PROJECT REPORT

on

MANUFACTURE OF ACRYLONITRILE
(Via SOHIO PROCESS)
Submitted in partial fulfilment for the award of the degree
of
BACHELOR OF TECHNOLOGY
in
CHEMICAL ENGINEERING
by

AKSHAY GROVER 10708004

MOHIT SHARMA 10708035
DIVYANSHU PATEL 10708017
SHASHWAT MITRA 10708053

Under the guidance of

Mr. BALASUBRAMANIAN SIVASWAMY, M.Tech.,
(Assistant Professor, School of Chemical Engineering)

FACULTY OF ENGINEERING AND TECHNOLOGY

SRM UNIVERSITY
(Under section 3 of UGC Act, 1956)
SRM Nagar, Kattankulathur – 603 203
Kancheepuram Dist

APRIL 2012
 BONAFIDE CERTIFICATE

This is to certify that the project report titled “MANUFACTURE OF

ACRYLONITRILE” is a bonafide record of the project work carried out by
“AKSHAY GROVER (10708004), MOHIT SHARMA (10708035),
DIVYANSHU PATEL (10708017) and SHASHWAT MITRA (10708053)”
during the academic year 2011 - 2012

HEAD OF THE DEPARTMENT INTERNAL GUIDE

EXTERNAL EXAMINER INTERNAL EXAMINER

DATE:

2
 ACKNOWLEDGEMENT

We take this opportunity to express our sincere thanks to Dr. R. Karthikeyan, B. E.,
Ph. D., Professor and Head of the department, School of Chemical and Material Technology,
SRM University for giving us permission to carry out this project work.

Great deals appreciated go to the contribution of our internal guide

Mr. S. Balasubramanian, M. Tech, (Ph. D), Assistant Professor (OG) for being patient in
helping us to complete the project work

Our greatful thanks also goes to Mrs. E. Poonguzhali, B. Tech, (M. Tech), Assistant
Professor (OG) for her contribution and hard work during the project is great indeed.

Besides, this project made us to realize the value of working together as team and as a
new experience in working environment, which challenges us at every minute.

Above all, we thank all our department faculty members and each and every one who
have helped us in successfully completing the project work

3
 TABLE OF CONTENTS
Chapters Contents Page. No.

1.0 Introduction 7
1.1 Properties of Acrylonitrile
1.1.1 Physical Properties 9
1.1.2 Chemical Properties 9
1.1.3 Uses of Acrylonitrile 10

2.0 Manufacture
2.1 Methods of Production
2.1.1 Sohio Process 13
Production from Ethylene
13
2.1.2 Cyanohydrin

2.1.3 Production from Acetylene 13

and Hydrocyanic Acid
2.1.4 Future Processes 14

3.0 Process Description 16

3.1 Material Balance 20

3.2 Energy Balance 23

4.0 Equipment Design 28

4.1 Fluidized bed reactor 28

4.1.1 Height of the reactor 28
4.1.2 Diameter of the reactor 29

4.2 Distillation column design

4.2.1 Number of Theoretical Plates 30
4.2.2 Height and Diameter of the column 32

5.0 Cost Estimation

5.1.1 Direct cost 34
5.1.2 Indirect cost 34
5.1.3 Estimation of total product cost 35
5.1.4 Determination of pay-back period 37

6.0 Plant Layout 39

6.1.0 Plant location and site selection 39
6.1.1 Plant layout 43
7.0 Storage and Transportation 45

4
Chapters Contents Page. No.

8.0 Health Aspects 47

8.1.0 Toxicology and Health Hazards 47

9.0 Nomenclature 49

10.0 Appendixes
Appendix I Process Block Diagram 52
Appendix II Process Flow Diagram 53
Appendix III Material Balance Diagram 54
Appendix IV Energy Balance 55
Appendix V Equilibrium Curve 56
Appendix VI Plant Layout 57
Appendix VII Fluidized Bed Reactor 58
Appendix VIII Distillation Column 59

11.0 Bibliography 60

5
INTRODUCTION

6
1.0 INTRODUCTION

Acrylonitrile (also called acrylic acid nitrile, propylene nitrile, vinyl

cyanide, propenoic acid nitrile) is a versatile and reactive monomer which can be
polymerized under a wide variety of conditions and copolymerized with an
extensive range of other vinyl monomers.

