrier
resins and adhesives. In addition, various antioxidants are used as a chemical
intermediate in the synthesis of pharmaceuticals, dyes and surfactants.
3) In the synthesis of compounds used for the production of adhesives, anti-
oxidants, binders for dyestuffs and emulsifiers [6]

Page | 4
1.5 Production of Acrylonitrile
Production of Acrylonitrile Today almost all acrylonitrile is produced by
ammoxidation of propene , Although the first report of the preparation of
acrylonitrile from propene occurred in a patent by the Allied Chemical and Dye
Corporation in 1947, it was a decade later when Standard Oil of Ohio ( Sohio )
developed the first commercially feasible catalyst for this process Nowadays , all of
the United States capacity and approximately 90 % of the world capacity for
acrylonitrile is based on the Sohi process , There are various methods for the
production of acrylonitrile . The main ones [2] :

➢ Sohio process

➢ Production from thylene cyanohydrin

➢ Production from Acetylene & hydrocyanic

➢ Production from Hydrogen Cyanide Process

1.5.1 Sohio Process

Approximately 90% of total acrylonitrile production follows the Standard Oil of
Ohio (SOHIO) process, which is based on propylene ammoxidation. Reaction is too
high selective, fast, acrylonitrile production without the need for excessive recycling
efforts [3] The cost of acrylonitrile production, where more than 70% of propylene
is produced, has increased in recent times. For this reason, is produced acrylonitrile
as a result of the work because it is necessary to find alternative, more economical
solutions. In particular, propane ammoxidation is seen as the brightest alternative
process in this process propene, oxygen (as air), and ammonia are catalytically
converted directly to acrylonitrile using a fluidized bed reactor operated at

Page | 5
temperatures of 400–500°C and gauge pressures of 30–200kPa(0,3–2bar) :
2CH2=CH-CH3+2NH3+3O2→2CH2=CH-C≡N+6H2O

1.5.2 Production from ethylene cyanohydrin

Germany (I.G. Farber, Leverkusen) and the United States (American Cyanamid)
earliest produced acrylonitrile on an industrial scale in the early 1940s.These
operations were based on the catalytic dehydration of ethylene cyanohydrin.
Ethylene cyanohydrin was produced from ethylene oxide and aqueous hydrocyanic
acid at 60°C in the presence of a basic catalyst. The intermediate was so dehydrated
in the liquid phase at 200°C in the presence of magnesium carbonate and alkaline or
alkaline earth salts of formic acid [1].

HO-CH2-CH2-C≡N→CH2=CH-C≡N+H2O
An advantage of this process was that it generated few impurities; but, it was not
economically competitive. American Cyanamid and Union Carbide closed plants
based on this technology in the mid-1960s.

1.5.3 Production from Acetylene & Hydrocyanic acid

Before the improving of the propene ammoxidation process, a major industrial route
to acrylonitrile involved the catalytic addition of hydrocyanic acid to acetylene [1].

H-C≡C-H+HCN→CH2=CH-CN 7

Though vapor phase reaction has been reported, the commercial reaction usually was
carried out at 80°C in dilute hydrochloric acid containing cuprous chloride.
Unreacted acetylene was recycled. The yield from this reaction was good; however,
the raw materials were relatively costly, some undesirable impurities,

Page | 6
divinylacetylene and methyl vinyl ketone, were difficult to remove, and the catalyst
required frequent regeneration.

1.5.4 Production from Hydrogen Cyanide Process

Many thousand patents have been issued on the production of acrylonitrile by the
dehydration of ethylene cyanohydrin (from HCN and ethylene oxide) and the
reaction of acetylene with HCN. Acetonitrile (isomeric with ethylene cyanohydrin)
produced by the reaction of acetaldehyde and hydrogen cyanide cannot be easily
dehydrated to yield acrylonitrile and Water because it decomposes into the original
reagents at high temperatures.

To avoid the decomposition of acetonitrile into acetaldehyde and HCN, it has been
proposed to acylate the acetonitrile and then pyrolyze the resulting dominant male
acid to generate acrylonitrile and the organic acid. Acetonitrile is therefore
combined with acetic anhydride to produce dominant male acid, which is
subsequently pyrolyzed to produce acrylonitrile and acetic acid. This method
necessitates the use of an extra reagent-acetic anhydride-as well as the recovery
and recycling of the acetic acid produced.
Recently, a process for producing acrylonitrile from acetaldehyde and hydrogen
cyanide has been developed, which involves reacting these compounds to form
acetonitrile, mixing the acetonitrile with phosphoric acid (nitrile-acid ratio about
2:1), and spraying this reaction mixture under pressure into a reaction chamber,
where it encounters pro-heated oxygen-free combustion gases at a temperature of
about 600 C. Dehydration takes between 0.1 and 0.6 seconds. The products of the
reaction are cooled, condensed, and separated.
In this process, phosphoric acid is recovered as a solution of approximately 30% acid
strength, which must then be concentrated to 80%85% acid strength before it can be

Page | 7
returned to the process. Around two-thirds of the acetonitrile is thus dehydrated to
acrylonitrile, with the remainder dissociating into acetaldehyde and HCN and being
recycled. Lactic acid and primary ammonium phosphate are formed when some of
the acetonitrile combines with the phosphoric acid and water present. For every 100
kg of acrylonitrile produced, approximately 7.5 kilogram of ammonium phosphate
is obtained. This salt accumulates in the recycling phosphoric acid and must be
removed from the system on a regular basis. This results in a somewhat lower
acrylonitrile yield, complicates phosphoric acid recovery, and necessitates a
concentration increase. and recycle system and involves the consumption of
additional phosphoric acid reagent. The overall yield of acrylonitrile by this process
is about 90% of theory. My invention seeks to provide a process for producing
acrylonitrile from acetaldehyde and hydrogen cyanide that does not require reagents
other than acetaldehyde and HCN, does not involve lay-product recovery, does not
require intermediate concentration and reconstitution, and produces yields in excess
of theory.

