Acrylonitrile Production

CONTENTS
LIST OF TABLE .............................................................................................................. vi
LIST OF FIGURES .......................................................................................................... vii
ABBREVIATION LIST ................................................................................................. viii
1. GENERAL INFORMATION................................................................................... 2
1.1 Physical Properties.................................................................................................... 3
1.2 Chemical Properties .................................................................................................. 4
1.3 Use of Acrylonitrile .................................................................................................. 4
1.4 Occurrence ................................................................................................................ 5
1.4.1 Natural occurrence ............................................................................................. 5
Acrylonitrile is not known to occur as a native product. ............................................ 5
1.4.2 Occupational exposure ....................................................................................... 5
1.5 Production of Acrylonitrile ....................................................................................... 5
1.5.1 Sohio process ..................................................................................................... 6
1.5.2 Production from ethylene cyanohydrin .............................................................. 6
1.5.3 Production from acetylene and hydrocyanic acid .............................................. 6
1.6 Toxicology of Acrylonitrile ...................................................................................... 7
1.7 Reactions of Acrylonitrile......................................................................................... 9
1.7.1 Reactions with nitrile class ................................................................................ 9
1.7.2 Reactions with olefins and alcohols ................................................................... 9
1.7.3 Reactions with aldehydes and methylol compounds ......................................... 9
1.7.4 Reaction of the double bond ................................................................................ 9
1.7.5 Reactions of both functional classses............................................................... 10
2. SITUATION IN THE WORLD AND TURKEY .................................................. 12
2.1 Acrylonitrile Marketing in theWorld ...................................................................... 12

I
2.2 Acrylonitrile Marketing InTurkey .......................................................................... 14
3.PROCESS SELECTION AND CAPACITY ................................................................ 16
3.1 Process Selection .................................................................................................... 16
3.1.1 Cost estimation for all production methods ..................................................... 16
3.2 Production of Acrylonitrile from SOHIO Process.................................................. 20
3.2.1 Catalysts ........................................................................................................... 23
3.3 Capacity of the Process ....................................................................................... 23
4.ACRYLONITRILE PRODUCTION FLOW DIAGRAMS I ....................................... 25
4.1 Block Flow Diagram............................................................................................... 25
4.2 Explain the Related Equipments............................................................................. 26
4.2.1 Used equipments .............................................................................................. 26
4.3 Explain the Raw Materials ..................................................................................... 30
4.3.1 Propylene ......................................................................................................... 30
4.3.2 Air .................................................................................................................... 31
4.3.3 Ammonia.......................................................................................................... 31
4.4 Explain the Byproduct Materials ............................................................................ 32
4.4.1 Hydrocyanic acid ............................................................................................. 32
4.4.2 Acetonitrile....................................................................................................... 32
4.4.3Carbon monoxides ............................................................................................ 34
4.5 Evaluation and Examination of By Products .......................................................... 34
5. PROCESS FLOW DIAGRAM II ................................................................................ 37
5.1 Acrylonitrile Production in Chemcad Simulation .................................................. 37
5.2 Chemcad Equipment Values ................................................................................. 38
5.2.1 Reactor ............................................................................................................. 38
5.2.2 Quencher .......................................................................................................... 39

II
5.2.3 Absorber ........................................................................................................... 40
5.2.4 Recovery column ............................................................................................. 41
5.2.5 Acetonitrile column.......................................................................................... 41
5.2.6 HCN column .................................................................................................... 42
5.2.7 ACN column .................................................................................................... 42
6. MATERIAL AND ENERGY BALANCE .................................................................. 44
6.1 MATERIAL BALANCE ........................................................................................... 44
6.1.1 Material Balance for Reactor ............................................................................... 44
6.1.2 Quench column ................................................................................................ 54
6.1.3 Absorber ........................................................................................................... 55
6.1.4 Recovery column and decanter ........................................................................ 56
6.1.5 Aceto column ................................................................................................... 57
6.1.6 HCN column .................................................................................................... 57
6.2 ENERGY BALANCE ............................................................................................ 58
6.2.1 Preheating of reactor ........................................................................................ 58
6.2.2 Energy Balance Around Reactor...................................................................... 59
6.2.3 Energy Balance Over Product Gas Cooler ....................................................... 61
6.2.4 Energy Balance Around Quench Column ........................................................ 63
6.2.5 Energy Balance Around After Cooler .............................................................. 65
6.2.6 Energy Balance Around Absorber and Heat Exchanges ................................. 67
6.2.7 Energy Balance Around Recovery Column ..................................................... 68
7. DESIGN OF EQUIPMENT ......................................................................................... 71
7.1 Fluidized Bed Reactor (FBR) ................................................................................. 71
7.1.1 Mechanical design of the reactor ..................................................................... 72
7.1.2 Checking tower height for various external and internalloads ........................ 73
III
7.1.3 To design the skirt support ............................................................................... 76
7.2 Distillation Column Design .................................................................................... 77
7.2.1 To find the diameter of the distillation column................................................ 80
7.2.2 Provisional Plate Design .................................................................................. 83
7.2.3 To check weeping rate .................................................................................... 83
7.2.4 To check plate pressure drop ........................................................................... 84
7.2.5 Plate layout ....................................................................................................... 85
7.3 Heat Exchanger Calculation ................................................................................... 85
7.4 Pump& Pipesizes Design........................................................................................ 86
7.5 Compressor Design................................................................................................. 89
8. PLANT PLAN AND SITE SELECTION .................................................................... 92
8.1 Marketing Area ....................................................................................................... 92
8.2 Raw Material Supply .............................................................................................. 92
8.3 Transport Facilities ................................................................................................. 92
8.4 Availability of Labor ............................................................................................. 93
8.5 Availability of Utilities ........................................................................................... 94
8.6 Availability of Suitable Land ................................................................................. 94
8.7 Environmental Impact and Effluent Disposal......................................................... 95
8.8 Local Community Considerations .......................................................................... 95
8.9 Climate.................................................................................................................... 95
8.10 Political & Strategic Considerations..................................................................... 96
8.11 Raw Material Source ............................................................................................ 97
8.12 Number of Working Staff ..................................................................................... 97
8.13 Storage Tanks ....................................................................................................... 99
8.14 Raw Materials Purchased From Domestic And Abroad...................................... 99

IV
8.15 Domestic and Distributed Products .................................................................... 100
8.16 Plan Layout ......................................................................................................... 101
REFERENCES ............................................................................................................... 104
V
LIST OF TABLE
Table 1.1: Some physical properties of acrylonitrile.................................................................................... 3

Table 1.2: The primarily toxic effects in humans of acrylonitrile ................................................................ 8
Table 2.1: The biggest manufacturers of Acrylonitrile in the World ......................................................... 13
Table 2.1: The amount of acrylonitrile produced by PETKIM over the years ........................................... 14
Table 3.1: Cost of each component ............................................................................................................ 16
Table 3.2: Reaction and cost of component ............................................................................................... 16
Table 4.1: Physical properties of propylene ............................................................................................... 30
Table 4.2:Propylene Values of thermophysical properties of the saturated liquid and vapor .................... 30
Table 4.3: Thermodynamic properties of air .............................................................................................. 31
Table 4.4: Physical and chemical properties of ammonia .......................................................................... 31
Table 4.5 Commercial acetonitrile specifications ...................................................................................... 33
Table 4.6 Properties of carbonmonoxides .................................................................................................. 34
Table 6.1: Conversion percentages............................................................................................................. 45
Table 6.2: Molecular weight in kg /kgmole ............................................................................................... 45
Table 6.4 Material balance over quench column ........................................................................................ 55
Table 6.3 Energy required for preheat the reactants................................................................................... 58
Table 6.4 Components and its properties ................................................................................................... 59
Table 6.5 Energy required .......................................................................................................................... 60
Table 6.6 Energy required .......................................................................................................................... 62
Table 6.7 Enthalpy out with gases .............................................................................................................. 63
Table 6.8 Enthalpy out with the mixture .................................................................................................... 66
Table 6.9 Enthalpy out with unabsorbed gases from top ........................................................................... 67
Table 6.10 Enthalpy out with bottom stream ............................................................................................. 68
Table 6.11 Enthalpy out with Distillate ...................................................................................................... 69
Table 7.1 X-Y composition ....................................................................................................................... 77
VI
LIST OF FIGURES
Figure1.1: Structure of acrylonitrile ............................................................................................................ 2

Figure 2.1: World acrylonitrile capacity..................................................................................................... 12
Figure 2.2: Historical prices in USA, Belgium and China ......................................................................... 14
Figure 3.1: SOHIO Process ........................................................................................................................ 20
Figure 4.1: Block Flow Diagram of Acrylonitrile, in SOHIO Process ...................................................... 25
Figure 4.2:Block diagram for fluidized bed reactor ................................................................................... 27
Figure 4.3: Chemical formula of acetonitrile ............................................................................................. 32
Figure 5.1: Process Flow Diagram on Chemcad Simulation...................................................................... 37
Figure 7.1 McCabe thiele chart .................................................................................................................. 79
Figure 8.1 Labor productivity growth of different countries ..................................................................... 94
Figure 8.2 Average temperatures and precipitation in Gebze, 2017 . ........................................................ 96
Figure 8.3 Pathways of deciding plant layout . ........................................................................................ 101
Figure 8.4 The site location of the company . ......................................................................................... 102
Figure 8.5 Plant layout. ............................................................................................................................ 103
VII
ABBREVIATION LIST
SOHIO: Standard Oil of Ohio

ACN: Acrylonitrile
ABS: Acrylonitrile-butadiene-styrene
PAM: Polyacrylamide
VOC: Volatile organic compound
VIII
SECTION -I
GENERAL INFORMATION
1
1. GENERAL INFORMATION
Figure1.1: Structure of acrylonitrile[1]
Acrilonitrile (also called acrylic acid nitrile, propylene nitrile, vinylcyanide, propenoic 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. Chemical formula C3H3N[1].
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 impacts, the process is viable for modification [33]. If
there is no leakage during storage and transportation was not found. However, in cigarette smoke
and motor vehicle exhaust, acrylonitrile it increases its importance, in terms of human health. In
addition, exposure can create a potential risk. Acrylonitrile on health and environment researches
and evaluations were carried out that examine the effects in a multifaceted way [34].
2
1.1 Physical Properties
Acrylonitrile (C3H3N,molwt = 53.064) is an unsaturated molecule having a carbon-carbon double

bond combinated with a nitrile group. It is a uncolored liquid. With the faintly pungent odourof
peach pits. Its properties are summerized in Table 1. Acrylonitrile is misciple with most organic
solvents, including aceton, benzene, carbontetrachloride, ether, ethanol, ethyl acetate, ethylene,
cyanohydrin, liquid carbon dioxide, methanol , petroleumether, toluene, xylene, and some
kerosene. The water solubility of acrylonitrile at a number of temperatures is shown in Table1
[1].
Table 1.1: Some physical properties of acrylonitrile [2]
Molecular formula C3H3N
Molar mass 53,06
Density 0,8060 g/cm3(20oC)
Freezing point -83,55 ± 0,05 oC
Boiling point (760mmHg) 77,3oC
Flash point -5oC
Critical temperature 246,0 oC
Criticalpressure 3,535 x 103kPa
Ignition temperature 481,0oC
Vıscosity at 25oC 0,34
3
1.2 Chemical Properties
The presence of both the olefinic (carbon-carbon double bond ) group and the nitrile group in
acrylonitrile gives the molecule its matchless and varied reactivity. This reactivity leads to the
great versatility of acrylonitrile as a raw material. The olefinic group can undergo polimerization
and co-polymerization, hydrogenation, oxidation, addition and cyclization. The nitrile group can
undergo hydrogenation, hydrolysis, hydration, esterification, cyclization and reduction [3].
1.3 Use of Acrylonitrile
Acrylonitrile is used as:
•A pure material for the production of synthetic fibres, plastics and synthetic rubber. One of the
causes for the versatility of acrylonitrile is that it can form copolymers with other unsaturated
compounds, such as styrene and butadiene [1].
•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 [4].
•In the synthesis of compounds used for the production of adhesives, anti-oxidants, binders for
dyestuffs and emulsifiers [1].
4
1.4 Occurrence
1.4.1 Natural occurrence
Acrylonitrile is not known to occur as a native product.
1.4.2 Occupational exposure
Occupational emptying to acrylonitrile have been measured in monomer production and in the
production of staples, resins, polymers and other chemical intermediates from acrylonitrile [5].
(a) Monomer production
(b) Fibre production
(c) Resin production
(d) Rubber and polymer production
(e) Organic chemical synthesis
(f) Miscellaneous
1.5 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 Sohio process [1].
There are various methods for the production of acrylonitrile. The main ones [2]:
• Sohio process
• Production from ethylene cyanohydrin
• Production from acetylene and hydrocyanicacid
5
1.5.1 Sohio process
Approximately 90% of total ACN production follows the Standard Oil of Ohio (SOHIO)
process, which is based on propylene ammoxidation. Reaction is too high selective, fast, ACN
production without the need for excessive recycling efforts [3].
The cost of ACN production, where more than 70% of propylene is produced, has increased in
recent times. For this reason, ACN is produced 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 [3].
In this process propene, oxygen (as air), and ammonia are catalytically converted directly to
acrylonitrile using a fluidized-bed reactor operated at temperatures of 400 – 500 °C and gauge
pressures of 30 – 200 kPa (0,3 – 2 bar) [1]:
2CH2=CH-CH3 + 2NH3 + 3O2 → 2CH2=CH-C≡N + 6H2O
1.5.2 Production from ethylene cyanohydrin
Germany (I.G. Farben, 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].
1.5.3 Production from acetylene and 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
6
Though a vapour 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, divinylacetylene and methyl vinyl ketone, were difficult to
remove, and the catalyst required frequent regeneration. Du Pont, American Cyan-amid and
Monsanto employed this method until about 1970 [1].
1.6 Toxicology of Acrylonitrile
Acrylonitrile is toxic if inhaled or ingesting or in touch with the skin. Skin touch causes
blistering; the eyes and mucous membranes are particularly at risk. Symptoms of acute exposure
are headache, nausea, dizziness and vomiting. After substantial exposure, the symptoms are
unconsciousness, spasms and cessation of breathing.
These symptoms can be delayed a few hours after exposure. Acrylonitrile must be regarded as if
it is potentially carcinogenic to man. If any contact with Acrylonitrile has taken place or is
suspected, immediate advice of medical service is strongly recommended [6].
If somebody breathe in these gases, these gases can generate serious sharp toxicity, loss of
consciousness also death. However, antidotes can prevent from serious harm [7].
Violent body soreness and allergic dermatitis occurs when contacting with acrylonitrile directly.
Death of users of acrylonitrile can happens. Because of death, industries of pharmaceutical
developed fumigants [8].
Acrylonitrile is a carcinogen chemical, and it is depending proof carcinogenicity from studies in