Prior to 1960, acrylonitrile was produced commercially by processes based on either

ethylene oxide and hydrogen cyanide or acetylene and hydrogen cyanide. The growth in
demand for acrylic fibers, starting with the introduction of Orlon by Du Pont around 1950,
spurred efforts to develop improved process technology for acrylonitrile manufacture to meet
the growing market. This resulted in the discovery in the late 1950s by Sohio and also by
Distillers of a heterogeneous vapor-phase catalytic process for acrylonitrile by selective
oxidation of propylene and ammonia, commonly referred to as the propylene ammoxidation
process.

Commercial introduction of this lower cost process by Sohio in 1960 resulted in the
eventual displacement of all other acrylonitrile manufacturing processes. Today over 90% of
the approximately 4,000,000 metric tons produced worldwide each year use the Sohio-
developed ammoxidation process. Acrylonitrile is among the top 50 chemicals produced in
the United States as a result of the tremendous growth in its use as a starting material for a
wide range of chemical and polymer products. Acrylic fibers remain the largest use of
acrylonitrile; other significant uses are in resins and nitrile elastomers and as an intermediate
in the production of adiponitrile and acrylamide.

7
PROPERTIES

8
1.1.1 Physical Properties

Acrylonitrile (C3H3N, mol wt = 53.064) is an unsaturated molecule having a

carbon–carbon double bond conjugated with a nitrile group. It is a colorless
liquid, with the faintly pungent odour of peach pits. Its properties are summarized
in Table 1. Acrylonitrile is miscible with most organic solvents, including acetone,
benzene, carbon tetrachloride, ether, ethanol, ethyl acetate, ethylene,
cyanohydrin, liquid carbon dioxide, methanol, petroleum ether, toluene, xylene,
and some kerosenes. The water solubility of acrylonitrile at several temperatures is shown
in Table 1

1.1.2 Chemical Properties

Acrylonitrile is a very reactive compound. The double bond in the acrylonitrile

molecule is activated by conjugation with the polar nitrile group and will react in a variety of
ways. Acrylonitrile can undergo spontaneous, exothermic polymerization and so must be
inhibited for storage. The homo- and co- polymerization of acrylonitrile take place rapidly in
the presence of radiation, anionic initiators, or free-radical sources, such as peroxides or
diazo compounds. The reaction involves charge transfer complexes between various
monomers and can be produced in the vapor, liquid, or solid phase, in solution, and in dual-
phase systems. Only the latter two methods have had industrial impact.

Other notable reactions of the double bond of acrylonitrile include Diels-Alder reactions,
hydrogenation, cyanoethylation, hydrodimerization, and hydroformylation.

The most important reactions of the nitrile moiety of acrylonitrile are hydrolysis and
alcoholysis. Acrylonitrile can be hydrolyzed partially to acrylamide or completely to acrylic
acid, depending on the concentration of the acid used. For years the first step in the
commercial production of acrylamide was the partial hydrolysis with sulfuric acid to
acrylamide sulfate; however, now acrylonitrile is converted directly to acrylamide using
various copper-based catalysts.

Hydrolysis with hydro-chloric acid leads to hydrochlorination of the double bond as well,
forming 3- chloropropionamide or 3-chloropropionic acid. Although base-catalyzed
hydrolysis of acrylonitrile is possible, it can lead to undesired reactions of the double bond.
Acrylic esters can be produced from acrylonitrile and primary alcohols in the presence of
sulfuric acid. This reaction has been used commercially to produce methyl acrylate.
9
Other sulfuric acid-catalyzed reactions of acrylonitrile include those with olefins or tertiary
alcohols to yield N-substituted acrylamides and with formaldehyde to form

N,N ′-methylenebisacrylamide or 1,3,5-triacrylhexahydro-s-triazine

1.1.3 Uses of Acrylonitrile

Acrylonitrile is used as:

• A raw material for the production of synthetic fibres, plastics and synthetic rubber.
One of the reasons for the versatility of Acrylonitrile is that it can form copolymers
with other unsaturated compounds, such as styrene and butadiene, for example.
• A raw material for acrylic acid, acrylic esters, acrylic amide, carbon fibre.
• In the synthesis of compounds used for the production of adhesives, anti-oxidants,
binders for dyestuffs and emulsifiers.