Page | 8
1.6 Process Description
SOHIO process is selected for the production of acrylonitrile. Today, approximately
90% of total acrylonitrile production follows the Standard Oil of Ohio (SOHIO)
process, which is based on propylene ammoxidation. Reaction is too high selective,
fast, acrylonitrile production without the need for excessive recycling effort.

The cost of acrylonitrile production, where more than 70% of propylene is produced,
has increased in recent times. For this reason, acrylonitrile is produced as a result of
the work because it is necessary to find alternative, more economical solutions. In
particular, propane am oxidation is seen as the brightest alternative process, The am
oxidation reaction is formed by catalytic oxidation of hydrocarbons in the presence
of mixed metal oxides, or organic nitriles used as catalysts and ammonia in order to
produce water. Typical reagents are alkenes.

The reaction consists of three main processes: the oxidation of hydrocarbons to the
introduction of intermediates in active sites, the introduction of nitrogen and the
oxidative dehydrogenation of N-linked species. One of the most innovative ways of
producing acrylonitrile is the traditional SOHIO process , All the reaction takes place
in the vapor.

phase in the presence of a catalyst. The primary by-products of the process are
hydrogen cyanide, acetonitrile, and carbon oxide. The recuperation of these
byproducts depends on influences such as market conditions, plant location, and
energy costs. Hydrogen cyanide and acetonitrile, although they carry a market value,
are usually specified, specifying that the production of these by-products has little
effect on the economics of producing acrylonitrile [1].

Page | 9
In Figure (1-2) the standard SOHIO process, as given air, ammonia, and propylene
are introduced in to a fluid bed catalytic reactor operating at 0.3-2 bar pressure and
400-510°C. Ammonia and air are fed to the reactor in slight extra of stoichiometric
proportions because extra ammonia drives the reaction closer to integration and air
continually regenerates the catalyst. An important feature of the process is the high
conversion of reactants on a once-through basis with only just a few second
habitation times. The heat generated from the exothermic reaction is recovered via
a waste-heat-recovery boiler.

Figure 1-2 Block Flow Diagram Sohio Process

1.6.1 Used Equipment

➢ Fluidized Bed Reactor
➢ Quencher
➢ Recovery
➢ Ammonium sulphate unit
➢ Purification

Page | 10
Flowing of small solid particles, usually in a cylindrical bed, into the process of
moving these solid particles in a suspended manner by sending them through the
plate at a rate as low as the fluid by means of a field distributor plate on the lower
side of the bed. Here the velocity of the particles equals the velocity of the fluid.
Such fluidized workout makes the solid particles move quickly in the bed, creating
a perfect mixing between them.

The reactor off-gas must be quenched to the condensation temperature and the
excess ammonia removed. Due to the presence of impurities, it is impossible to
recycle the ammonia and it needs be removed with sulfuric acid. The two others for
the quench system are: quench and acid treatment in one step (‘acidic quench’);
quench and acid treatment in two separate steps (‘basic quench’). In the ‘acidic
quench’, reactor off-gas is touched with a circulating solution of sulfuric acid and
ammonium sulfate in water. Fresh sulfuric acid is added to keep the system acidic
and to avoid ammonia breakthrough. Water or, preferably, recycle streams from the
plant are added to balance the evaporative losses come by quenching hot reactor off-
gas. A purge is taken to avoid over-saturation of ammonium sulfate. The quench also
removes the catalyst which then is removed from the purge by settling or filtration.

Having change to the quench section, organics are typically recovered from the
reactor off gases by absorption (scrubbing with chilled water). The remaining waste
gas is sent to treatment. The scrubber liquor is passed to an extractive distillation
column (recovery column) where the acrylonitrile and hydrogen cyanide products
are separated in the overheads from the acetonitrile. The acetonitrile is rather refined

Page | 11
for sale as a product, but it may be stripped and incinerated (with energy recovery).
The recovery column bottoms contain high-boiling organic compounds (for
incineration) and some ammonium and/or sodium salts of organic acids which are
sent as an aqueous stream to waste water treatment.

The overheads from the recovery column, containing acrylonitrile, hydrogen

cyanide and a small amount of water, are distilled to produce acrylonitrile and
hydrogen cyanide products. In some plant designs, the‘ heads column’ (to refine the
hydrogen cyanide) and the ‘drying column ’(to remove the water) are sectional to
reduce energy consumption. The hydrogen cyanide may be incinerated, or
transformed in to other products on site, or sold (if a market is available ) If stored,
it has to be maintained at a low temperature and kept acidic, by the addition of acetic
acid, phosphoric acid, sulfuric acid and Sulphur dioxide, to prevent polymerization.
Due to the reactive and toxic nature of hydrogen cyanide, it is not stored for longer
than a few days. If the material cannot be sold or used, then it is incinerated. All sites
must therefore have the capability to overthrowal of the hydrogen cyanide produced.
The final step is the purification of the acrylonitrile by rectification in the
acrylonitrile column. The drying column and the acrylonitrile column may be
operated at low pressure to reduce the distillation temperature and to reduce
acrylonitrile polymer creation [3].

Page | 12
1.6.2 Raw Martials

Propylene (C3H6) is a colorless gas. It is occurred by thermal cracking of ethylene

at low concentration it forms an explosive and flammable mixture with air, while at
high concentrations it can reason asphyxiation and skin burns. It is used in the
petrochemical industry for the production of polypropylene, isopropyl alcohol
propylene oxide and other chemical .

Figure 1-3 Physical Properties of propylene

Air is a consist of gases, 79% nitrogen and 21% oxygen with traces of water vapor,
carbon dioxide, argon, and various other components .

Ammonia is also commercially and commonly available as an aqueous solution;

the most common commercial formulation is 28-30% NH3 .