experimental animals. Oral exposure to acrylonitrile caused cancer of the fore stomach and
increased benign tumors in mice [8, 9].
Acrylonitrile must be stayed away from, effective oxidizers, principally bromine and strong
bases, strong acids, copper, copper alloys, ammonia and amines. Bromine is reactive with these
chemicals. Contacting with these chemicals could cause chemical reaction which could
consequently of a fire or explosion. Before acrylonitrile comes in contact via any other chemical,
chemical suitability should be determined [10].
7
Table 1.2: The primarily toxic effects in humans of acrylonitrile [2].
Toxidity Routes of Dose Time
Exposure
Headache, tremor, convulsions Inhalation ---- Acute
Nausea, Inhalation 35-220 Acute
vomiting, headache, dizziness mg/kg
Dizziness, fever, nausea, vomiting Dermal, ---- Acute
inhalation
Erythema, Dermal Acute
Skin swelling, skin burning Dermal Acute
Headache, sleep disorder, chest pain Inhalation ---- For
months
Headache, weakness, tiredness,Inhalation ---- For years

nausea, vomiting, nosebleed,insomnia
Decreasing of hemoglabin Inhalation 2,5-5 Chronic
mg/kg
Headache, tiredness, swelter Inhalation ---- Chronic
8
1.7 Reactions of Acrylonitrile
1.7.1 Reactions with nitrile class
Hydration and Hydrolysis
Hydrolysis of the nitrile class in part manufactures acrylamide sulfate, which upon
neutralization yields acrylamide; this is the principle for acrylamide's traditional produced in
concentrated 85% sulfuric acid. In dilute acid or alkali, finalized hydrolysis occurs to yield
acrylic acid [35,36].
1.7.2 Reactions with olefins and alcohols
Compounds like olefins and secondary and tertiary alcohols which form carbonium ions in acid,
and N-substituted acrylamides are created via The Ritter reaction [36].
1.7.3 Reactions with aldehydes and methylol compounds
When sulphuric acid catalyzed, formaldehyde and acrylonitrile reactive to form any of N,N'-
methylene bisacrylamide or 1,3,5-triacrylylhexahydro-s-triazine, based on the conditions. Such ,
N-methylol benzamide reactive along with yield mixed bisamides in the presence of sulfuric
acid. N-Methylol phthalimide reactive long with occur N-phthalimido methylacrylamide[35].
1.7.4 Reaction of the double bond
Hydrogenation
The excellent yield of propionitrile is achieved along with the catalysts of metal. This
propionitrile can be more easier hydrogenated to propylamine [36].
Halogenation
For generationing of 2,3-dihalopropionitriles at low temperatures halogenation yields going

quietly. If there is pyridine, addition of chlorine constitutes 2,3-dichloropropionitrile. 2,2,3-
trihalopropionitrile is admitted when there is no UV light in risen temperatures; with UV light,
both 2,2,3- and 2,3,3-isomers are formed. For giving 2,3-dichloropropionic acid esters
chlorination and alcoholysis occur [36].
9
Hydroformylation
The other name of this process is the oxo-synthesis. For giving β-cyanopropionaldehyde,
acrylonitrile in contact with a blend of hydrogen and carbon monoxide cobalt octacarbonyl
has been catalyzed. This reacts via HCN and ammonia after that hydrolysis produces glutamic
acid on a huge traditional measure[35,36].
Hydrodimerization
Adiponitrile have been done for consisting the induce of acrylonitrile’s dimerization
electrochemically and chemically. Hydrodimerization with its derivatives happens [36].
1.7.5 Reactions of both functional classses
For fabricating 3-chloropropionic acid, hydrolysis of acrylonitrile have been catalyzed by

hydrochloric acid. Alcoholysis and chlorination happens in the presence of sulfuric acid and
alcoholysis and hydrochlorination also happens. Glycidamide is consisted by intervention of
acrylonitrile with hydrogen peroxide. Such, forms bis (2-carboxamidoethyl) sulfide or poly (β-
alanine) treatment with water, a weak base sulfide or, containing ammonium [36].
10
SECTION-II
SITUATION IN THE
WORLD AND TURKEY
11
2. SITUATION IN THE WORLD AND TURKEY
2.1 Acrylonitrile Marketing in the World
Its worldwide production is approximately 5 million tons per year, and besides being used in the
manufacture of acrylic fibers responding for almost 50% of consumption [19].
Acrylonitrile profitability will remain low because capacity is expanding faster than demand is
growing. However very little acrylonitrile is consumed, carbon fibre production is growing
rapidly [11].
Demand for acrylonitrile is broadly tied to the general economy and is therefore cyclical. Most of
acrylonitrile’s major end markets—ABS resins, acrylic fiber, and adiponitrile, for instance—are
cyclical and impacted by economic downturns, when consumer spending contracts. In 2016,
China alone accounted for 32% of the global acrylonitrile market. Further growth is forecast for
acrylonitrile through 2021. Northeast Asia is forecast to account for about 55% of the global
incremental demand over the next five years. The acrylonitrile market’s dependence on the state
of the economy was evidenced during the global recession in 2008–09, when it dropped by 12%
in just a year[12].
Figure 2.1: World acrylonitrile capacity[11]
12
Production of acrylonitrile-butadiene
butadiene-styrene
styrene (ABS) resins is the primary end use for
acrylonitrile globally, accounting for 34% of the overall demand. ABS is the largest
largest-volume
thermoplastic engineering resin in the market because of its unique properties of strength,
rigidity, heat resistance, and toughness, which make it a prime copolymer for diverse technical
and demanding applications. The composition of ABS resins can vary widely, allowing the
production of many different grades that can be tailored for different end-use
use applications [12].
Acrylic fiber was once the single largest outlet for acrylonitrile, accounting for more than half of
the market in 2000. Over the past decade, the acrylonitrile volumes used to produce acrylic fiber
have contracted att an average rate of 3.3% annually, and now account for ab
about 29% of
acrylonitrile demand [12].
Acrylamide is the world’s third-largest acrylonitrile end use, accounting for 13% of the market
for acrylonitrile. More than 90% of acrylamide is used for polyacrylamide
polyacrylamide (PAM) production.
PAMs are organic flocculants and their dominant use is as wastewater treatment agents. They are
used primarily as conditioning and dewatering aids for sludges, thickening of waste sludges in
municipal sewage treatment, and in industrial
industrial operations such as pulp and paper plants [12].
Over the next five years, acrylonitrile demand is expected to increase at an average annual rate of
3,2%.
2%. Overall, 55% of the global demand growth is expected to come from Northeast Asia,
followed by the Middle East and North America. Acrylamide and ABS resin applications will
account for most acrylonitrile demand growth through 2021 [12].
Table 2.1: The biggest manufacturers of Acrylonitrile in the World[26]

World[26]
Ineos, DSM and Asahi Kasei are leader companies in the world[26].
13
Figure 2.2: Historical prices in USA, Belgium and China[14]
2.2 Acrylonitrile Marketing InTurkey
30% of ACN locally sourced from PETKIM, the rest is heavily imported from Europe [15].
AKSA imports more Acrylonitrile than any other fiber producer in the world [15].
In 1985, Petkim began producing 70000 tons of acrylonitrile. Petkim currently produces 90000
tons / year of acrylonitrile [16].
Table 2.1: The amount of acrylonitrile produced by PETKIM over the years [20].
2007 2008 2009 2010 2011
Acrylonitrile 91,538 ton 90,367 ton 93,552 ton 94,045 ton 98,072 ton
14
SECTION-III
PROCESS
SELECTION
AND CAPACITY
15
3.PROCESS SELECTION AND CAPACITY
3.1 Process Selection
3.1.1 Cost estimation for all production methods
Production from ethylene cyanohydrin
Main reaction:
HO-CH2-CH2-C≡N→ CH2=CH-C ≡N + H2O
Table 3.1: Cost of each component[37]
Chemical Cost(dollar/kg)
(CH2CH2)O (ethyleneoxide) 7,15
HCN (hydrocyanicacid) 6,37
C3H3N(acrylonitrile) 4,5
H2O(water) 0,5
Table 3.2: Reaction and cost of component[37]

(CH2CH2)O + HCN→ CH2=CH–CN + H2O
Mol 1 1 1 3
MW (g/mol) 42 27 53 18
Mol/mol of 0,792 0,509 1 0,339

Propylene
Dollars/mol 7,15 6,37 4,25 0,5
Gross profit;
[4,25x(1)+0,5(0,339)]-[(7,15x0,792)+(6,37x0,509)]=-4,486dollars/kg of acrylonitrile. This

method is not suitable for producing AN.
16
Production from acetylene and hydrocyanic acid
Main reaction:
H-C≡C-H + HCN → CH2=CH-CN

C2H4 (acetylene) 1,625
HCN 6,37
H2O(water) 0,5

H-CC-H + HCN → CH2-CH-CN
Mol 1 1 1
MW (g/mol) 26 27 53
Mol/mol of 0,490 0,509 1

Propylene
Dollars/mol 1,625 6,37 4,25
Gross profit;
4,25x(1)-[(1,625x0,490)+(6,37x0,509)]= 0,2114 dollars/kg of acrylonitrile.
0,2114x0,60=0,1268 dollars per kg of AN, this method is not profitable.
17
Sohio process ammoxidation of propylene
Main reaction:
CH2=CH-CH3+ NH3+ 3/2 O2→C3H3N+ 3 H2O

C3H6(propylene) 0,9
NH3(ammonia) 0,3
O2(oxygen) -
H2O(water) 0,5

C3H6 +NH3 +3/2O2 → C3H3N + 3 H2O
Mol 1 1 3/2 1 3
MW (g/mol) 42 17 48 53 54
Mol/mol of 0,792 0,320 0,905 1 1,019