10
 Table 1. Physical Properties of Acyrlonitrile Monomer

Property Value

Molecular weight 53.06

Boiling point, ◦ C
At 101.3 kPa 77.3

Critical pressure, kPa 3.535 × 103

Critical temperature, ◦ C 246.0
Density, g/L
At 20◦ C 806.0

At 25◦ C 800.4
At 41◦ C 783.9
Dielectric constant at 33.5 MHz 38
Entropy, vapor at 25◦ C, 101.3 kPa, J/(mol·K) 273.9

Explosive mixture with air at 25◦ C, vol%

Lower limit 3.05
Upper limit 17.0 ± 0.5
Flash point (tag open cup), ◦ C −5
Freezing point, ◦ C −83.55 ± 0.05

Gibbs energy of formation, vapor at 25◦ C, kJ/mol 195.4

Heat capacity, specific, liquid, kJ/(kg·K) 2.094
Heat capacity, specific, vapor, kJ/(kg·K)
At 50◦ C, 101.3 kPa 1.204

Heat of combustion, liquid at 25◦ C, kJ/mol −1.7615 × 103

Heat of fusion, kJ/mol 6.635 × 103

Heat of polymerization, kJ/mol −72.4 ± 2.1
Heat of polymerization at 74.5◦ C, kJ/mol −76.5 f
Heat of vaporization at 101.3 kPa, kJ/mol 32.65

Ignition temperature, ◦ C 481.0

Molar refraction, D line 15.67
Vapor density, relative 1.83 (air = 1.0)

Viscosity at 25◦ C, mPa·s(=cP) 0.34

11
MANUFACTURE

12
2.0 MANUFACTURE

2.1 Methods of Production

Today nearly 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 viable catalyst for this process. Today, all of the
United States capacity and approximately 90 % of the world capacity for acrylonitrile is
based on the Sohio process.

2.1.1 Sohio Process

In the Sohio 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):

2CH2=CH-CH3 + 2NH3 + 3O2 ⎯→ 2CH2=CH-C≡N + 6H2O

2.1.2 Production from Ethylene Cyanohydrin

Germany (I.G. Farben, Leverkusen) and the United States (American Cyanamid) first
produced acrylonitrile on an industrial scale in the early 1940s. These processes 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 then dehydrated in the liquid phase at 200 °C in the presence
of magnesium carbonate and alkaline or alkaline earth salts of formic acid.

HO-CH2-CH2-C≡N ⎯→ CH2=CH-C≡N + H2O

An advantage of this process was that it generated few impurities; however, it was not
economically competitive. American Cyanamid and Union Carbide closed plants based on
this technology in the mid-1960s.

2.1.3 Production from Acetylene and Hydrocyanic Acid

Before the development of the propene ammoxidation process, a major industrial

route to acrylonitrile involved the catalytic addition of hydrocyanic acid to acetylene.

H-C≡C-H + HCN ⎯→ CH2=CH-CN

13
Although 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 expensive, 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 process until about 1970.

2.1.4 Future Processes

Several other chemicals have been studied as possible alternative precursors to

acrylonitrile. Ethylene, propane, and butane react with ammonia at high temperatures (750 –
1000 °C) to yield acrylonitrile. Monsanto, Power Gas, and ICI have developed catalytic
ammoxidation processes based on propane. Propane is of particular interest because of a cost
advantage over propene. However, this price difference is not likely to be great enough in the
near future to dictate change. High conversions to acrylonitrile also have been obtained on a
laboratory scale from ethylene, hydrogen cyanide, and oxygen using a palladium-based
catalyst.

14
 PROCESS
DESCRIPTION

15
3.0 PROCESS DESCRIPTION

Due to the broad expanse and complexity of the chemical manufacturing industry,
acrylonitrile manufacturing has been selected as being representative of it; however, process
procedures may vary somewhat between different chemical industries.

Nearly all of the acrylonitrile (ACN) produced in the world today is produced using
the SOHIO process for ammoxidation of propylene and ammonia. The overall 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 oxides.