Figure 1-4 Physical Properties of

Ammonia

Page | 13
Chapter 2 / MATERAIL BALANCE
The Block Flow Diagram :

Page | 14
2.1 Material Balance on Reactor
Basis = 1 hour

Working day = 310 day

𝑡𝑜𝑛𝑒
Production rate of Acrylonitrile = 140,000
𝑦𝑒𝑎𝑟

𝑡𝑜𝑛𝑒 1000 𝑘𝑔 1 𝑦𝑒𝑎𝑟 1 𝑑𝑎𝑦 𝑘𝑔

Production = 140,000 𝑦𝑒𝑎𝑟 ∗ 1 𝑡𝑜𝑛𝑒
∗
310 𝑑𝑎𝑦
∗
24 ℎ𝑜𝑢𝑟
= 18817.20
ℎ𝑜𝑢𝑟

𝑊𝑡 𝑘𝑔 1 𝐾𝑚𝑜𝑙𝑒 𝐾𝑚𝑜𝑙𝑒
No.Mole = → Production = 18817.20 ∗ = 354.64
𝑀.𝑤𝑡 ℎ𝑜𝑢𝑟 𝐾𝑔 53.06 ℎ𝑜𝑢𝑟

Main Reaction :

2C3 H6 + 2NH3 + 3O2 → 2C3 H3 N + 6H2 O …..….. (1)

Side Reactions :

4C3 H6 + 6NH3 + 3O2 → 6C2 H3 N + 6H2 O …….… (2)

C3 H6 + 3NH3 + 3O2 → 3HCN + 6H2 O ……..……. (3)

2C3 H6 + 3O2 → 6CO2 + 6H2 O ………………........ (4)

By Stichometry :
Input + Generation = Output - Consume

Conversion of C3 H6 into C3 H3 N is 80% [1]

354.64∗2 1
So, mole of C3 H6 in feed gas = ∗ ∗ = 886.6 𝑘𝑚𝑜𝑙𝑒
0.80 1

No. of Mole C3 H6 converted to ACR is = 354.64 kmole

Page | 15
Reaction (1)
No. of Mole of NH3
𝐶3𝐻6 𝑁𝐻3
2 2 X = 886.6 kmole
886.6 𝑋

No. of Mole of O2
𝐶3𝐻6 𝑂2
2 3 X = 1329.9 kmole
886.6 𝑋

No. of Mole of H2O

𝐶3𝐻6 𝐻2𝑂
2 6 X = 2040.1 kmole
886.6 𝑋

Reaction (2)
No. of Mole of C2H3N
𝐶3𝐻6 𝐶2𝐻3𝑁
4 6 X = 1329.9 kmole
886.6 𝑋

Reaction (3)
No. of Mole of HCN
𝑁𝐻3 𝐻𝐶𝑁
3 3 X = 886.6 kmole
886.6 𝑋

Page | 16
Reaction (4)
No. of Mole of CO2
𝐶3𝐻6 𝐶𝑂2
3 6 X = 2659.8 kmole
886.6 𝑋

No. of Mole of N2 inter the reactor

𝑂2 𝑁2
21 79 X = 5002.95 kmole
1329.9 𝑋

C Reactor D

Over all Material Balance :

Input = Output
B + C =D

Stream B ( Input ) = ( Ammonia % Propylene ) 50% * 50%

Total Mole of NH3 + C3H6 → 1,773.2 Kmole → 52336 Kg

Stream C ( Input ) = Air

Total Mole of Air ( O2 + N2 ) → 6332.857 Kmole → 182639.6 Kg

Page | 17
Stream D ( Output ) = ( C3H3N ) + ( H2O + CO2 + C2H3N +HCN)

Comp K Mole M.wt Kg

C3H3N 354.64 53.06 18817.2
H2O 2040.1 18.01528 47876.4
CO2 2659.8 28.0134 89784.8
C2H3N 1329.9 41.02 54552.5
HCN 886.6 27.01 23947.07
Total 15668.72 ------- 234978

Stream ( Input ) B + C = 234975.59 Kg

Stream ( Output ) D = 234978 Kg

Checking → Input = Output

Comp Stream B (kg) Stream C (kg) Stream D (kg)

NH3 15072.2 ------- -------
C3H6 37263.798 ------- -------
O2 ------- 42556.8 -------
N2 ------- 140082.8 -------
C3H3N ------- ------- 18817.2
C2H3N ------- ------- 54552.5
H2O ------- ------- 47876.4
HCN ------- ------- 23947.07
CO2 ------- ------- 89784.8
Total 52336 182639.6 234978

Page | 18
2.2 Material Balance on Absorber

E H
Absorber
F G

An absorber column is used in the SOHIO process to recover unreacted propylene,

which can be recycled back into the process, reduce waste, and improve efficiency
It also ensures a higher-purity product stream by removing unreacted propylene
Over allfurther
....before Material Balance
processing or :discharge.
Input = Output
E+F=H+G Stream H
Comp No.Mole Percent
Stream E
C3H3N 354.64 7%
Comp No.Mole Percent
C2H3N 1329.9 25%
C3H3N 354.64 5%
HCN 886.6 17%
C2H3N 1329.9 18%
CO2 2659.8 51%
H2O 2040.1 28%
Total 5230.94 100%
HCN 886.6 12%
CO2 2659.8 37%
Total 7271.04 100% Stream G
Comp No.Mole Percent
Stream F [1]
(NH4)2SO4 2040 53%
Comp No.Mole Percent
H2O 1800 47%
H2O 1260 70%
Total 3840 100%
H2SO4 540 30%
Total 1800 100%

Streams Input ( kmole ) Output ( kmole )

E 7271.04 ------
F 1800 ------
H ------ 5230.94
G ------ 3840
Total 9071.04 9070.94
Page | 19
2.3 Material Balance on Distillation 1

I
H Distillation 1
J

First distillation , the advantage of this column is that it allows for efficient
separation of the various components, resulting in a crude acrylonitrile stream
that can be further purified in subsequent steps.

Over all Material Balance :

Input = Output
H=I+J
Stream I
Stream H Comp No.Mole Percent
Comp No.Mole Percent HCN 886.6 100%
C3H3N 354.64 7% Total 886.6 100%
C2H3N 1329.9 25%
HCN 886.6 17%
CO2 2659.8 51% Stream J
Total 5230.94 100% Comp No.Mole Percent
C3H3N 354.64 8%
C2H3N 1329.9 31%
CO2 2659.8 61%
Total 4344.34 100%

Streams Input ( kmole ) Output ( kmole )

H 5230.94 ------
I ------ 886.6
J ------ 4344.34
Total 5230.94 5231.5

Page | 20
2.4 Material Balance on Distillation 2

L
J Distillation 2
K

This column has the advantage of removing any remaining impurities and
byproducts from the crude acrylonitrile stream, resulting in a higher quality
acrylonitrile product.