Propylene
Dollars/mol 0,90 0,30 - 4,25 0,5
Gross profit is;
[4,25x(1)+0,5(1,019)]-[(0,9x0,792)+(0,3x0,320)]=3,9507 dollars/kg of acrylonitrile.
Propylene conversion is higher than 95%, also a selective yield in AN close to 80%;
3,9507x0,8= 3,1605 dollars per kg of acrylonitrile.
• Cost is cheaper than other production methods [1].
• It is the most commonly used procedure in the production of acrylonitrile [1].
18
• Propylene conversion can be higher than 95% [3].
• The resulting by-products can be used for other processes [3].
SOHIO process is selected for the production of acrylonitrile. Today, approximately 90% of total
ACN production follows the Standard Oil of Ohio (SOHIO) process, which is based on
propylene amoxidation. Reaction is too high selective, fast, ACN production without the need for
excessive recycling efforts [21].
The cost of ACN production, where more than 70% of propylene is produced, has increased in
recent times. For this reason, ACN is produced 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 [21]. The ammoxidation 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 ACN is the traditional SOHIO process [21]. All the reaction
takes place in the vapour 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 by-
products 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 ACN [1].
Variations within the SOHIO process may provide for purification, storage, and loading facilities
for these recoverable by-products. Other diversities of the SOHIO process contain the recovery
of ammonium sulfate from the reactor effluent to allow for biological processing of a waste
water stream and variations in catalysts and reactor situations [1].
19
3.2 Production of Acrylonitrile from SOHIO Process
In the standard SOHIO process, as given air, ammonia, and propylene are introduced into 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
seconds habitation time.
The heat generated from the exothermic reaction is recovered via a waste-heat-recovery boiler
[1].
Exhaust Gas
2 5
Ammonia 4 16
HCN
3
20
7
18
3
Propylene 2 6
1
7 Acrylonitrile
8 17
9 28
4 9 21
1 12
Air 5 16
6 14 23
22
11 15
10 8
Impurities
Sulfuric acid Water 14 29
10 24
13
12
25
11
17
18 Acetonitrile
Ammonium
Sulfate
19 Water
Figure 3.1: SOHIO Process
20
Main Reaction:
2 3 6 +2 3 +3 2 →2 3 3 +6 2O
Side Reactions:
4 3 6+ 6 3 +3 2 →6 2 3 +6 2
3 6 +3 3 +3 2→ 3 +6 2
2 3 6 +3 2 →6 2 +6 2O
The product stream then flows through aopposite current water absorber-stripper to reject inert
gases and recover reaction products. The operation yields a mixture of ACN, acetonitrile, and
water and then is sent to a fractionator to remove hydrogen cyanide. The final two steps involve
the drying of the ACN stream and the final distillation to rout out heavy ends. The fiber-grade
ACN obtained from the process is 99+% pure. Several fluid-bed catalysts have been used since
the inception of the SOHIO ammoxidation process [1].
21
Catalyst 49, which represents the fourth major level of improvement, is currently recommended
in the process. Emissions of ACN during start-up are radically higher than during normal
operation. During start-up, the reactor is heated to operating temperature before the reactants
(propylene and ammonia) are introduced. Effluent from the reactor during start-up begins as
oxygen-rich, then passes through the explosive range before reaching the fuel-rich zone that is
maintained during normal plant operation. To prevent explosions in the line to the absorber, the
reactor effluent is vented to the atmosphere until the fuel-rich effluent mixture can be achieved.
The absorber vent gas contains nitrogen and unconverted oxygen from the air fed to the reactor,
propane and unconverted propylene from the propylene feed, product ACN, by-product
hydrogen cyanide and acetonitrile, other organics not recovered from the absorber, and some
water vapour [1].
The ACN content of the combined column purge vent gases is slightly high, about 50% of the
total VOCs emitted from the recovery, acetonitrile, light ends, and product columns. The rest of
the vent gases occur non-condensibles that are dissolved in the feed to the columns, the VOCs
that are not condensed, and, for the columns operating under vacuum, the air that leakages into
the column and is removed by the vacuum jet systems [1].
For the ACN process, by-product hydrogen cyanide and acetonitrile are incinerated along with
product column bottoms. The primary impurity problem related to the incinerator stack is the
formation of NOx from the fuel nitrogen of the acetonitrile stream and hydrogen cyanide. Carbon
dioxide and fewer amounts of CO are emitted from the incinerator stack gas. Other emission
sources contain the volatilization of hydrocarbons through process leaks (fugitive emissions) and
from the deep well ponds, breathing and working losses from product storage tanks, and losses
during product loading operations. The fugitive and deep well/pond emissions consist primarily
of propane and propylene, while the storage tank and product loading emissions comprise
primarily of ACN [1].
22
3.2.1 Catalysts
Numerous catalyst formulations have been proposed to counterpoise the lower yield coming
about because of the improvement of side responses, and their execution has reliably enhanced
with time. They are on the whole utilizing blended oxides relies upon antimony, arsenic,
bismuth, cobalt, tin, iron, molybdenum, nickel, phosphorus, tellurium, uranium, vanadium, with
or without help [17].
3.3 Capacity of the Process
When determining capacity for acrylonitrile production plant to be established in Turkey, the
domestic market in Turkey is necessary to take into consideration. PETKIM is known to produce
about 90000 tons of acrylonitrile annually [16]. Likewise, AKSA, which has become the world's
largest producer of acrylic fibers when it turns its inner market, meets a part of the production of
acrylonitrile by taking the full amount produced by PETKIM. However, AKSA 315000 tons /
year, with the largest capacity in the world, because it is the only acrylic fiber manufacturer in
Turkey meets the needs of the remaining acrylonitrile from abroad. Therefore, all the needs of
acrylonitrile in Turkey which also aims at establishing a facility is provided.As is known, about
90% acrylonitrile raw material is present in the production of acrylic fibers. According to AKSA
producing 315000 tons of fiber per year, the amount of ACN is 283500 tons[15]. 90000 tons of
acrylonitrile PETKIM per year [16].The remaining amount of acrylonitrile will be 193500 tons.
The acrylonitrile capacities produced in different parts of the world are shown in table 2.1 and
table 2.2. Inos, DSM and Asahi Kasei are world leaders in the production of acrylonitrile[25,26].
These include Turkey, which we determine by looking at the needs of 193500 tonnes of
acrylonitrile as a target of generating 75% of capacity, the facility will have an annual production
capacity of approximately 146000 tons of acrylonitrile [15,16].
23
SECTION-IV
PRODUCTION FLOW
DIAGRAMS
24
4.ACRYLONITRILE PRODUCTION FLOW DIAGRAMS I
4.1 Block Flow Diagram
Figure 4.1: Block Flow Diagram of Acrylonitrile, in SOHIO Process[45]
25
4.2 Explain the Related Equipments
4.2.1Usedequipments
• Fluidized Bed Reactor
• Quencher
• Recovery
• Ammonium sulphate unit
• Purification
In the standard SOHIO process, as given air, ammonia, and propylene are introduced into a fluid-
bed catalytic reactor operating at 0,3-2 atm and 400-5100C. Ammonia and air are fed to the
reactor in slight excess of stoichiometric proportions because excess ammonia drives the reaction
closer to completionand air continually regenerates the catalyst. An important feature of the
process is the high conversion of reactants on a once-through basis with only a few seconds
residence time. The heat generated from the exothermic reaction is recovered via a waste-heat-
recovery boiler [1].
4.2.1.1Fluidized bed reactor
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 [22].
The air is introduced below the bottom grid whereas mixed propene and ammonia are introduced
through the spiders above the grid. Residence time in the reactor is between 2 to 20 seconds.
There is almost complete transformation of propene and the selectivity of acrylonitrile is around
80%[9-10]. The main reactions and side reactions of the process in reactor are as follows.
The gaseous phase product stream is remove in liquid phase through counter current water
absorber to remove inert gases and recover reaction products. Mixture of acrylonitrile,
acetonitrile, carbon oxides and hydrogen cyanide are formed. Product surge is sent to
fractionator to remove hydrogen cyanide.
26
Acrylonitrile is separated from acetonitrile by extractive distillation. Acrylonitrile obtained after
extractive distillation is subjected for drying. The acrylonitrile obtained after drying is 99% pure.
Acetonitrile and hydrogen cyanide which are the primary byproducts of the process are subjected
to incineration. Incineration leads to the formation of nitrogen oxides, carbon oxides which are
the primary pollutants. Other emission resource involve the volatilization of hydrocarbons
through process leaks and from the deep well ponds, breathing and the working losses from the
product storage tanks and losses during product loading operations. Primarily propene and
propane are emitted in the fugitive and deep well or pond emissions, whereas storage tank and
product loading emissions consists of acrylonitrile [23].
Figure 4.2:Block diagram for fluidized bed reactor[23]
The equipment of the following table fluidized bed reactors is summarized[23].
27
4.2.1.2 Quencher
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 [24].
Advantages
• Higher recovery efficiency of acrylonitrile due to low pH
• Lower polymer production in the quench section
• Opportunity to reuse waste water streams
Disadvantages
• Lower recovery of acrylonitrile due to high pH in the quench
• Higher polymer formation in the quench
In the first step of the ‘basic quench’, reactor off-gas is quenched with water. Water losses are
made up by adding fresh water or recycling plant waste water streams. Mainly the catalyst fines
are removed from the reactor off-gas. However, the addition of water causes the reaction of
high-boiling oligomeric compounds and organic ammonium salts which must be purged from the
system, in common with organic acids. In the second step, the gas is treated isothermally with
sulfuric acid to remove excess ammonia. Fresh acid has to be added to maintain the acidity, but
no additional water is required [24].
28
4.2.1.3 Recovery
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 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) [24].
4.2.1.4 Ammonium sulfate unit
The ammonium sulfate in the quench purge is recovered by crystallisation to produce a saleable
by-product. The crystallisation stage generates a waste liquor stream. The effluent streams from
the crystallisation process that include some ammonium sulfate, organics and possibly catalyst
fines are incinerated or routed to the final waste water treatment [24].
4.2.1.5 Purification
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 into other products on site, or sold (if a market is available) [24].
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 polymerisation. 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 overthrow all 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. In order to protect the final
product against possible polymerisation reactions during storage, small quantities of inhibitors,
such as MEHQ (monomethyl ether of hydroquinone), are added to the acrylonitrile.
29
The ruins from the bottom of the acrylonitrile column contains some high boiling-point nitriles
[24].
4.3 Explain the Raw Materials
4.3.1 Propylene
Propylene (C3H6) is a colorless gas. It is occured 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 chemicals [25].
Table 4.1: Physical properties of propylene [25]
Table 4.2:Propylene Values of thermo physical properties of the saturated liquid and vapor [26]
30
4.3.2 Air
Air is a consist of gases, 78% nitrogen and 21% oxygen with traces of water vapor, carbon
dioxide, argon, and various other components [27].
Table 4.3: Thermodynamic properties of air [28]
4.3.3 Ammonia
Ammonia is also commercially and commonly available as an aquaeous solution; the must
common commercial formulation is 28-30% NH3 [29].
Table 4.4: Physical and chemical properties of ammonia[30]

Property Value
Molecular weight 17,03
Color Colorless
Physical state Gas at room temperature
Melting point -77,70C
Boiling point -33,350C
Density (gas) 0,7710 g/l
Odor Sharp
31
4.4 Explain the Byproduct Materials
4.4.1 Hydrocyanic acid
4.4.1.1 Chemical properties of hydrocyanic acid
Hydrocyanic acid has a density of 0,688 g/cm3 at 20°C, a boiling point of 25,7°C, and a freezing
point of – 14°C. It burns in air to yield H2O, CO2, and N2; a mixture of hydrocyanic acid vapors
and air explodes when ignited. Hydrocyanic acid, a very weak acid, distilleted upon storage,
especially in the presence of impurities. Its salts are called cyanides, and its organic derivatives,
nitriles. Hydrocyanic acid is created upon hydrolysis of amygdalin, present in bitter almonds and
apricots. An aqueous hydrocyanic acid solution can be provided by the distillation of potassium
ferrocyanide, K4[Fe(CN)6], with dilute sulfuric acid, H2SO4 [31].
4.4.1.2 The uses of hydrocyanic acid
The greater part of the hydrocyanic acid manufactured in this way is spended in the manufacture
of acrylonitrile, either by condensation with ethylene oxide to form ethylene cyanhydrin, or
directly by liquid phase catalytic combination with acetylene. Acrylonitrile is polymerised with
butadiene to form special-purpose synthetic rubbers. These nitrile rubbers are used for
mechanical rubber pads, textile and paper sizings, and for petrol and oil resistant goods. They are
marketed in the United States under brand names Hycar, Paracril, Butaprene and Chemigum.
Hycar will shortly be produced in this country by British Geon Ltd.. [32].
4.4.2Acetonitrile
Acetonitrile (CH3CN) is a by-product of acrylonitrile manufacture [38].
Figure 4.3: Chemical formula of acetonitrile[38]
32
4.4.2.1Physical and chemical properties
Physical properties
Acetonitrile is a volatile, colourless liquid with a sweet, ether-like odour [38]. It is extremely
soluble in water and easily miscible with ethanol, ether, acetone, chloroform, carbon
tetrachloride and ethylene chloride [39].It is immiscible with many saturated hydrocarbons
(petroleum fractions)[40].
Table 4.5 Commercial acetonitrile specifications [38]
Chemical properties
Although acetonitrile is one of the most stable nitriles, it under goes typical nitrile reactions and
is used to produce many types of nitrogen-containing compounds. It can be trimerized to S-
trimethyltriazine and has been telomerized with ethylene an copolymerized with alpha-epoxides
[38]. Acetonitrile produces hydrogen cyanide when heated to decomposition or when reacted
with acids or oxidizing agents[41].
4.4.2.1 Use of acetonitrile
It is used as a solvent for spinning synthetic fibres and in casting and moulding plastics. In
laboratories, it is commonly used in high-performance liquid chromatographic (HPLC) analysis
and as a solvent for DNA synthesis and peptide sequencing [42].
33
4.4.3 Carbon monoxides
Carbon monoxide is a colorless, odorless gas. Prolonged exposure to carbon monoxide rich
atmospheres may be fatal. It is easily fired. It is just lighter than air and a fire can flash back to
the source of leak very easily. Under prolonged exposure to fire or intense heat the containers
may strongly rupture and rocket [43].
Table4.6Properties of carbon monoxides [44]
Main Reaction :
2C3H6 + 2NH3+ 3O2 → 2C3H3N + 6H2O
Side Reaction:
4C3H6 + 6NH3 + 302 → 6 C2H3N + 6H2O
C3H6 + 3NH3 + 3O2 → 3HCN + 6H2O
2C3H6 + 3O2 → 6CO2+ 6H2O
4.5 Evaluation and Examination of By Products
Nearly all of the acrylonitrile (ACN) produced in the world today is produced using the SOHIO
process for ammoxidation of propylene and ammonia. The all reaction happen in the vapour
phase in the presence of a catalyst. The primary by-products of the process are hydrogen
cyanide, acetonitrile, and carbon oxides. The save of these by-products depends on factors such
as market conditions, plant location, and energy costs.
34
Hydrogen cyanide and acetonitrile, although they carry a market value, are usually incinerated,
indicating that the production of these by-products has little effect on the economics of
producing ACN. Variations within the SOHIO process may ensure for purification, storage, and
loading facilities for these retrievable, by-products. Other variations of the SOHIO process added
the recovery of ammonium sulfate from the reactor effluent to allow for biological treatment of a
waste water stream and variations in catalysts and reactor conditions [44].
35
SECTION-V
PRODUCTION FLOW
DIAGRAMS-II
36
5. PROCESS FLOW DIAGRAM II
5.1 Acrylonitrile Production in Chemcad Simulation
Exhaust Gas
2 5
Ammonia 4 16
HCN
3
20
7
18
Propylene 3
2 6
1
7 Acrylonitrile
8 17
9 28
4 9 21
1 12
Air 5 16
6 14 23
22
11 15
10 8
Impurities
Sulfuric acid Water 14 29
10 24
13
12
25
11
17
18 Acetonitrile
Ammonium
Sulfate
19 Water
Figure 5.1: Process Flow Diagram on Chemcad Simulation
37
5.2 Chemcad Equipment Values
5.2.1 Reactor
7
8
10 8
In (kg/h) Out (kg/h)