The recovery of these by-products depends on factors such as market conditions,

plant location, and energy costs. 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 provide for purification, storage, and
loading facilities for these recoverable by-products. Other variations of the SOHIO process
include the recovery of ammonium sulfate from the reactor effluent to allow for biological
treatment of a wastewater stream and variations in catalysts and reactor conditions.

In the standard SOHIO process, as given Appendix II, air, ammonia, and propylene
are introduced into a fluid-bed catalytic reactor operating at 0.3 − 2 𝑎𝑡𝑚 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
and 400 − 510°𝐶 (750 − 950°𝐹). Ammonia and air are fed to the reactor in slight excess of
stoichiometric proportions because excess ammonia drives the reaction closer to completion
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 a few seconds residence time. The
heat generated from the exothermic reaction is recovered via a waste-heat-recovery boiler.

In the reactor following reaction take place:

Main Reaction:

2C3H6 + 2NH3 +. 3O2 2C3H3N + 6H2O

(Propylene) (Ammonia) (Oxygen) (Acrylonitrile) (Water)

16
Side Reactions:

4C3H6 + 6NH3 + 3O2 6C2H3N + 6H2O

(Acetonitrile)

C3H6 + 3NH3 + 3O2 3HCN + 6H2O

(Hydrogen Cyanide)

2C3H6 + 3O2 6CO2 + 6H2O

(Carbon dioxide)

The product stream then flows through a counter 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 remove
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. Catalyst 49, which represents the fourth major level of improvement, is currently
recommended in the process. Emissions of ACN during start-up are substantially 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.

The ACN content of the combined column purge vent gases is relatively high, about 50% of
the total VOCs emitted from the recovery, acetonitrile, light ends, and product columns. The
rest of the vent gases consist of 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 leaks into the column and is removed by the vacuum jet systems.

17
For the ACN process illustrated in Exhibit 1, by-product hydrogen cyanide and acetonitrile
are incinerated along with product column bottoms. The primary pollutant 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 lesser amounts of CO are emitted from the
incinerator stack gas.

Other emission sources involve 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 consist primarily of ACN.

18
MATERIAL
BALANCE

19
3.1 Material Balance

Basis:
• Total Production
• Working hours
• Working days
• Production rate
• Molar feed ratio =
: 100000 𝑡𝑜𝑛𝑠/𝑦𝑒𝑎𝑟
: 24𝑕𝑟𝑠 𝑎 𝑑𝑎𝑦
: 300 𝑑𝑎𝑦𝑠 𝑝𝑒𝑟 𝑎𝑛𝑛𝑢𝑚
: 13889 𝑘𝑔/𝑕
= 3.858 𝑘𝑔/𝑠
= 0.07278 𝑘𝑚𝑜𝑙/𝑠
𝑃𝑟𝑜𝑝𝑙𝑦𝑙𝑒𝑛𝑒 ∶ 𝑁𝐻3 ∶ 𝐴𝑖𝑟 = 1 ∶ 1.2 ∶ 9.5

Process Unit Acrylonitrile Recovery

Fluidised Bed Reactor 85%

Absorber column 100%

Extractive distillation column 99.5%

Acetonitrile stripping column 99%

Lights fractionation column 99.9%

Product column 85%

Fluidised Bed Reactor

Acrylonitrile (C3H3N)

Propylene 1 Acetonitrile (C2H3N)

FLUIDIZED BED
Ammonia 2 REACTOR 4 HCN

Air 3 Conversion = 99 % H20

O2

CO2

20
In the reactor the following reactions take place:

Conversion
Main Reaction:

2C3H6 + 2NH3 +. 3O2 2C3H3N + 6H2O 0.85

(Propylene) (Ammonia) (Oxygen) (Acrylonitrile) (Water)

Side Reactions:

4C3H6 + 6NH3 + 3O2 6C2H3N + 6H2O 0.02

(Acetonitrile)

C3H6 + 3NH3 + 3O2 3HCN + 6H2O 0.02

(Hydrogen Cyanide)

2C3H6 + 3O2 6CO2 + 6H2O 0.100

(Carbon dioxide)

INPUT OUTPUT
STREAM
(kmol/s) (kmol/s)