Over all Material Balance :

Input = Output
J=L+K
Stream L
Stream J Comp No.Mole Percent
Comp No.Mole Percent ACR (pure) 350 100%
C3H3N 354.64 8% Total 350 100%
C2H3N 1329.9 31%
CO2 2659.8 61%
Total 4344.34 100% Stream K
Comp No.Mole Percent
ACR 5 0.1%
(Not pure)
C2H3N 1325 33%
CO2 2660 66%
Total 3992.8 100%

Streams Input ( kmole ) Output ( kmole )

J 4344.34 ------
L ------ 350
K ------ 3992.8
Total 4344.34 4342.8

Page | 21
Streams Material Balance :

Streams K Mole

B 1773.2

C 6332.857
D 234978
E 7271.04
F 1800
G 3840
H 5230.94
I 886.6
J 4344.34

K 350
L 3992.8
Total 15668.72

Page | 22
[1] Akshay Grover, Mohit Sharma, Divyanshu Patel, Shashwat Mitra, Manufacture
of Acrylonitrile, April 2012.
[2] GülinGüvendik,İ.İpekBoşgelmez, ‘Akrilonitril,(2000).

[3] Daniele Cespi, FabrizioPassarini*, Esmeralda Neri, IvanoVassura, Luca Ciacci,

FabrizioCavani, ‘Life Cycle Assessment comparison of two ways for acrylonitrile
production: the SOHIO process and an alternative route using propane’,(2014).
[4] https://www.lenntech.com/hazardous-substances/acrylonitrile.htm.
[5] Kauppinen, T., Toikkanen, J., Pedersen, D., Young, R., Kogevinas, M., Ahrens,
W., Boffetta, P., Hansen, J., Kromhout, H., Blasco, J.M., Mirabelli, D., de la
Orden- Rivera, V., Plato, N., Pannett, B., Savela, A., Veulemans, H. & Vincent, R.
(1998) Occupational Exposure to
Carcinogens in the European Union in 1990–93, Carex (International Information
System on Occupational Exposure to Carcinogens), Helsinki, Finnish Institute of
OccupationalHealth.
[6] Guidelines for the distribution of Acrylonitrile,(2009).
[7] Naziev, Y.M., Guseinov, S.O., Shakhmuradov, S.G. Proc. Symp.Thermophys.
Prop., 1982, 8th (1) Horsley, Analyt. Chem., 1947 -Pagerey, P.F., St. Clair, C.R.,
Sibbitt, W.L. Transactions of the ASME, 1956
[8] National Toxicology Program, Report on Carcinogens (Thirteenth Edition),
Department of Health and Human Services.
[9] Air Quality Guidelines (Second Edition), Chapter 5.1, Acrylonitrile,
Copenhagen, Denmark,2000.
[10] IneosAsssesment, Report on Acrylonitrile for Developing an Ambient Air
Quality Guideline, 2007.

Page | 23
Ministry of Higher Education and Scientific Research

College of Chemical Engineering

Fourth stage, Project: Part 2

Production of Acrylonitrile

By
Alseddiq Oday

Supervisor
Marwa N. Muhammad

Page | 0
Table of Contents
Chapter 3 / ENERGY BALANCE .........................................................................2

THE GENERAL EQUATION FOR ENERGY BALANCE IS ...............................................2

3.1 FRANCE (1-101) .................................................................................................4

3.2 REACTOR ( FBR 1-101)......................................................................................5

3.3 HEAT-EXCHANGER (1-101) ..............................................................................10

3.3 ABSORBER (1-101) ...........................................................................................12

STREAMS ENERGY BALANCE .................................................................................13

Chapter 4 / DESIGN ..............................................................................................14

4.1 REACTOR ( FBR 1-101 ) ...................................................................................14

4.1.1 Data Information .......................................................................................14

4.1.2 Data Information .......................................................................................15

4.1.3 Reactions Kinetic and Configuration ........................................................15

4.1.4 Mole Balance ............................................................................................16

4.1.5 Rate Law Equation ....................................................................................16

4.1.6 Unit’s .........................................................................................................16

4.1.7 Stoichiometry ............................................................................................17

4.1.8 Polymath Code ..........................................................................................18

4.1.9 Mechanical Design ....................................................................................19

Chapter 5 / PROCESS CONTROL .....................................................................20

5.1 REACTOR ( FBR 1-101 ) ...................................................................................20

Page | 1
Chapter 3 / ENERGY BALANCE
THE GENERAL EQUATION FOR ENERGY BALANCE IS
𝛥𝛥𝛥𝛥𝛥𝛥 + 𝛥𝛥𝛥𝛥𝛥𝛥 + 𝛥𝛥𝛥𝛥 = 𝑄𝑄 − 𝑊𝑊

We don't have velocity, height, or moment elements in this project, so

𝛥𝛥𝛥𝛥𝛥𝛥 = 𝛥𝛥𝛥𝛥𝛥𝛥 = 𝑊𝑊 = 𝑍𝑍𝑍𝑍𝑍𝑍𝑍𝑍

So, the general equation will be :
𝑄𝑄 = 𝛥𝛥𝛥𝛥 → 𝛥𝛥𝛥𝛥 = 𝐻𝐻2 − 𝐻𝐻1
𝛥𝛥𝛥𝛥 = 𝑚𝑚 𝐶𝐶𝐶𝐶 𝛥𝛥𝛥𝛥
𝑇𝑇 𝑇𝑇
𝑚𝑚 ∫𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝐶𝐶𝐶𝐶 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 ∗ 𝑑𝑑𝑑𝑑 = 𝑛𝑛 ∫𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝐶𝐶𝐶𝐶 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 ∗ 𝑑𝑑𝑑𝑑

Where : ( 𝑚𝑚 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ) , ( 𝑛𝑛 = 𝑁𝑁𝑁𝑁. 𝑜𝑜𝑜𝑜 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 )