Ammonia 7005,03 -
Propylene 16443,63 -
Air 112580,95 -
ACN - 16678,66
HCN - 1897,14
Acetonitrile - 561,58
Acrolein - 155,63
Acrylic Acid - 428,7
Acetic Acid - 71,45
Carbon Dioxide - 2672,04
Carbon Monoxide - 621,43
Water - 20769,946
38
5.2.2 Quencher
12
11 15
14
25

Ammonia - -
Propylene - -
Air - -
ACN 16678,66 16678,66
HCN 1897,14 1897,14
Acetonitrile 561,58 561,58
Acrolein 155,63 155,63
Acrylic Acid 428,7 428,7
Acetic Acid 71,45 71,45
Carbon Dioxide 2672,04 2672,04
Carbon Monoxide 621,43 621,43
Water 20877,0547 20877,0547
Sulfuric Acid 524,8331 524,8331
Ammonium Sulfate 707,1408(waste)
39
5.2.3 Absorber

Ammonia - 181,934(waste)
Propylene - -
Air - -
ACN 16678,66 16678,66
HCN 1897,14 1897,14
Acrolein 155,63 155,63(waste)
Acrylic Acid 428,7 428,7(waste)
Acetic Acid 71,45 71,45(waste)
Carbon Dioxide 2672,04 2672,04(waste)
Carbon Monoxide 621,43 621,43(waste)
Water 20877,0547 20877,0547
40
5.2.4 Recovery column
16
16
23

ACN 16678,66 16678,66(distillate)
HCN 1897,14 1897,14(distillate)
Acetonitrile 561,58 561,58(bottom)
Water 20877,0547 20877,0547(bottom)
5.2.5 Acetonitrile column
11
17
18
19

Acetonitrile 561,58 561,58(distillate)
Water 20877,0547 20877,0547(bottom)
41
5.2.6 HCN column
17
21
24

ACN 16678,66 16678,66(bottom)
HCN 1897,14 1897,14(distillate)
5.2.7 ACN column
18
28
29

ACN 16678,66 16678,66(distillate)
42
SECTION-VI
MATERIAL AND
ENERGY BALANCE
43
6. MATERIAL AND ENERGY BALANCE
6.1 MATERIAL BALANCE
Material balances are the basis of process design. A material balance taken over complete
processs will determine the quantities of raw materials required and products produced. Balances
over. Individual process until set the process stream flows and compositions. The general
conservation equation for any process can be written as;
Material out = material in + generation - consumption + accumulation
For a steady state process the accumulation term is zero. If a chemical reaction is taking place a
particular chemical species may be formed or consumed. But if there is no chemical reaction, the
steady state balance reducesto,
Material out = Material in
A balance equation can be written for each separately identifiable species present, elements,
compounds and for total material.
6.1.1 Material Balance for Reactor
Basis:
Plant capacity: 146000 tons/annum Consider 365 working days/annum
Therefore output/day = 146000 tons/ 365days = 400 tons/day
Capacity = 400 tons /day x 1day/24 hours x 1000kg/ 1tons= 16666,67 kg/h
(16666,67 kg/h) / (53,03kmol/kg) = 314,28 kmol/h
44
Catalyst Performance:
AsusingcatalystBi-MogivenbySohio,theconversionofC3H6istakenas, [76].
Table 6.1: Conversion percentages
80% to ACN
2.3% to Aceto
5.9% to HCN
1.5% to Acrylic acid
0.7% to Acrolein
0.2% to Aceticacid
5.1% to CO2
2.9% to CO
1.4% to UnconvertedC3H6
Molecular Weight:
Table 6.2: Molecular weight in kg /kgmole
Acrylonitrile [C2H3CN] 53,03
Acetonitrile [CH3CN] 41,02
Hydrogen cyanide [HCN] 27,01
Propylene [C3H6] 42,03
45
Ammonia [NH3] 17
Oxygen [O2] 32
Nitrogen [N2] 28
Acrolein [CH2CHCHO] 56,03
Carbon monoxide [CO] 28,01
Water [H2O] 18
Carbon dioxide [CO2] 44,01
Acrylic acid [CH2CHCOOH] 72,03
Acetic acid [CH3COOH] 60,02
Acrylonitrile formation reaction:
C3H6+ 3/2 O2+ NH3CH2= CHCN +3H2O
Assume there is 1% loss of ACN as in any outlet stream or which may polymerized.
16666,67 / 0,99 = 16835,02 kg/h
314,28 / 0,99 = 317,45 kmol/h
So, actual capacity of plants are16835,02 kg/hand 317,45 kmol/h.
But only 80% is being converted to acrylonitrile;
Therefore actual C3H6 supplied = 317,45 / 0.8 = 396,81 kmol/h
Propylene/ammonia/air: 1/1.2/9.5 (Mole ratio)[76]
46
Acrylonitrile :
2C3H6+ 3O2+ 2NH32CH2= CHCN +6H2O
rC3H6= kC3H6 x C2C3H6xC2NH3 x C3O2
C3H6+ 3/2O2+ NH3CH2= CHCN + H2O
(42.03) (48) (17) (53.03) (54)
Propylene required (for 80% conversion to ACN)
= (16835,02x 42,03) / 53,03 = 13342,93 kg/h (for 80% conversion)
Actual C3H6used = 13342,93 /0,80 = 16678,66kg/h
Hydrogen Syanide :
C3H6+ 3NH3+ 3O2 3HCN +6H2O
rC3H6 = kC3H6 x C C3H6 xC3NH3 x C3O2
C3H6+ 3NH3+ 3O2 3HCN +6H2O
(42.03) (51) (96) (81.03) (108)
Hydrogen Cyanide produced = (0,59 x 16678,66)x (81,03) / 42,03 = 1897,14 kg/h
Acetonitrile :
2C3H6+ 3NH3+3O23CH3CN +6H2O
rC3H6 = kC3H6 x C2C3H6 xC3NH3 x C3O2
C3H6+ 3/2NH3+ 3/2O23/2CH3CN + 3H2O
(42.03) (48) (25.5) (61.53) (54)
Acetonitrile produced = (0,023x16678,66) x (61,53) /42,03 = 561,58 kg/h
47
Acrolein:
C3H6 + O2 CH2 = CHCOOH + H2O
rC3H6 = kC3H6 x C C3H6 x C O2
C3H6 + O2CH2CHCHO+ H2O
(42.03) (32) (56.03) (18)
Acrolein produced = (0,007 x 16678,66) x (56,03) / 42,03 = 155,63 kg/h
Acrylic Acid :
2C3H6+ 3O22 CH2= CHCOOH + 2H2O
rC3H6 = kC3H6 x C2C3H6 x C3O2
C3H6+ 3/2O2CH2= CHCOOH + H2O
(42,03) (48) (72,03) (18)
Acrylic acid produced= (0,015x16678,66) x (72,03) / 42,03 = 428,7 kg/h
Acetic Acid :
2C3H6+ 3O23CH3COOH
C3H6 + 3/2O23/2CH3COOH
(42,03) (48) (90,03)
Acetic Acid produced = (0,002 x 16678,66) x (90,03) / 42,03 = 71,45 kg/h
48
CarbonDioxide:
2C3H6+ 9O26CO2+ 6H2O
C3H6+ 9/2O23CO2+ 3H2O
(42.03) (144) (132.03) (54)
Carbon Dioxide produced = (0,051 x 16678,66) x (132,03) / 42,03 = 2672,04 kg/h
Carbon Monoxide :
C3H6 + 3O23CO + 3H2O
rC3H6 = kC3H6 x C C3H6 x C3O2
C3H6 + 3O23CO + 3H2O
(42,03) (96) (84,03) (54)
Carbon Monoxide produced = (0,029x16678,66) x (54) / 42,03 = 621,43 kg/h
Ammonia :
(a) 2C3H6+ 3O2+ 2NH3 2CH2= CHCN +6H2O
Reactants :
C3H6= 396,81x0.80 = 317,448 kmol
NH3= 1 x 317,448 = 317,448 kmol
O2=1.5 x 317,448 = 476,172 kmol
Products :
C3H3N = 1× 317,448 = 317,448 kmol
H2O = 3 x 317,448 = 952,344 kmol
49
(b)C3H6+ 3NH3+ 3O2 3HCN + 6H2O (Hydrogen Syanide)
Reactans :
C3H6 = 396,81 x 0,059 = 23,41 kmol
NH3 = 3 x 23,41 = 70,23 kmol
O2 = 3 x 23,41 = 70,23 kmol
Products :
HCN = 3 x 23,41 = 70,23 kmol
H2O = 3 x 23,41 = 70,23 kmol
(c) C3H6+ 3/2NH3+ 3/2O23/2CH3CN + 3H2O
Reactans :
C3H6 = 396,81 x 0,023 = 9,12 kmol
NH3 = 1,5 x 9,12 = 13,68 kmol
O2 = 1,5 x 9,12 = 13,68 kmol
Products :
CH3CN = 1,5 x 9,12 = 13,68 kmol
H2O = 3 x 9,12 = 27,36 kmol
Total Ammonia = (a) + (b) + (c)  317,448 + 70,23 + 13,68 = 401,358 kmol
401,358 kmol/h x 17 kg/kmol = 6823,086 kg/h
NH3 / C3H6 = 0,42
16678,66 x 0,42 = 7005,03 NH3 consumed
NH3excess unreacted : 7005,03 – 6823,086 = 181,944 kg/h
50
Water :
(a) C3H6+ 3/2O2+ NH3CH2= CHCN + H2O (Acrylonitrile)
Reactans :
C3H6 = 396,81 x 0,80 = 317,448 kmol
NH3 = 1 x 317,448 = 317,448 kmol
O2 = 1,5 x 317,448 = 476,172 kmol
Products :
CH3CN = 1,5 x 317,448 = 476,172 kmol
H2O = 3 x 317,448 =952,344 kmol
(b)C3H6+ 3NH3+ 3O2 3HCN +6H2O (Hydrogen Syanide)
Reactans :
C3H6 = 396,81 x 0,059 = 23,41 kmol
NH3 = 3 x 23,41 = 70,23 kmol
O2 = 3 x 23,41 = 70,23 kmol
Products :
HCN = 3 x 23,41 = 70,23 kmol
H2O = 3 x 23,41 = 70,23 kmol
(c)C3H6+ 3/2NH3+ 3/2O23/2CH3CN + 3H2O (Acetonitile)
Reactans :
C3H6 = 396,81 x 0,023 = 9,12 kmol
NH3 = 1,5 x 9,12 = 13,68 kmol
O2 = 1,5 x 9,12 = 13,68 kmol
51
Products :
CH3CN = 1,5 x 9,12 = 13,68 kmol
H2O = 3 x 9,12 = 27,36 kmol
(d) C3H6+ O2CH2CHCHO + H2O (Acrolein)
Reactans :
C3H6 = 0,007 x 396,81 = 2,77
O2 = 1 x 2,77 = 2,77
Products :
C3H4O = 1 x 2,77 = 2,77
H2O = 1x 2,77 = 2,77
(e)C3H6+ 3/2O2CH2CHCOOH + H2O (Acrylic Acid)
Reactans :
C3H6 = 0,015 x 396,81 = 5,95 kmol/h
O2 = 1,5 x 5,95 = 8,925 kmol/h
Products :
C3H4O2 = 1 x 5,95 = 5,95 kmol/h
H2O = 1x 5,95 = 5,95 kmol/h
(f)C3H6+ 9/2O23CO2+ 3H2O (Carbon Dioxide)
Reactans :
C3H6 = 0,051 x 396,81 = 20,237 kmol/h
O2 = 1,5 x 20,237 = 30,35 kmol/h
52
Products :
CO2 = 3 x 20,237 = 60,711 kmol/h
H2O = 3 x 20,237 = 60,711 kmol/h
(g) C3H6 + 3O23CO + 3H2O ( Carbon Monoxide)
Reactans :
C3H6 = 0,029 x 396,81 = 11,507 kmol/h
O2 = 3 x 11,507 = 34,521 kmol/h
Products :
CO = 3 x 11,507 = 34,521 kmol/h
H2O = 3 x 11,507 = 34,521 kmol/h
Total Water : (a) + (b) + (c) + (d) + (e) + (f) + (g) 1153,886 kmol/h x 18 kg/kmol = 20769,946
kg/h
Air :
(h) C3H6 + 3/2O23/2CH3COOH (Acetic Acid)
Reactans :
C3H6 = 0,002 x 396,81 = 0,7936 kmol/h
O2 = 1,5 x 0,7936 = 1,19 kmol/h
Products :
CH3COOH = 1,5 x 0.7936 = 1,19 kmol/h
Total O2 = (a) + (b) + (c) + (d) + (e) + (f) + (g) + (h)
Total = 637,838 kmol/h x 32 kg / kmol = 20410,816 kg/h
53
Air contains 20,95% O2and 78,07 % N2
20410,816 / 0,2095 = 97426,329
Air / C3H6 = 6,75
Air in = 16678,66 x 6,75 = 112580,95
O2in = 112580,95 x 0,2095 = 23585,71
N2 in = 112580,95 x 0,7807 = 87891,94
O2 excess = 23585,71 - 20410,816 = 3174,894 kg/h
N2 out = 87891,94 kg/h
ACN = 16835,02 kg/h
2NH3 + H2SO4 → (NH4)2SO4
NH3 present in gas (unconverted) = 181.944 kg/h / 17kg/kgmol =10.702 kmol /h
H2SO4 required = 10.70258 /2 = 5.35129 kmol /h =5.35129 × 98.076 = 524.8331kg/h
But 98% H2SO4 includes 2% water = 0.02/0.98 × 524.8331= 107.1087kg/h
(NH4)2SO4 formed = 107.0258 /2 = 5.35129 x 132.144 = 707.14086 kg/h
For 33% (NH4)2SO4 solution, the amount of water added =707.14086 / 0.33-(707.14086)
=2142.85109-707.14086 =1435.7 kg/h
6.1.2 Quench column
Input stream = Effluent from Reaction via effluent cooler. Two section provided in Quench
column
Water is circulated over both section from stripper i.e. water in = Water from Aceto stripper
15480.16
Excess NH3= 185.9264 kg/h
54
NH3react with H2SO4
Reaction:
2NH3+H2SO4(NH4)2SO4
(34,02)(98,06) (138,08)
H2SO4required: (185,9264 x 98,06)/34,02 =535,9 kg/h
Table 6.4 Material balance over quench column
Component Material in, kg/h Material out ,

kg/h
Acrylonitrile 16833,266 16833,266
HCN 1896,94 1896,94
CO2 2671,7 2671,7
CO 621,36 621,36
Water 17750,882 (as feed) 13572,492 (at

top) 19658.55(at
15480,16 (as Lean
bottom)
Water)
Total 55815,82 55815,82
6.1.3 Absorber
Assumption: Off-gases containing CO, CO2, N2, unreacted O2, unreacted C3H6.
Not absorbed in water and are remove from top of column. Also HCN of 0.5% in is removed in
it i.e.
55
= (0,005) (1896,94)
= 9,4847 kg/h
ACN out at top as off gases = 54 kg/h
Off – gases contains some entrained water = 108,59 kg/h and all CO2, CO, N2, Unconverted
C3H6 data:
Solubility of Acrylonitrile in water, wt %
At 40oC 7.9%
At 30oC 7.5%
At 20oC 7.3%
o o o
Top of absorber have temperature 40 C and at 40 C water added at top. Feed at bottom also 40 C
o o
and feed enter at bottom is also at 40 C. But about 25 C maintain in column using side stream
cooling.
So, take solubility of Acrylonitrile around 7,7 wt% in water Therefore, for 8927,66 kg/h ACN is,
Water required for absorb ACN
= (16833,266 x 92,3) / 7,7 = 201780,57 kg/h
Acetonitrile & HCN have infinite solubility in water for absorption.
6.1.4 Recovery column and decanter
Recovery Column:
We have Separation of Acetonitrile as bottom and Acrylonitrile as overhead using extractive

distillation using water as solvent.
All Acrylonitrile and all HCN feed separated as overhead. Also, separation such as, total Aceto –
98% to bottom and 2% as overhead.
56
Aceto at bottom= (561,52) x(0,98) = 550,28kg/h
Aceto attop= 561,52x0,02 = 11,23kg/h
Now, bottom has 1.7% dilute solution of Aceto of water with Aceto at bottom = (561,52x 100) /
1,7 =33030,58 kg/h Water as overhead =16197,31 kg/h
Decanter:
Now, consider top stream have is separated out in decanter in aqueous (water) phase and organic
(ACN) phase. Separate out 95% of aqueous phase as water in decanter.
Water goes with organic phase = 5% of top stream
= 0,05 x 16197,31 =809,86 kg/h
Water removed: 16197,31- 809,86=15387,44 kg/h
6.1.5 Aceto column
Total Acetonitrile in feed separated as overhead. Acetonitrile is overhead=550,28kg/h
In Aceto-stripper, the total Acetonitrile go as overhead with water and get 70% acetonitrile as
overhead.
Acetonitrile is over head= 550,28 kg/h (70%) Water with Acetonitrile as over head= 235,83 kg/h
(30%)
Water out a bottom= 33030,58 –235,83 = 32794,75 kg/h
6.1.6 HCN column
The feed of HCN column is generally ACN & HCN with little amount of H2O and Acetonitrile.
Hence, it can be treated as binary distillation considerably HCN & ACN alone.
From feed, all ACN and 99% pure HCN is recovered from top.
F = D + W 10295.15 = D + W
Where, F related to feed, D related to distillate (overhead) products, W related to bottom

products.
57
For HCN Balance:
F XF = D XD+ W XW
1001,03= D (0,99) + W(0,01)
Solving above two equations for D &W D = 1001,02kg/h
6.2 ENERGY BALANCE
The reference temperature = 25ᴼC
6.2.1 Preheating of reactor
Preheating is required to initiate the exothermic reaction. Preheating is also carried out at 425ᴼC.
Table 6.3 Energy required for preheat the reactants

Component Kg/h Mole.wt. Kg Cp.at ni.cpi
mol/h 425ᴼC
C3H6 16676,9 42,03 396,78 28,3 11228,87
Ammonia 7004,30 17 412,02 10,05 4140,80
Air 112569,2 29 3881,70 7,21 27987,06
Σ ni Cpi = 43356,73
ΔT = 425-25 = 400 ᴼC
Energy Supplied to preheat reactant = Σ ni Cpi x ΔT 17342,7 kcal energy supplied by the
heater.
58
6.2.2 Energy Balance Around Reactor
Reactants in at 425ᴼ C Products out at 425ᴼC
At 25ᴼ C  At 25ᴼ C
(a) Energy supplied by the heater.= 17342,7 Kcal
(b) Total heat of reaction:
Formation of Acrolein, Acetic acid, Acrylic acid is small. So neglected.
1. C3H6 + NH3 + 1.5O2 CH2CHCN + 3H2O
2. 2/3C3H6 + NH3 + O2 CH3CN + 2H2O
3. 1/3C3H6 + NH3 + O2HCN + 2H2O
4. C3H6 + 4.5O23CO2 + 3H2O
5. C3H6 + 3O2 3CO + 3H2O
Table 6.4 Components and its properties

Compound Kcal/gmol
Propylene 4,88
Ammonia -11,0
Water -57,8
Acrylonitrile 45,37
Dioxide -94,05
Carbon Oxide -32,81
Hydrogen 31,1
Cyanide
Acetonitrile 19,80
59
Heat of reaction = [Σ (heat of product formation)] – [Σ (heat of reactants formation)]
Acrylonitrile
= [(45,37) + 3(-57,8)] – [4,88 + (-11,0)] = - 132,91 Kcal/gmol  - 132910 Kcal/kgmol
Hydrogen Cyanide
= [3(31,1) + 6(-57,8)] – [4,88 + 3(-11,0)] = -291,38 Kcal/gmol  - 291380 Kcal/kgmole
Acetonitrile
= [1,5(19,80) + 3(-57,8)] – [4,88+1.5(-11,0)] =- 165,07 Kcal/gmol  - 165070 Kcal/kgmole
Carbon Dioxide
= [3(- 94.05) + 3(-57.8)] – [4.88] =- 460.43 Kcal/gmol  - 460430 Kcal/kgmole
Carbon Monoxide
= [3(32,81) + 3(-57,8)] – [4,88] = - 276,71 Kcal/gmol  - 276710 Kcal/kgmole
Total ΔH = Σni. ΔHR
=57130676,23 Kcal
Table 6.5 Energy required

Compo Kg/h Mol. K Cpi at ni.cpi
nent 4250C
Wt. Mol/h
ACN 16833,266 53,03 317,429 24,88 7897,63
Aceto 561,52 41,02 13,363 17,63/19,86 11,862
HCN 1896,94 27,01 70,231 9,95 698,79
CO2 2671,7 44,01 60,706 10,05 610,09
CO 621,36 28,01 22,183 7,44 165,04
H2O 17129,923 18 951,662 8,45/7,25 1109,17
60
C3H6 349,73 42,03 8,249 28,3 233,44
NH3 185,9264 17 10,936 9,28 101.48
O2 9898,1276 32 309,316 7,45 2304,40
N2 86340,5 28 3083,6 7,1 3076,5
Σ ni Cpi = 15938.40
ΔT = 425-25 = 400 oC
Σ ni Cpi x ΔT = 6375360 kcal
→Enthalpy of the cooler = Enthalpy of Reactant at 25ᴼC - Heat of reactions -
Enthalpy of product 425ᴼC
= (-17342,7) - (- 57130676.23) - (6375360) = - 50737973.5 Kcal
→Coolant required
This heat is removed using steam at 110ᴼC which is superheated up to 370ᴼC.
Msteam x Cpsteam x ΔT = 50737973.5 Kcal
[Msteam] x [1] x [370-110] = 50737973.5 Kcal
Msteam = 195146.052 kg/h
This is the amount of steam required to removed the heat at evolved in the reactor.
6.2.3 Energy Balance Over Product Gas Cooler
Inlet temperature of gases = 425°C Outlet temperature of gases = 230°C
→ Enthalpy in with gases
= 6375360 Kcal
→ Enthalpy out with gases:
61
Table 6.6 Energy required
Compon Kg/h Mol. K Cpi at ni.cpi
ent 230̊C
Wt. Mol/h
ACN 16833,266 53,03 317,429 21.91 6954,86
Aceto 561,52 41,02 13,363 17.43 232,91
HCN 1896,94 27,01 70,231 9.35 656,65
CO2 2671,7 44,01 60,706 10.03 608,88
CO 621,36 28,01 22,183 7.13 158,16
H2O 17129,923 18 951,662 7.47 7108,91
C3H6 349,73 42,03 8,249 22.7 187,25
NH3 185,9264 17 10,936 9.28 101,486
O2 9898,1276 32 309,316 7.27 2248,72
N2 86340,5764 28 3083,6 7.0 21585,2
Σ ni Cpi = 39843,026
ΔT = 230-25 = 205°C
Σ ni Cpi x ΔT = 8167820,33 kcal
→Coolant Required:
Steam required to cool the effluent at temperature 110°C which is heated upto heated up to
200°C temperature.
Msteam x Cpsteam x ΔT = (Enthalpy out with gases) – (Enthalpy out with gases )
= (6375360) - (8167820,33) = -1792458,33 Kcal
[Msteam] x [1] x [200-110] = 1792458,33Kcal
62
Msteam = 19916,20 kg/h
6.2.4 Energy Balance Around Quench Column
(1) Enthalpy in with product gases:
= 8167820,33 Kcal
(2)Enthalpy due to heat of reaction:
In the Quench column the neutralization of ammonia using Sulphuric acid take place.
2NH3 + H2SO4 (NH4)2SO4
(34,02) (96,06) (138,08)
ΔHR = -76662 Kcal / Kmol Ammonium Sulphate Amount of (NH4)2SO4 formed = 390,72
kg/h[from Material Balance] Total heat liberated due to reaction
= (-76662) x (390,72/138,08) = - 216927,7 Kcal
(3) Enthalpy out with gases [at top]:
Table 6.7 Enthalpy out with gases

Compo Kg/h Mol. K Cpi at ni.cpi
nent 850C
Wt. Mol/h
ACN 16833,266 53,03 317,429 19,78 6278,74
Aceto 561,52 41,02 13,363 17,21 229,97
HCN 1896,94 27,01 70,231 8,88 623,65
CO2 2671,7 44,01 60,706 9,22 559,70
CO 621,36 28,01 22,183 6,98 154,83
H2O 17129,923 18 951,662 4,73 4501,36
C3H6 349,73 42,03 8,249 17,6 145.18
63
O2 9898,1276 32 309,316 7,02 2171,39
N2 86340,57 28 3083,6 6,96 21461,85
Σ ni Cpi = 36126.67
ΔT = 85-25 = 60 0C
Σ ni Cpi x ΔT = 2167600.2 kcal
(d) Enthalpy out with bottom stream:
= (Σ ni Cpi) ΔT
= (6.5 x 390.72) + (1 x 1762)
[Cp of (NH4)2SO4 =6.5 Kcal /kg]
= 258100.80 Kcal
Heat carried away by H2SO4 polymer neglected in bottom stream as it is very very small.
(e) Heat required liquefying the water vapor which out from bottom and cool from 230 to 85 ᴼC
= (to cool water vapor to 230 to 100ᴼC) + (Exchange of latent heat of vaporization)
+ (cool liquid water from 100 to 85ᴼC)
= (19658,55x 1 x 130) + (19658,55 x 550) + (19658,55x 1 x 15) = 11126609,3 kcal Enthalpy

removed.
So, water added
= (a) - (b) - (c) - (d) - (e)
= -5167562,27 Kcal
Msteam x Cpsteam x ΔT = -5167562,27 Kcal
[Msteam] x [1] x [23] = 5167562,27Kcal
Msteam = 224676,62 kg/h