So, we'll start with the heat capacity constant :
Cp Constant Based on the gas-phase of all compounds [1]
Comp A B C D ΔȞf °
NH3 35.15 0.02954 4.4E-06 -6.7E-09 -46.191
C3H6 59.58 0.1771 -0.0001 2.4E-08 -103.85
O2 29.7045 0.999 3.4E-05 3.39E-09 0
C3H3N 10.96 0.0211 1.6E-05 3.77E-08 -1760.9
C2H3N 20.48 0.012 4.5E-05 3.2E-09 -84.6
H2O 33.46 0.00688 7.6E-06 -3.6E-09 -241.826
HCN 30.191 0.0683 4.2E-06 1.05E-10 34.082
CO2 36.11 0.0433 -3E-05 7.46E-09 -393.51
(NH4)2SO4 39.861 0.0513 1.3E-05 3.97E-09 -1180.9

Page | 2
Tref = 25C° = 298K
And all the temperature will be taken for all the equipment’s [1]

Page | 3
3.1 FRANCE (1-101)
A
NH3 400 C°
25 C° France 1-101 B
C3H6
A∗
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 + 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠∗
Ammonia Cp :
673
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝑠𝑠𝑠𝑠 � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 886.6 ∗ 15586.72 = 13819186.5 𝐾𝐾𝐾𝐾
298

Propylene Cp :
673
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠∗ = 𝑛𝑛𝑠𝑠𝑠𝑠∗ � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 886.6 ∗ 34475.94141 = 𝐾𝐾𝐾𝐾
298

Total Enthalpy :
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 13819186.5 + 30635321.53 = 44454508 𝐾𝐾𝐾𝐾
Which :
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑄𝑄

Page | 4
3.2 REACTOR ( FBR 1-101)
400 C°
B 500 C°
Reactor 1-101 D
C 450 C°
250 C°

2C3 H6 + 2NH3 + 3O2 → 2C3 H3 N + 6H2 O …..….. Reaction (1)

4C3 H6 + 6NH3 + 3O2 → 6C2 H3 N + 6H2 O …….… Reaction (2)

C3 H6 + 3NH3 + 3O2 → 3HCN + 6H2 O ……..……. Reaction (3)

2C3 H6 + 3O2 → 6CO2 + 6H2 O ………………........ Reaction (4)

𝛥𝛥𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟 = 𝛥𝛥𝐻𝐻𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 − 𝛥𝛥𝐻𝐻𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 + 𝛥𝛥𝐻𝐻°𝑟𝑟𝑟𝑟𝑟𝑟

𝛥𝛥𝐻𝐻°𝑟𝑟𝑟𝑟𝑟𝑟 = � 𝑛𝑛 𝛥𝛥𝐻𝐻𝑓𝑓 (𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃) − � 𝑛𝑛 𝛥𝛥𝐻𝐻𝑓𝑓 (𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅)

Reaction (1) Exothermic:

𝛥𝛥𝐻𝐻°𝑟𝑟𝑟𝑟𝑟𝑟 = [(2)(−1760.9) + (6)(−241.826)] − [ (2)(−103.85)
+ (2)(−46.191) + (3)(0) = −4672.674 𝐾𝐾𝐾𝐾
Reactant :
673
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

C3H6 2 886.6 30566369.65
NH3 2 886.6 13819186.52
O2 3 1329.9 13200615.53

Page | 5
� 𝛥𝛥𝛥𝛥 = 57586171.74 𝐾𝐾𝐾𝐾

Product :
673
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

C3H3N 2 354.64 2286442.679
H2O 6 2040.1 27000589.29
� 𝛥𝛥𝛥𝛥 = 29287031.97𝐾𝐾𝐾𝐾

𝑄𝑄1 = 𝛥𝛥𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟 = 29287031.97 − 57586171.71 − 4672.674

= −28303812 𝐾𝐾𝐾𝐾
Reaction (2) Exothermic:
𝛥𝛥𝐻𝐻°𝑟𝑟𝑟𝑟𝑟𝑟 = [(6)(−84.6) + (6)(−241.826)] − [ (4)(−103.85)
+ (6)(−46.191) + (3)(0) = −11323.81 𝐾𝐾𝐾𝐾
Reactant :
723
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

C3H6 4 886.6 35824480.25
NH3 6 886.6 15946535.93
O2 3 1329.9 31494044.68
� 𝛥𝛥𝛥𝛥 = 83265060.85 𝐾𝐾𝐾𝐾

Page | 6
Product :
723
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

C2H3N 6 1329.9 15043374.42
H2O 6 2040.1 30823969.61
� 𝛥𝛥𝛥𝛥 = 45867344.02 𝐾𝐾𝐾𝐾

𝑄𝑄2 = 𝛥𝛥𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟 = 45867344.02 − 83265060.85 − 11323.81

= −37409040.6 𝐾𝐾𝐾𝐾

Reaction (3) Exothermic:

𝛥𝛥𝐻𝐻°𝑟𝑟𝑟𝑟𝑟𝑟 = [(3)(34.082) + (6)(−241.826)] − [ (−103.85)
+ (3)(−46.191) + (3)(0) = −967.714 𝐾𝐾𝐾𝐾
Reactant :
723
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

C3H6 1 886.6 35824480.25
NH3 3 886.6 15946535.93
O2 3 1329.9 31494044.68
� 𝛥𝛥𝛥𝛥 = 83265060.85 𝐾𝐾𝐾𝐾

Page | 7
Product :
723
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

HCN 6 886.6 17602954.27
H2O 6 2040.1 30823969.61
� 𝛥𝛥𝛥𝛥 = 48426953.87 𝐾𝐾𝐾𝐾

𝑄𝑄3 = 𝛥𝛥𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟 = 48426953.87 − 83265060.85 − 967.714

= −34839074.7 𝐾𝐾𝐾𝐾

Reaction (4) Endothermic:

𝛥𝛥𝐻𝐻°𝑟𝑟𝑟𝑟𝑟𝑟 = [(6)(−393.51) + (6)(−241.826)] − [ (2)(−103.85)
+ (3)(0) = −3604.316 𝐾𝐾𝐾𝐾
Reactant :
773
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