64
This is water added to quench column.
6.2.5 Energy Balance Around After Cooler
Inlet temperature of gases = 85oC
Outlet temperature for gases = 40oC
Boiling point of ACN = 78oC
Boiling point of Aceto = 82oC
Therefore, at 400C temperature, ACN and Aceto will get condensed.
(a) Heat in with gases
= 2167600,2 Kcal
(b) Heat required to condense ACN:
= MACN x ZACN
= (16833,266/53,03) x (780) = 247594,71 Kcal
(c) Heat required to condesese Aceto:
= MACETO x Z ACETO
= (561,52/41,02) X (711) = 9732,83 Kcal
(d) Enthalpy out with the mixture:
65
Table 6.8 Enthalpy out with the mixture
Component Kg/h Mol. K Cpi at ni.cpi
Wt. 40ᴼC
Mol/h
ACN(L) 16833,266 53,03 317,429 26,87 8529,31
Aceto(L) 561,52 41,02 13,363 21,06 281,42
HCN 1896,94 27,01 70,231 8,66 608,20
CO2 2671,7 44,01 60,706 8,9 540,28
CO 621,36 28,01 22,183 6,97 154,61
C3H6 349,73 42,03 8,249 15,85 130,74
O2 9898,1276 32 309,316 7,0 2165,21
N2 86340,5764 28 3083,6 6,96 21461,85
H2O(L) 17129,923 18 951,662 18 17129,91
Σ ni Cpi = 51001,53
ΔT = 40-25 = 15 0C
(e) Enthalpy absorbed by the water added
= (a) – (b) – (c) – (d) = 1145249,71 Kcal
Mwater .Cpwater . ΔT
Cooling water temperature is 30ᴼC is added and out let temperature is 40ᴼC.
Mwater x (1) x (10) = 1145249,71
Mwater = 114524,971
66
114524,971 kg cooling water required.
6.2.6 Energy Balance Around Absorber and Heat Exchanges
Inlet temperature of Absorber = 40ᴼC
Outlet temperature of Absorber = 40ᴼC [at top]
Maintain temperature in absorber = 25ᴼC
(a) Enthalpy in with feed mixture: 765022,95 kcal
(b) Enthalpy out with unabsorbed gases from top:
Table 6.9 Enthalpy out with unabsorbed gases from top

Component Kg/h Mol. K Cpi at ni.cpi
40oC
Wt. Mol/h
CO2 2671,7 44,01 60,706 8,9 540,28
CO 621,36 28,01 22,183 6,97 154,61
O2 9898,12 32 309,316 7,0 2165,212
N2 86340,57 28 3083,6 6,9 21276,84
C3H6 349,73 42,03 8,249 15,85 130,74
H2O(G) 17129,92 18 951,662 16,2 15416,92
HCN 1896,94 27,01 70,231 8,66 608,20
Σ ni Cpi = 40292,8
ΔT = 40-25 = 15oC
Σ ni Cpi x ΔT = 604392 kcal
(c)Enthalpy out with bottom stream
67
Table 6.10 Enthalpy out with bottom stream
Compone Kg/h Mol. K Cpi at ni.cpi
nt 300C
Wt. Mol/h
ACN (L) 16833,266 53,03 317,429 26,57 8434,08
Aceto (L) 561,52 41,02 13,363 21,34 285,16
HCN 1896,94 27,01 70,231 8,06 566,06
H2O (L) 17129,923 18 951,662 18 17129,91
Σ ni Cpi = 26415,21
ΔT = 30-25 = 5 oC
(d) Enthalpy in with lean water:
Mlean water x Cp x ΔT
= 2106,33 x (1) x (40 -25) = 31595,091 Kcal
(e) Enthalpy removed by cooling system:
Heat evolved = [Heat in with feed + Heat with lean water] – [heat out with gases + Heat out with
bottom product]
= [(a) + (d) ] – [ (b) + (c) ]
= 165810,83 Kcal
6.2.7 Energy Balance Around Recovery Column
(a) Heat in with feed= 31595,091 Kcal = F HF
Temperature of column = 85ᴼC (at top)
(b) Load on reboiler, Qb:
68
Feed at 80ᴼC, It is Saturated liquid.
Load on reboiler, Qb = [for vaporization of ACN, Aceto, H2O as distillate] + [H.T. in Remaining
comp. coming from bottom]
= Σm x Z + Σ ni Cpi x ΔT
= [(8873,66 x 147) + (5,96 x 173,68) + (8476,39 x 550)] + [(177,8+17358,39)x (110-80)]
= 6518895,503 Kcal
Let, stream is used in reboiler at 1 atm having, Z stream = 550 K cal/kg
Steam required in reboiler
Mstream x Zstream = 6518895,503
Mstream = 11852,54 kg/h
(c)Enthalpy out with Distillate: [DHD]
Table 6.11 Enthalpy out with Distillate: [DHD]

Component Kg/h Mol. Kmol/h Cpi at ni.cpi
(wt.) 85ᴼC
ACN 16833,266 53,03 317,429 16,77 5323,28
Aceto 561,52 41,02 13,68 13,5 184,68
HCN 1896,94 27,01 70,231 9,2 646,12
H2O 17129,923 18 951,662 6,19 5890,78
Σni Cpi = 12044,86
ΔT = 85-25 = 60ᴼC
Entalpy out with distillate = Σni Cpi ΔT
= 722691,6 Kcal =D HD
69
SECTION-VII
DESIGN OF
PROCESS EQUIPMENTS
70
7. DESIGN OF EQUİPMENT
7.1 Fluıdızed Bed Reactor (FBR)
Data for catalyst bed:
Catalyst : C-49 (Ferobysmuth Molibdate)
Density : (ρs) = 1500 kg/m3
WHSV : = 0,2 /sec
Shape factor : = 0,7
Average diameter of catalyst particle Dp = 60 μm
Data for gase reactants
Mass flow rate G : = 16666,67 Kg/h
Average density at 4250C & 1 atm =PM/RT
=0,53 kg/m3
Viscosity of gas μg:3.6 x10-5kg/ms-1
Now,
WHSV=weight hourly space velocity
Weigh of reactants /sec
Weight of catalyst
Weight of catalyst:50 kg
Cross-sectional area of reactor =π/4D2
Surface area of reactor = π DL = 3 π D2
And mf =0,55
71
Gmf=0.005Dp2gρ(ρs-ρg)∅ mf3
μ(1- mf)
Substituting the above values:
Gmf = 0,031 kg/m2S
Gactual =15 x Gmf
= 0,465kg/m2s
Gactual = mass flowrate
c/s area of reactor
c/s area of reactor =4,62/0,465
= 9,93 m2
π/4D2 = 16,65
D = 4,6 m
L =3D=13,3 m
The top diameter of the fluized bed reactor is kept langer.
Taking,
Dtop =1,2 x D=5,52 m
7.1.1 Mechanical design of the reactor
(1) To find out the thickness of the reactor : P = 0,78 atm = 0,82 kg/cm2 = 0,078 MN/m2
Do = Di = 5m
2
Material of construction = IS: 2825 -1969 Fallow = 98,1 MN/m
J = 0,9
t = (1,05 p .Do) / (2 fJ + p )
72
= 2.38 mm
Take carrosion alowance :3mm
t = 2.38 mm
Taking standart value t = 6mm
(2) To find the thickness of coil ensured to circulate the cooling water:
Internal coils are provided inside the reactor attached with the reactor wall. Water is fed at
o
40kg/fcmand 250 C.
Designing for half coil jacket. p = 40 kg/cm2
pd = 40 x 1.05 kg/cm2 fa = 980 Kg/cm2
di = 550 mm
tc= (( pdi/ 2 fa) + Ca)
= 15 mm (standard)
uo= 0,5 m/s
= [lm .( 1- m)] / (0,5)] = 14,22 s
Checking for total circum ferential shear :
fps= [(ptDi)/ (2ts)] + [(p2di)/ (4tc+2.5ts)] = 610,11kg/cm2
7.1.2 Checking tower height for various external and internalloads
Data
Height of the reactor = 13.8 + 2 = 15.8
Internal diameter of the reactor = 4.6m
Thicknessofshell =6mm
Designpressure = 0.82Kgf/cm2
73
J =0.85
MOC = Carbon steel
Specific gravity =8.8
Corrosionallowance = 3mm
(1) Axial stress due topressure
fap = [(0.82 x 4600) / (4 x 3)]
2
= 314.33 Kgf/cm
(2) Stress due to deadloads
(a) Compressive stress due to weight of Shell upto distance‘x’
Fds=ρs (x) = 7.7 x 10-3 (x)Kgf/cm2
(b) Compressive stress due to weight of insulation upto distance ‘x’ fdins=[ρ(tins.ins.X) / (ts –
c)]
= 0.0564 (x) Kgf/ cm2
(c) Compressive stress due to the attachments such as internals headetc.
Weight of catalyst = 60 kg
Weight of standart dished head =( /4) (D x 1.2)2 xtxρs
= 921,35 kg
fdatt= [(60+921,35) /D (ts –c)]
= 3,55 (x) Kgf/ cm2
Total compressive stresses,
fds= fds + fdins+fdatt = 7,7 x 10-3 (x) + 0,0564 (x) + 3,55 = 0,0641 (x) +3,52
74
(3) Stresses due to the wind load
Wind pressure : pw = 0.06 Vw2 Where,
Vw = Maximum windvelocity
= 70 km/h
Pw = 294 N/m2 = 293,7Kgf/cm2
Windlow :(pw) = 0,7 pw x Do x(x)
= 0,7 x 294 x 4,6 x (x)
= 946,68 (x) N
Bending moment due towind : = pw (x/2)J
= 394,45 (x)2J
Stressfwx = Mw /Z
= [(Mw/(π/4) Do2(ts-c)] x 10-6 MN/m2
= 0,0079 (x)2MN/ m2
= 0,0805 (x)2kg/m2
(4) Resultant axialstress:
(a) Upwind size:
fJ= ftmax = fwx + fap - fdx
980 x 0,85 = 0,0805 (x)2+ 314,33 – 0,0641 x – 3,52
X= 80,94 m
(b) Downwind size:
ftmax (comp.) = fwx - fap + fdx 0,125E (t/Do) = fwx - fap + fdx
75
0,125 x 2,03 x 106 (0,006/4,6) = 0,0805 (x)2- 314,33 + 0,0641 x + 3,52
X= 88,89 m
7.1.3 To design the skirt support
Since column height is large (14m), skirt assistance is used the cross-section of the skirt is
uniformly deployed at a enough distance from the axis. This gives a large value of the section
modulus and helps to rise the resistance to bending action.
Data:
Diameter of vessel D =4.6m
Height of the vessel n=13,8 m
Weight of vessel , attachments etc.W = 12600 kg
Wind pressure = 128,5 kg/m2
Skirt height =5m
Diameter of skirt =4500 nm
Various stresses are:
(1) Stresses due to dead load,
Fd=W/ π Dsk tsk
12600/ π x 460 x tsk
=8.7 / tsk kg/cm2
(2) Stress due to wind load
Fwb= 0.7 x ρ1 x h1 Do (h1/2)
π x 460 x tsk
=3502,96 / tsk kg/cm2
76
Maximum sensile stress
Fd+fwh=fallowable
8.7/tsk=3502,96/tssk=980
Take,
Tsk =7,38 mm
7.2 Distillation Column Design
To estimate relative volatility ∞av
At top =T=280C
PHCNsat =794,3 mmHg
PACNsat =116,01 mmHg
∞1 =7,097 mmHg
At bottom T =820C
PHCNsat =4646,23
PACNsat = 5,029
∞av =√∞1∞2 =5,89
Equilibrium data is given by:
y= ∞x
H (∞-1)x
Table 7.1 X-Y composition