C3H6 2 886.6 41308031.06
O2 3 1329.9 37129467.27
� 𝛥𝛥𝛥𝛥 = 78437498.33 𝐾𝐾𝐾𝐾

Page | 8
Product :
773
𝛥𝛥𝐻𝐻𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 � 𝐶𝐶𝐶𝐶𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑑𝑑𝑑𝑑
298

Comp Stoic K mole 𝛥𝛥𝐻𝐻

CO2 6 2659.8 57100567.84
H2O 6 2040.1 34706188.25
� 𝛥𝛥𝛥𝛥 = 91806756.09 𝐾𝐾𝐾𝐾

𝑄𝑄4 = 𝛥𝛥𝐻𝐻𝑟𝑟𝑟𝑟𝑟𝑟 = 91806756.09 − 78437498.33 − −3604.31

= 13365653.44 𝐾𝐾
𝑄𝑄𝑅𝑅 = 𝑄𝑄1 + 𝑄𝑄2 + 𝑄𝑄3 + 𝑄𝑄4
So, the total enthalpy will be :
𝑄𝑄𝑅𝑅 = (−28303812) + (−37409040.6) + (−34839074.7)
+ (13365653.44) =
( − 87186274 𝐾𝐾𝐾𝐾 )𝑗𝑗 → ( −87186.274 𝑗𝑗 )

The heat is removed using at 250 C° Which us superheated up to 450 C°

Msteam x CPsteam x ΔT = − 87186274

( Msteam ) x ( 1 ) x ( 450 – 250 ) = − 87186274

Msteam = 435931.37

This is the amount of steam needed to evacuate the heat that has been
generated in the reactor.

Page | 9
3.3 HEAT-EXCHANGER (1-101)
22 C° 50 C°
W W∗
Heat-Exchanger 1-101
D E
500 C° 250 C°

𝑄𝑄 = ( 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠∗ + 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 ) − ( 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 + 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 )

Data taken from (M-B) Ch2 :

C3H3N C2H3N H2O HCN CO2

Percent 0.08 0.23 0.2 0.1 0.38
K mole 354.64 1329.9 2040.1 886.6 2695.8

Under this equation :

A mix B mix C mix D mix

29.0201 0.029188 2.58E-0.6 5.88E-9

Page | 10
 773
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝑠𝑠𝑠𝑠 � 𝐶𝐶𝐶𝐶𝑚𝑚𝑚𝑚𝑚𝑚 ∗ 𝑑𝑑𝑑𝑑 = 7307 ∗ 17623.37 = 128774678 𝐾𝐾𝐾𝐾
298
523
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝑠𝑠8 � 𝐶𝐶𝐶𝐶𝑚𝑚𝑚𝑚𝑚𝑚 ∗ 𝑑𝑑𝑑𝑑 = 7307 ∗ 7451.70 = 54449885.7 𝐾𝐾𝐾𝐾
298

Water 𝐶𝐶𝐶𝐶 :

295
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝑠𝑠𝑠𝑠 � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 2040.1 ∗ (−100.87) = −205800.21 𝐾𝐾𝐾𝐾
298
323
𝛥𝛥𝐻𝐻𝑠𝑠𝑊𝑊 ∗ = 𝑛𝑛𝑠𝑠𝑊𝑊 ∗ � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 2040.1 ∗ (843.22) = 1720257.13 𝐾𝐾𝐾𝐾
298

So, the Q will be :

𝑄𝑄 = ( 54449885.7 + 1720257.13 ) − ( 54449885.7)
+ (−205800.21 )
𝑄𝑄 = −72398435 𝐾𝐾𝐾𝐾

And the heat reduced by cooling is :

𝑄𝑄𝑟𝑟 = −74324792 𝐾𝐾𝐾𝐾

Page | 11
3.3 ABSORBER (1-101)

250 C° 120 C°
E H
Absorber 1-101
F G
70 C° 140 C°
𝑄𝑄 = ( 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 + 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 ) − ( 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 + 𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 )

523
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝐸𝐸 � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 7371.04 ∗ 34511.47
298
= 56672184.77 𝐾𝐾𝐾𝐾

343
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝐹𝐹 � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 1800 ∗ 9726.54 = 6347609.96 𝐾𝐾𝐾𝐾
298

343
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝐻𝐻 � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 5230.94 ∗ 10311.97
298
= 15995727.88 𝐾𝐾𝐾𝐾

413
𝛥𝛥𝐻𝐻𝑠𝑠𝑠𝑠 = 𝑛𝑛𝐺𝐺 � 𝐶𝐶𝐶𝐶 ∗ 𝑑𝑑𝑑𝑑 = 3840 ∗ 9002.6724 = 17424712.94 𝐾𝐾𝐾𝐾
298

𝑄𝑄 = (−29599354 𝐾𝐾𝐾𝐾 ) → ( −29599.354 𝑗𝑗 )

Page | 12
Streams Energy Balance :

Streams Temperature °C Enthalpy ΔH Kj

A 25 13819186.5

A∗ 25 30635321.53

B 400 44454508

C 250 -87186274.8

D 500 128774678
E 250 54449885.7
W 22 -205800.217
W∗ 50 1720257.13
F 70 634709.96
G 140 17424712.94
H 120 15995727.88
Total --------- 220516912.623

Page | 13
Chapter 4 / DESIGN
4.1 REACTOR ( FBR 1-101 )

4.1.1 Data Information

Table 4.1 ( Condition )

Condition Value
Temperature in 400 °C
Temperature inside 450 °C
Temperature out 500°C
Molar flow rate 7271.04 kmol.hr
Pressure in 1 Bar
Pressure out 2 Bar
Type of reactor Fixed Bed Reactor
Working condition Adiabatic

Page | 14
4.1.2 Data Information

Table 4.2 (Details about the catalyst)

Name Ferro-bismuth Molybdate

Chemical Formula FeBiMoO4
Appearance yellowish-green solid
Density 1500 kg/cm3
Solubility in water Not Soluble
Purity 95% - 99%
Price 50$ to 150$ USD per kg

4.1.3 Reactions Kinetic and Configuration

k1
4C3 H6 + 6NH3 + 3O2 �� 6C2 H3 N + 6H2 O …….… Reaction (1)

k2
C3 H6 + 3NH3 + 3O2 �� 3HCN + 6H2 O ……..……. Reaction (2)

k3
2C3 H6 + 3O2 �� 6CO2 + 6H2 O ………………........ Reaction (3)

We considered the Fixed bed reactor for production of ACR with catalyst
Oxidation of propylene in high temperature accord to We have 3 reactions
first one is the main 1st order irreversible and the ither reactions is side ,
its all-Gas Phase and specific reaction and rate law and activation energy
and Arrhenius constant down below [3][4][5]

Page | 15
4.1.4 Mole Balance
𝑑𝑑𝑑𝑑 −𝑟𝑟𝐴𝐴
=
𝑑𝑑𝑑𝑑 𝐹𝐹𝐴𝐴𝐴𝐴

𝑑𝑑𝐹𝐹𝐴𝐴
= −𝑟𝑟1
𝑑𝑑𝑑𝑑
𝑑𝑑𝐹𝐹𝑏𝑏
= −𝑟𝑟2
𝑑𝑑𝑑𝑑
𝑑𝑑𝐹𝐹𝑐𝑐
= −𝑟𝑟3
𝑑𝑑𝑑𝑑
4.1.5 Rate Law Equation
𝐾𝐾1 𝑃𝑃𝐶𝐶3𝐻𝐻6
−𝑟𝑟𝐴𝐴 =
( 1 + 𝐾𝐾2 𝑃𝑃𝑁𝑁𝑁𝑁3 + 𝐾𝐾3 𝑃𝑃𝑂𝑂2 )2
4 6 3
−𝑟𝑟1 = 𝐾𝐾1 𝐶𝐶𝐶𝐶3𝐻𝐻6 𝐶𝐶𝑁𝑁𝑁𝑁3 𝐶𝐶𝑂𝑂2
3 3
−𝑟𝑟2 = 𝐾𝐾2 𝐶𝐶𝐶𝐶3𝐻𝐻6 𝐶𝐶𝑁𝑁𝑁𝑁3 𝐶𝐶𝑂𝑂2
2 3
−𝑟𝑟3 = 𝐾𝐾3 𝐶𝐶𝐶𝐶3𝐻𝐻6 𝐶𝐶𝑂𝑂2
63 99 112
𝐾𝐾1 = 0.13 ∗ 𝐸𝐸𝐸𝐸𝐸𝐸−�𝑅𝑅𝑅𝑅� , 𝐾𝐾2 = 2.6 ∗ 𝐸𝐸𝐸𝐸𝐸𝐸−�𝑅𝑅𝑅𝑅� , 𝐾𝐾3 = 4.4 ∗ 𝐸𝐸𝐸𝐸𝐸𝐸−[ 𝑅𝑅𝑅𝑅 ]

4.1.6 Unit’s
K1 kmol·m-3 hr-1 bar-2

K2 , K3 kmol·m-3 hr-1·bar-1

R Kj / Mole . K
CC3H6 CO2 CNH3 Mol/dm3
E Kj/mol
𝐅𝐅𝐀𝐀 𝐅𝐅𝐛𝐛 𝐅𝐅𝐜𝐜 Mol/hr-1

Page | 16
4.1.7 Stoichiometry
Data Taken from M-B ( Ch2 ) for Feedstocks

Comp Kmol / hr. Mol Frc Kg / hr Mass Frc

NH3 886.6 11 % 15072.2 6%
C3H6 886.6 11 % 37263.798 16 %
Air ( N2 + O2) 6332.857 78 % 182639.6 78 %
Total 8106.057 100 % 234975.59 100 %
𝑃𝑃𝑃𝑃 100 𝐾𝐾𝐾𝐾𝐾𝐾
𝐶𝐶𝐴𝐴0 = 𝑌𝑌𝐴𝐴𝐴𝐴 → 0.11 ∗
𝐾𝐾𝐾𝐾. 𝐾𝐾𝐾𝐾𝐾𝐾
= 0.0025 𝑚𝑚𝑚𝑚𝑚𝑚/𝐾𝐾𝐾𝐾
𝑅𝑅𝑅𝑅𝑅𝑅 8.3144 ∗ 523.15 𝐾𝐾
𝑚𝑚𝑚𝑚𝑚𝑚. 𝐾𝐾

2 6
Reaction (1) δ = � � + � � − � � + � � + � � = 0.84→
1 2 1 3 2
2 2 3
ε → 0.11 ∗ 0.84 =
0.0924
𝑏𝑏 𝐶𝐶
1−𝑋𝑋 𝑃𝑃 𝑇𝑇𝑇𝑇 𝛷𝛷𝛷𝛷− 𝑋𝑋 𝑃𝑃 𝑇𝑇𝑇𝑇 𝛷𝛷𝛷𝛷− 𝑋𝑋 𝑃𝑃 𝑇𝑇𝑇𝑇
𝐶𝐶𝐶𝐶3𝐻𝐻6 = 𝐶𝐶𝐴𝐴0 � � , 𝐶𝐶𝑁𝑁𝑁𝑁3 = 𝐶𝐶𝐴𝐴0 � 𝑎𝑎
� , 𝐶𝐶𝑂𝑂2 = 𝐶𝐶𝐴𝐴0 � 𝑎𝑎
�
1+εx 𝑃𝑃𝑃𝑃 𝑇𝑇 1+εx 𝑃𝑃𝑃𝑃 𝑇𝑇 1+εx 𝑃𝑃𝑃𝑃 𝑇𝑇