X 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Y 0,4 0,6 0,72 0,8 0,85 0,9 0,93 0,96 0,98 1
77
Equilibrium curve is plotted using the above data
Here, xF=0,21
xD=0,999
xW=0,008
Since feed is at its temperature online is verical
From the graph,
xD = 0,52
Rm+1
Rm =0,88
Rop= 1.2 x Rm =1,06
The number of theoretical stages=13-1
=12
Taking all efficiency =0,6
Number of actual stages = 12/0,6
=20
78
Figure 7.1 McCabe thiele chart
79
7.2.1 To find the diameter of the distillation column
Step 1 Calculation of bottom liquid and vapor flow rates :
Kmol/h kg/
-Vapor rate at top HCN 14,74 398,1
ACN 0.02 1,5
Entire vapor rate 399,6
-Bottom product =5564 kg/h
-Material balance on the bottom plate
LM’=VM’+w
Hence,VM=2787,9 kg/h
LM =8349.9 kg/h
LM’=VM’+5564
LM’/ VM’ slope of operating line
=3
Step 2 Physical properties estimation at top and bottom conditions
Top pressure =1 atm
-Assume 100 mm water pressure drop per plate
Total pressure drop =∆ = hdg x n
=100 x 10-3 x1000x 9,81 x 20
= 0,1962 h = 0,1936 atm
Hence, bottom pressure =1+0,1936=1,1936
-Top pressure =28OC
80
-Bottom temperature =82OC
At top of the density ρHCN=697 kg/m3
ρv Density of HCN vapor =PM /RT =1.099 kg/m3
[P] = [P]c +[P]H + [P]N =9,0+15,6+17,6 =42,2
ρL = Density of ACN(liquid) of saturation
=ρsat
ρv = Density of ACN vapor =PM/RT =2.18 kg/m3
ρsat is estimated bySpencer and Danner equation
ρsat= Pc/RTC Zc [1+(1-Tc)]2/7
where,
Pc= Vc=1,389(m3/g)
Tc=520K
Zc=PcVc
RTc
=0,045
Therefore ρsat=ρL = 103,54
Surface tension of ACN =22,4 x 10-3N/M dyn/cm
Step-4 To estimate column diameter from flooding consideration
i. At bottom
FLV= L (ρG)0,5 = 3,0 (2,18)0.5 = 0,042
ρL103,54
CS67 flood =Unf (20)0,2 (2,18)0,5
σ ρL-ρG
81
CS67 flood =Unf (20)0,2 (2,18)0,,5
22,4 103,5-2,18
Unf =1.873 ft/s=0,57 m/s
ii. At top
FLV =L(ρG)0.5 = 0,5 (1,098) =0,198
G ρL 697
Csb flood = Unf (20)0.2(ρG)0.5 =0,32
σ (ρL- ρG)0.5
Unf =4,75 ft/s =1,44 m/s
-Designing for 85% flooding flow rate
Bottom Unf =0,57 x 0,85 =0,485 m/s
Top Unf = 1,44 x0,85 =1,22 m/s
-Maximum volumetric flow rate of vapour
At bottom Q1 =2781,9 / (2,18 x 3600)
=0,35 m3/s
At top Q1= 8345,9/(1,098 x 3600)
=2,11 m3/s
Net area requıred
Bottom= 0,35/0,485 =0,72 m2
Top= 2,11/1,22 =1,72 m2
Top greater value An =0,72 m2
Providing %15 for downcomer
An= 0.15 At
82
At = 4.8
Therefore π /4 dc =0.456
Hence dc 0.78 = 0.8 m
Area At π /4 dc2 =0.505 m2
7.2.2 Provisional Plate Design
(1) Down comer area Ad = 0,15 x 0,503
= 0,075 m2
(2) Net area An = At – Ad = 0,43 m2
(3) Active area Aa = At – 2Ad = 0,3m2
Assume hole area An = 0,1 x Aa = 0,03m2
Hole diameter dh = 5 mm
Weiz height = 55 mm
Plate thickness = 5 mm
Weiz length = 0,76 Dc = 0,608 m
Single cross flow pattern is used
7.2.3 To check weeping rate
hw = Height of weiz = 55 mm
how = height of crest over weiz ,
equivalent clear liquid mm
Equation (18-12a)
how = 664 (q\ Lw) 2/3
Maximum liquid rate 75% turn down
83
q = 0,75 x 1,23 = 0,92 kg/s = (0,92 /102,5) = 8,97 x 10-3 m3/s
Lw = Weir length = 0,6 m
how = 664 [(8,97 x 10-3)2/3 / (0,608)] = 47,14 mm
hw + how = 102,14 mm
hd = (50,8 / Cv2 ) (pg,pl)un2
Cv = 0,75
Here Uh = linear gas velocity trough perforation
= [( 2781,9) / (3600 x 2,18 )] x [(1 / 0,0353)]
= 10,04 m/s
Hence ,
hd = 102,79
h σ = 409.[σ /(ρ1dh)] = 409. ( 22,4 / (102,5 x 5)) = 17,87
hd + h σ = 120,67
7.2.4 To check plate pressure drop
Total pressure drop plate,
ht = hd + h1’ = 103 mm
h1’ = hw + howmax + hr
hr =( 12,5 x 103 ) / (ρl) = 121,5 mm
hw = 50 mm
how(max) = 48,2 mm
ht = 220 mm of liquid
= 95,2 mm of water
84
7.2.5 Plate layout
Lw/ Dc = 0,77 Qc = 1050C
Assuming width of calming zone = 50 mm
Width of stiffening ring = 50 mm
Angle subtended at plate edge by unperforated strip = 180 – 105 = 750C
Mean length , unperforated edge strips = λ(dc - 50 x 10-3 ). (75 / 180)
= 1,058 m
Area of unperforated edge strips = 50 x 10-3 x 1,058
= 0.0529 m2
Area of claming zone = 2 x 50 x 10-3(0.637-2 x 50 x 10-3)
= 0,537 m2
Area of perforations Ap = Aa + aue – Acz = 0,3026 m2
( Ah / Ap ) = (0,0353 / 0.3026 ) = 0,117
(lp / dh ) = 2,65
lp = 2,65 x 5 = 13,25 mm
No of holes = [( hole area ) / ( Area of one hole )]
= (0,0353 / [(π/4) .(0,005)2]
= 1800
7.3 Heat Exchanger Calculation
Total ΔH = Σni. ΔHR
=57130676,23 kcal=66335,06 kj/s
Heat exchanger:vertical tubes 0,15 m
85
houtside=300 W/m2K
hinside=1800 W/m2K
Overall heat transfer coefficient is
U=(1/ hinside +1/ houtside)-1
(1/300+1/1800)-1=257,1 W/m2K
Hence the exchanger surface area needed to remove this heat is
Aw =q / U∆ = 66335,06 x103/ ( 257,1 x (425-25) )
=645,03 m2
The number of long tubes required is
NT =Aw / ( )
=645,03 / ( 0,15 13,3)=102.96
7.4 Pump& Pipesizes Design
Pump selection: Centrifugal Pump
Pump 1:
The feed point to be reactor is 15.8 m above the base of the tank. The pipeline is 80 mm internal
diameter commercial steel pipe. From the reactor to the pump inlet, the line is
15.8 m long and contains 4 standard elbows and a fully open gate valve.
 (900 standard radius elbow )[47]

 K(number of velocity heads):0.7 [47]
 Number of equlvalent pipe diameter: 40[47]
 Misscellaneous losses are equivalent to 600 pipe diameter.
Densitiy ammonia: 600 kg/m3[48]
Viscosity ammonia:1.862x10-4Ns/m2[48]
86
Cross sectional area of pipe : ᴨ/4(80x10-3)2= 5,03x10-3 m2
Design flow rate:7004,3 kg/h
= 7004.3/(3600x600) = 3,24x10-3m3/s
Pipe velocity = 3,24x10-3/ ((3,14x0,0802)/4)= 0,64 m/s
Re = (ρ x V x d)/ µ = (600 x 0,64 x 0,080) / 1,862x10-4= 164983,88
Absolute roughness = 0,046 mm (steel pipe)[47]
Relative roughness= absolute roughness/ pipe inside diameter
= 0,046 / 80 = 5,75x10-4
Friction factor= 0,0037[47]
Length including misscellaneous losses = 15,8 + (600 x 80x 10-3)
= 63,8 m
Equivalent length of pipe, use values :
İnlet line = 15,8 m
Elbows= 4x40 =160
Gate valves = 7,5[47]
Total = 183,3 m
L’ = (15,8+183,3) x 0,080 = 15,92 m
∆Pf = 8f x (L/d) x ((ρ x V2)/2)
∆Pf =(8x0,0037)x(15,8/0,080)x(600x((0,642)/2))
= 7183,56 N /m2
7183,56/ (600x9,8) = 1,22 m liquid
Total head= 15,8+1,22= 17,02m
87
Pump 2:
Density propylene: 514,4 kg/m3[49]
Viscosity propylene: 0,00009 Ns/m2[50]
Design flow rate:15193,17 kg/h
= 15193,17/(3600x514,4) = 8,2x10-3m3/s
Pipe velocity = 8,2x10-3 / ((3,14x0,0802)/4)= 1,63 m/s
Re = (ρ x V x d)/ µ =(514,4 x 1,63 x 0,080) / 0,00009 =745308,44
Absolute roughness = 0,046 mm (steel pipe)[47]
Relative roughness= absolute roughness/ pipe inside diameter
= 0,046 / 80 = 5,75x10-4
Friction factor= 0,0025[47]
Length including misscellaneous losses = 15,8 + (600x 80x 10-3)
=63,8 m
Equivalent length of pipe, use values :
İnlet line = 15,8 m
Elbows= 4x40 =160
Gate valves = 7,5[47]
Total = 183,3 m
L’ = (15,8+183,3) x 0.080 = 15,92 m
∆Pf = 8f (L/d)x ((ρ x V2)/2)
∆Pf = (8x0,0025)x(15,8/0,080)x(514,4x((1,632)/2)) = 2699,21 N /m2
2699.21/ (514.4x 9.8) = 0.53
88
Total head = 15,8 + 0,53 = 16,33 m
7.5 Compressor Design
-W = P1x V1x (n/n-1) x [(P2/P1)n-1/n -1] [51]
P= nxRxT/ V Vhava=112569.2 kg/h x (1/1.226 m3/kg )= 91818,27m3/h
n= 3881,70 mol / h
P2 = [(3881,70)mol/h x (0,082)L.atm/mol.K x (425+273)K]/[ 91818,27x 103] L /h
= 2,41x 10-3 atm
P1 = [(3881,70) mol/h x (0,082)Latm/mol.K x(25+273) K ] /[ 91818,27x103] L /h
= 1,03x 10-3atm
Compressor ratio = P1/ P2 = [(1,03x 10-3)/(2.41x 10-3)] = 0,42
ƐP = % 86
Ɣ = CP/CV = 1.4[51]
m= (Ɣ – 1) / (ƔxƐP) [51]
= [(1,4 – 1) /(1,4) x (0,86)] = 0,33
n= 1/(1-m)
= 1/ (1-0.33) = 1,49
-W =nxRxTx(n/n-1) x [(P2/P1)n-1/n -1]
First section work, inlet 250C
W1= 3881,70 mole/h x (8314) J/mole.K (25+273)K x (1,49/(1,49-1))x[(2,41x10-3/ 1,03x10-3)(1.49-

1/1.49)
-1]
W1=9418106818 J/h x (1h/3600s)
=2616140 watt
89
Second section work, inlet 4250C
W2 = 3881,70 mole/h x (8314) J/mole.K (25+425)K x (1,49/(1,49-1))x[(2,41x10-3/ 1,03x10-

3 (1.49-1/1.49)
) -1]
W2 = 2,21x1011 J/h x 1h/3600s
=61424585 watt
Total work :W1+ W2 = 64040725,81 watt
= 64040 k
90
SECTION-VIII
PLANT LOCATION
AND
SITE SELECTION
91
8. PLANT PLAN AND SITE SELECTION
8.1 Marketing Area
Acrylonitrile is a very important raw material in the production of large number of chemical
products. It can be used as a raw material in the manufacture of acrylonitrile, and many other
chemical with many different applications. Demand for acrylonitrile is broadly tied to the
general economy and is therefore cyclical. Most of acrylonitrile’s major end markets ABS
resins, acrylic fiber, and adiponitrile, for instance are cyclical and impacted by economic
downturns, when consumer spending contracts. In 2016, China alone accounted for 32% of
the global acrylonitrile market. Further growth is forecast for acrylonitrile through 2021.
Northeast Asia is forecast to account for about 55% of the global incremental demand over
the next five years [12].
8.2 Raw Material Supply
Another most important factor for the site selection is availability and price of favorable raw
material. If the costs of shipping the product are not major than the cost of shipping feed,
plants that produce bulk chemicals are best located close to the source of the major raw
material. The main raw materials for the manufacture of acrylonitrile have been amonia, air,
and propylene fractions. The choice between these has varied from country to country and has
been strongly influenced by economic and affected factors [52].
8.3 Transport Facilities
In order to move personnel, equipment, raw materials, and products to the desired plant site, a
good transportation substructure is needed. In this case, a site should be determined by
considering at least two great forms of transport: road, rail, waterway (canal or river), or a
seaport. Especially, three things are considered related to transportation while selecting site.
Firstly, it is considered that since the yields will be delivered from abroad suppliers and
transportation will be needed, there must be more than one transport facility. The other one is
that transportation facilities are important when cost and delivery time are considered. Site
location is convenient more than one transportation option. By this way, raw material can be
obtained with lower transportation cost and less delivery time [52].
92
The last one is availability of airports. It is important because during the start-up stage and
when the factory is running, it will be required to provide technical and management support
from the head-office to the factory. If airport is close to factory as much as probable, total
travel time and cost will be reduced.
8.4 Availability of Labor
Availability of labor, especially skilled labor is considered as one of the most important
factors while making site selection studies. Nowadays, companies require much more than
just a dense labor pool; they want to reach the labor that has the right skills in order to meet
the specific needs of the industry. Over the past five to six years, availability of skilled labor
has become even more important in business relocation and expansion decisions. In order to
have qualified labor, governments are also playing critical roles over the last few years. States
and group across the country have become more proactive in working with companies and
industries in order to provide that they have access to skilled labor. In fact, training programs
and training grants have become a standard part of encouraging packages. However, there are
some challenges that countries may have to face in terms of labor force[53].
One of the challenges facing manufacturing companies across the country is a growing
population of veteran workers that are approaching retirement age. Although this may be a
very important problem for some countries, Turkey has great labor potential with its young
and dynamic population all over the country. However, quality and education of this young
population also carry great importance. 45% of Turkey’s population is under 25 years old and
unemployment is striking high amongst those aged 15-24 (18%). Turkey’s economy has been
undergoing a structural shift from agriculture to industry and services. For instance, GDP
composition of industry increased from 7 % to 34 % between 1990 and 2010 [40]. But this
structural shift has not been paralleled by a shift in the skills of the labor force to the ones
needed for the new sectors, causing imbalances in the Turkish labor market. All in all, Turkey
has better labor potential compare to the countries which Turkey is in competition with. With
proper education and help of the state, big companies will make more and more investment by
trusting that strong labor force [53].
93
Figure 8.1 Labor productivity growth of different countries [53].
8.5 Availability of Utilities
Availability of utilities including electrical power, natural gas, water and sewer carrygreat
importance in order to make investment for a specific area. In order to construct a new facility
to a new area, that place should either have the enough natural sources that are needed for
utility studies or the industry where electrical power, water and fuel can be purchased from.
Utilities are needed for the maintenance of chemical processes. For example; electricity is
needed in the electrochemical processes, motors, lightings and general uses. Steams required
for the process are generated by using the most economic fuel. Most importantly, water is
used in almost each part of the process. By looking the current industry areas and the natural
resources of Turkey, it can be seen that most of the heavy industry areas are located in the
sea-side or close to the water resources. The reason behind this situation is that, a company
should have located within maximum of one mile of founded power lines, natural gas supplies
or other fuel supplies. In terms of the water, a water main should be located at or adjacent to
the site, or within the maximum distance of one mile of major base line. The acceptable
minimum diameter for a water line to a site is known as eight inches [54].
8.6 Availability of Suitable Land
It is considered that the soil is resistant to slip, is robust, is ideal for cargo handling, is flat for
proper factory landing, and is used for expansion that may be needed in the future. It is an
important detail to choose the land far from the earthquake zone. In this case, the danger of
flooding and erosion is an important factor in determining appropriate land. When these
94
factors are evaluated, the land cost is also optimized [52].
8.7 Environmental Impact and Effluent Disposal
Facilities should be designed without any public anxiety for proper disposal of wastes. When
choosing an installation site, the tolerance levels for various wastewater should be considered
and the requirements that may arise for additional waste treatment facilities should be taken
into account. While all industrial processes produce waste products, they must provide the
necessary precautions to the difficulties and costs of disposal. Disposal of toxic and harmful
wastes will be provided by local regulations and should be discussed with the authorities
during the first field survey to determine if the standards are met [52]. In the chemical process
plant, the environmental impact must be assessed. As a result, an environmental impact
assessment study should be undertaken by the local council prior to project approval.
8.8 Local Community Considerations
The proposed facility should be accepted by the local community. The local community
should provide adequate facilities for facility personnel. These; schools, banks, housing,
entertainment and cultural facilities. In order for the plant to be safe, the place should be given
importance and the collection should be prevented from creating additional risk ethnicity [52].
8.9 Climate
In the case of climate effects on a chemical plant, it can lead to some significant consequences
on the process conditions. The adverse climatic conditions that the plant can suffer can
increase costs. Some changes or modifications may be made to the equipment. The most
important climate factors to consider are rain, temperature changes, harsh wind conditions
such as hurricanes. If abnormally low temperatures occur, additional insulation and special
heating must be provided for equipment and pipelines. In addition, if hard winds usually wind
up in the area, more robust constructions and installations are needed. Climate conditions are
also of great importance for facilities located around water resources such as rivers and seas.
Sea transport of raw materials can be badly affected [41]. Production may start unexpectedly.
The possibility of flooding should also be investigated and necessary precautions should be
taken in the field [53].
95
Figure 8.2 Average temperatures and precipitation in Gebze, 2017 [59].
8.10 Political & Strategic Considerations
Being established in the right place is an important component of an enterprise and its
industrial success. When the company chooses the wrong location, it can be used for
customers, workers, transportation, materials etc. it can be difficult to reach. As a result, the
place of a company's success and general profit is a significant influence. However, there are
some other things to consider in this process [55]. Political risks and governmental regulations
also play an important role in determining the stage. If companies consider expanding to other
countries, political risk should be considered when developing a location strategy. Because
some countries have unstable political environments, companies should be cautious about
outbreaks and chaos if they plan long-term operations in such foreign countries [56]. Another
problem in expanding to other countries is that they may face some government obstacles and
excessive restrictions and regulations. For this reason, government regulations should be
examined in detail. It should also be considered that the government can provide incentives,
such as tax concessions, to new investment areas where the level of unemployment is high.
These incentives can be beneficial for companies to make their election decisions.
96
8.11 Raw Material Source
Propylene, ammonia and air are important steps in determining the source of raw materials
since they are identified as raw materials and then provide more cost-effective options with
raw materials that have strategic and economic qualification. Raw material needs can be met
either by domestic resources or by government regulations.
It is also determined by careful analysis of the raw material source, cost and utility for
domestic and international sources in the detailed process designs. In addition to these
situations, it is also very important to make appropriate planning as the necessary raw
materials may result in unwanted production in any process [55].
8.12 Number of Working Staff
Production units:
The production unit is divided into 2 sections. The first unit in the reactor is the quench and
absorber, the second unit in which the recovery colon is located. The number of staff to work
here is as follows:
 2 units
 4 shifts ( 4 shifts are worked in 24 hour production plants )
 4 workers in each shift
 2 workers to work daytime
 3 engineers
 2 managers
 1 director
*** (2x4x4)+(2x(3+2+2+1)) = 48 employees
Maintenance unit:

 3 engineers
 1 manager
 1 director
97
*** (4x4)+4+3+1+1 = 25 employees
Human resources, purchasing, marketing, finance, administrative affairs departments:

 Human resources: 7 employees
 Purchasing: 2 employees
 Marketing: 2 employees
 Finance: 3 employees
 Administrative: 6 employees
*** = 20 employees
Security unit:
 1 shift supervisor
 1 shift organizer
*** (4x2)+2+1+1 = 12 employees

Stocking unit:
 1 manager
 1 director
*** (4x2)+2+1+1 = 12 employees

Subcontractors: 6 employees
Outsourcers: catering services, transport, canteen service
Total: 123 employees
98
8.13 Storage Tanks
Proper classification and storage of chemicals is very important. Much of the workplace
accidents in laboratories and factories are the result of improper storage of chemicals.
Chemicals should be classified and stored in such a way that they do not give a hazardous
reaction in any adverse situation. Products that can be chemically reacted with each other
should not be stored in the immediate vicinity. Storage tanks must be at ground level and
open area. Storages tanks should be kept away from a potential ignition source, including the
possibility of radiation from an adjacent adjacent fire. Stainless steel or carbon steel is
generally used for storage tanks.
Tank roofs should be fixed inside the ceiling or without roof. Floating roofs reduce steam
emissions. These roofs can be made from aluminum for weight saving and lower costs.
Vertical and horizontal tanks are used to store chemicals. These proceses were used for
vertical storage tanks. Sulfuric Acid;storage tank for acids should be 85% full. The storage
tank is made of carbon steel for sulfuric acid. Acetonitrile and Hydrogen Cyanide;storage tank
must be 90% full. The storage tank is made of stainless steel for acetonitrile. Acrylonitrile;
copper materials should not be used in the construction of the acrylonitrile storage tank.
Copper may induce polymerization and may color Acrylonitrile. Ammonia; storage tank is
made of stainless steel for ammonia [70-75].
8.14 Raw Materials Purchased From Domestic And Abroad
Propylene
In Japan, Asahi Kasei Mitsubishi Chemical Ethylene Corp and Mitsui Chemicals have cracker
maintenance scheduled. Their crackers’ combined propylene capacity are said to be around
670,000 tonnes/year. our company will buy 25 thousand tons from this company.
JXTG Nippon Oil & Energy will take its Sakai the unit, which has a propylene capacity of
105,000 tonnes/year. Our company will buy 5 thousand tons from this company.
In South Korea, Korea Petrochemical Industry Co (KPIC) which has close to 240,000
tonnes/year in propylene capacity. Our company will buy 10 thousand tons from this
company [61].
Ammonia
China, Vietnam sign MoU for Vietnamese ammonia/urea project 14 October 2004.The
company currently produces 90 000 tonne/year of ammonia and 150 000 tonne/year of urea at
99
its existing plant in Ha Bac province in northern Vietnam. Our company will buy 5830
thousand tons from this company [62].
Sulfuric acid
Eti Maden produces 55 thousand tons of sulfuric acid per year. The amount of sulfuric acid
we need is 4131 tons per month. We take the entire sulfuric acid as Eti Maden [63].
8.15 Domestic and Distributed Products
Acrylonitrile
We produce 12166 tonnes of acrylonitrile per month.
AKSA is buying 7425 thousand tons of acrylonitrile per month from abroad. Our factory is
getting 3900 tons [64].
The branch of the Filofibra plant needs 10 thousand tons of acrylonitrile per month. Our
factory sells 8 thousand tons of acrylonitrile per month [65].
We give 269 tons per month to JILIN CITY CHINA factory [66].
Acetonitrile
We produce 409 tonnes of asetonitrile per month.
We sell 409 tons per month to the Annexy Chema Pharma Industries factory in India [67].
Ammonium sulfate
We produce 1048 tonnes of ammonium sulfate per month.
The Seasexports factory in India needs 5000 tons of ammonium sulphate per month. Our
factory sells 1048 tons to this company [68].
Hydrogen cyanide
We produce 2769 tonnes of hydrogen cyanide per month.
Hydrogen cyanide, Chi Mei Corp. ("CMC") in China, where Kempro Chemical Company has
purchased Methyl methacrylate-Styrene Copolymer [69].
100
8.16 Plan Layout
The area to be built by Fabrikan is in the vicinity of the airport, railway and other transport
facilities, with respect to the economical availability of the project. Facility placement
organizations are as important as the location of the least facilities in the economic direction
and are important for creating a safe production environment. In addition, other factors that
need to be taken into consideration when deciding on a plant layout are the minimum material
transport cost, flexibility and efficient use of space. The figure below shows the criteria that
must be taken into consideration when deciding on the layout of the facility [57].
Figure 8.3 Pathways of deciding plant layout[58].
There are a number of factory order examples mentioned in the literature. However, the
specimens may not meet the desired properties. Because the dimensions of the buildings and
the processes are seen to change too much. For this reason, changes and innovations are
always made on plant settlement types that are current and widely used.
According to the literature, there are four main facility arrangements: process order, product
order, fixed position order and group order. Before examining these in detail, we can refer to
the relation between different production volumes and product variety and plant layout types.
The increase in the production volume or the variation of the final product changes the kind of
facility arrangement. We see in ‘Figure 8.3’ how the relationship between production volume
and product variety affected the plant layout.
101
Figure 8.4 The site location of the company [60].
We chose Gebze because;

 Use the road and sea port for the transportation requirements. Our location is close to
Yılport and Evyaport.
 Datas show that if we consider the climate properties of Gebze; the weather conditions
are suitable for production of acrylonitrile.
 The place we choose is the organized industrial zone.
102
Figure 8.5 Plant layout.
103
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110
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Acrylonitrile Production

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CONTENTS

LIST OF TABLE .............................................................................................................. vi

LIST OF FIGURES .......................................................................................................... vii

ABBREVIATION LIST ................................................................................................. viii

1.1 Physical Properties.................................................................................................... 3

1.2 Chemical Properties .................................................................................................. 4

1.3 Use of Acrylonitrile .................................................................................................. 4

1.4 Occurrence ................................................................................................................ 5

1.4.1 Natural occurrence ............................................................................................. 5

Acrylonitrile is not known to occur as a native product. ............................................ 5

1.4.2 Occupational exposure ....................................................................................... 5

1.5 Production of Acrylonitrile ....................................................................................... 5

1.5.1 Sohio process ..................................................................................................... 6

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

1.5.3 Production from acetylene and hydrocyanic acid .............................................. 6

1.6 Toxicology of Acrylonitrile ...................................................................................... 7

1.7 Reactions of Acrylonitrile......................................................................................... 9

1.7.1 Reactions with nitrile class ................................................................................ 9

1.7.2 Reactions with olefins and alcohols ................................................................... 9

1.7.3 Reactions with aldehydes and methylol compounds ......................................... 9

1.7.4 Reaction of the double bond ................................................................................ 9

1.7.5 Reactions of both functional classses............................................................... 10

2. SITUATION IN THE WORLD AND TURKEY .................................................. 12

2.1 Acrylonitrile Marketing in theWorld ...................................................................... 12

3.PROCESS SELECTION AND CAPACITY ................................................................ 16

3.1 Process Selection .................................................................................................... 16

3.1.1 Cost estimation for all production methods ..................................................... 16

3.2 Production of Acrylonitrile from SOHIO Process.................................................. 20

3.2.1 Catalysts ........................................................................................................... 23

3.3 Capacity of the Process ....................................................................................... 23

4.ACRYLONITRILE PRODUCTION FLOW DIAGRAMS I ....................................... 25

4.1 Block Flow Diagram............................................................................................... 25

4.2 Explain the Related Equipments............................................................................. 26

4.2.1 Used equipments .............................................................................................. 26

4.3 Explain the Raw Materials ..................................................................................... 30

4.3.1 Propylene ......................................................................................................... 30

4.3.2 Air .................................................................................................................... 31

4.4 Explain the Byproduct Materials ............................................................................ 32

4.4.1 Hydrocyanic acid ............................................................................................. 32

4.4.3Carbon monoxides ............................................................................................ 34

4.5 Evaluation and Examination of By Products .......................................................... 34

5. PROCESS FLOW DIAGRAM II ................................................................................ 37

5.1 Acrylonitrile Production in Chemcad Simulation .................................................. 37

5.2 Chemcad Equipment Values ................................................................................. 38

5.2.1 Reactor ............................................................................................................. 38

5.2.2 Quencher .......................................................................................................... 39

5.2.4 Recovery column ............................................................................................. 41

5.2.5 Acetonitrile column.......................................................................................... 41

5.2.6 HCN column .................................................................................................... 42

5.2.7 ACN column .................................................................................................... 42

6. MATERIAL AND ENERGY BALANCE .................................................................. 44

6.1 MATERIAL BALANCE ........................................................................................... 44

6.1.1 Material Balance for Reactor ............................................................................... 44

6.1.2 Quench column ................................................................................................ 54

6.1.3 Absorber ........................................................................................................... 55

6.1.4 Recovery column and decanter ........................................................................ 56

6.1.5 Aceto column ................................................................................................... 57

6.1.6 HCN column .................................................................................................... 57

6.2 ENERGY BALANCE ............................................................................................ 58

6.2.1 Preheating of reactor ........................................................................................ 58

6.2.2 Energy Balance Around Reactor...................................................................... 59

6.2.3 Energy Balance Over Product Gas Cooler ....................................................... 61

6.2.4 Energy Balance Around Quench Column ........................................................ 63