𝑅𝑅𝑅𝑅 𝑏𝑏𝐶𝐶3𝐻𝐻6 𝑅𝑅𝑅𝑅 𝑏𝑏𝑁𝑁𝑁𝑁3

𝑃𝑃𝐶𝐶3𝐻𝐻6 = − 2 , 𝑃𝑃𝑁𝑁𝑁𝑁3 = − 2 ,
𝑉𝑉𝐶𝐶3𝐻𝐻6 − 𝑏𝑏𝐶𝐶3𝐻𝐻6 𝑉𝑉𝐶𝐶3𝐻𝐻6 𝑉𝑉𝑁𝑁𝑁𝑁3 − 𝑏𝑏𝑁𝑁𝑁𝑁3 𝑉𝑉𝑁𝑁𝑁𝑁3
𝑅𝑅𝑅𝑅 𝑏𝑏𝑂𝑂2
𝑃𝑃𝑂𝑂2 = − 2
𝑉𝑉𝑂𝑂2 − 𝑏𝑏𝑂𝑂2 𝑉𝑉𝑂𝑂2
1 1 1
𝑉𝑉𝐶𝐶3𝐻𝐻6 = , 𝑉𝑉𝑁𝑁𝑁𝑁3 = , 𝑉𝑉𝑂𝑂2 =
𝐶𝐶𝐶𝐶3𝐻𝐻6 𝐶𝐶𝑁𝑁𝑁𝑁3 𝐶𝐶𝑂𝑂2
𝑃𝑃 200 𝐾𝐾𝐾𝐾𝐾𝐾 𝑇𝑇𝑇𝑇 673.15 𝐾𝐾
= = , 𝑏𝑏𝐶𝐶3𝐻𝐻6 = 0.0574 , 𝑏𝑏𝑁𝑁𝑁𝑁3 = 0.03 , 𝑏𝑏𝑂𝑂2 = 0.05
𝑃𝑃𝑃𝑃 100 𝐾𝐾𝐾𝐾𝐾𝐾 𝑇𝑇 723.15 𝐾𝐾

𝐾𝐾1 𝑃𝑃𝐶𝐶3𝐻𝐻6
−𝑟𝑟𝐴𝐴 = , FT = FA + FB + FC
( 1 + 𝐾𝐾2 𝑃𝑃𝑁𝑁𝑁𝑁3 + 𝐾𝐾3 𝑃𝑃𝑂𝑂2 )2

Page | 17
4.1.8 Polymath Code

V𝑟𝑟 = 80 𝑚𝑚3

Page | 18
4.1.9 Mechanical Design
Assume For RFB (L = 8D) 𝑉𝑉 = 𝐷𝐷 2 𝐿𝐿 → 𝐷𝐷 = 2.3 𝑚𝑚 , 𝐿𝐿 = 18.4 𝑚𝑚
4

NUMBER OF TUBES :
𝜋𝜋 2
𝑉𝑉𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝐷𝐷 𝐿𝐿 → 𝐷𝐷 = 0.06𝑚𝑚 , 𝐿𝐿 = 12𝑚𝑚
4
Based on ASTMA213, ASTMSA312 304 Stainless Steel bar
Products - Shandong Qiyuan Steel Co., Ltd (qiyuangt.com)
𝜋𝜋
𝑉𝑉𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 0.062 ∗ 12 = 0.034 𝑚𝑚3
4
No of. Tubes = ( Reactor Volume ) / ( Tube Volume )
80
𝑁𝑁𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = = 2352 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇
0.034
The material of the tubes Stainless Steel bar Grade 1.4301 Used for
Petrochemical and can handle A high Temperature .
PIPE THICKENS :
𝑃𝑃𝑃𝑃
𝑡𝑡 = Where :
2𝑆𝑆

𝑡𝑡: 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑡𝑡ℎ𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 , 𝑃𝑃: 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃

𝐷𝐷: 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷

9.86 ∗ 0.06
𝑡𝑡 = = 3.1166𝑚𝑚𝑚𝑚
2 ∗ 95 ∗ 10−6

Page | 19
Chapter 5 / PROCESS CONTROL
5.1 REACTOR ( FBR 1-101 )

Schematic Diagram (FBR 1-101)

FC : Flow Control
FT : Flow Transmitter
AC : Air Control
AT : Air Transmitter
TC : Temperature Control
TT : Temperature Transmitter
I/P : Error Signal
Sp : Set-Point

Page | 20
 Block Diagram (FBR 1-101)

Controlled Variables (CV) : T as Temperature C°

Manipulated Variables (MV) : Q as Flow m3/min
Disturbance Variables (DV) : D as Air flow KJ/min

Page | 21
 [1] Akshay Grover, Mohit Sharma, Divyanshu Patel, Shashwat Mitra, Manufacture
of Acrylonitrile, April 2012.
[2] GülinGüvendik,İ.İpekBoşgelmez, ‘Akrilonitril,(2000).

[3] Daniele Cespi, FabrizioPassarini*, Esmeralda Neri, IvanoVassura, Luca Ciacci,

FabrizioCavani, ‘Life Cycle Assessment comparison of two ways for acrylonitrile
production: the SOHIO process and an alternative route using propane’,(2014).
[4] https://www.lenntech.com/hazardous-substances/acrylonitrile.htm.
[5] Kauppinen, T., Toikkanen, J., Pedersen, D., Young, R., Kogevinas, M., Ahrens,
W., Boffetta, P., Hansen, J., Kromhout, H., Blasco, J.M., Mirabelli, D., de la
Orden- Rivera, V., Plato, N., Pannett, B., Savela, A., Veulemans, H. & Vincent, R.
(1998) Occupational Exposure to
Carcinogens in the European Union in 1990–93, Carex (International Information
System on Occupational Exposure to Carcinogens), Helsinki, Finnish Institute of
OccupationalHealth.
[6] Guidelines for the distribution of Acrylonitrile,(2009).
[7] Naziev, Y.M., Guseinov, S.O., Shakhmuradov, S.G. Proc. Symp.Thermophys.
Prop., 1982, 8th (1) Horsley, Analyt. Chem., 1947 -Pagerey, P.F., St. Clair, C.R.,
Sibbitt, W.L. Transactions of the ASME, 1956
[8] National Toxicology Program, Report on Carcinogens (Thirteenth Edition),
Department of Health and Human Services.
[9] Air Quality Guidelines (Second Edition), Chapter 5.1, Acrylonitrile,
Copenhagen, Denmark,2000.
[10] IneosAsssesment, Report on Acrylonitrile for Developing an Ambient Air
Quality Guideline, 2007.

Page | 22

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