STREAM No. 1 2 3 4

Temperature(oC) 400 400 400 130

C3H6 0.086944 ---- ---- 0.000869
O2 ---- ---- 0.173450 0.043312
N2 ---- ---- 0.652518 0.652080
NH3 ---- 0.104333 ---- 0.022600
CO2 ---- ---- ---- 0.026080
HCN ---- ---- ---- 0.005216
AN ---- ---- ---- 0.073900
CAN ---- ---- ---- 0.002608
H2 0 ---- ---- ---- 0.260800
TOTAL 0.086944 0.104333 0.825968 1.088109

Similarly material balance is carried out for all the unit operations and presented as PFD
(Process Flow Diagram) as shown in the Appendix III.

21
ENERGY
BALANCE

22
3.2 Energy balance

The first law of thermodynamics says that energy be neither created nor destroyed.
The following is a systematic energy balance performed for each unit of the process. The
datum temperature for calculation is taken as 25 OC. The pressure is taken to be 1 atm
throughout the process.

The physical properties such as density, specific heat, heat of reaction, and heat of formation
were assumed as constant over the temperature range.

Acrylonitrile (C3H3N)

Propylene 1 Acetonitrile (C2H3N)

FLUIDIZED BED
Ammonia 2 REACTOR 4 HCN

Air 3 Conversion = 99 % H20

O2

CO2

In the reactor the following reactions take place

Main Reaction:

2 C3H6 + 2 NH3 +. 3 O2 2C3H3N + 6H2O

(Propylene) (Ammonia) (Oxygen) (Acrylonitrile) (Water)

Side Reactions:

4C3H6 + 6NH3 + 3O2 6C2H3N + 6H2O …(1)

(Acetonitrile)

C3H6 + 3NH3 + 3O2 3HCN + 6H2O …(2)

(Hydrogen Cyanide)

2C3H6 + 3O2 6CO2 + 6H2O …(3)

(Carbon dioxide)

23
Table 2 Heat capacity and Enthalpy data

 kJ  æ kJ ö
H
0
Cp ç
è mol ÷ø
COMPONENT f 298  
 mol 

Propylene +20.41 0.05

Ammonia -46.19 0.03

----
Oxygen 0.03
----
Nitrogen 0.03

Acrylonitrile +184.93 1.204

Acetonitrile +74.56 0.06

HCN +130.5 0.035

CO2 -393.50 0.039

H2O(g) −241.83 2.013

H2O(l) −285.83 4.184

*Cooling water is available at 25𝑜 𝐶 and dry steam is available at 150𝑜 𝐶

Fluidised Bed Reactor
Enthalpy of formation of reaction:

 For main reaction

∆𝐻 𝑜 𝑓 = Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑃 − Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑅
= (2 × 184.93 + 6 × −285.83 − 2 × −46.19 − 2 × 20.41)

= − 1293.36 𝑘𝐽/𝑠

 For reaction 1
∆𝐻 𝑜 𝑓 = Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑃 − Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑅
= 6 × 74.56 + 6 × −285.83 − 4 × 20.41 − 6 × (−46.19)

= − 1072.12 𝑘𝐽/𝑠

24
 For side reaction 2

∆𝐻 𝑜 𝑓 = Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑃 − Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑅
= 6 × −241.83 + 3 x 130.5– 3 × (−46.19) – 20.41

= − 941.32 𝑘𝐽/𝑠

 For side reaction 3

∆𝐻 𝑜 𝑓 = Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑃 − Σ 𝑣𝑖 ∆𝐻 𝑜 𝑓𝑅
= 6 × (−241.83) + 6 × (−393.5) – 2 x 20.41

= −3852.8 𝑘𝐽/𝑠

Total enthalpy of formation = (−𝟏𝟐𝟗𝟑. 𝟑𝟔 – 𝟏𝟎𝟕𝟐. 𝟏𝟐 – 𝟗𝟒𝟏. 𝟑𝟐 – 𝟑𝟖𝟓𝟐. 𝟖)

= − 𝟕𝟏𝟓𝟗. 𝟔 𝒌𝑱/𝒔

Enthalpy of reactants:

 Reactants are added at 400oC.

∆𝐻𝑅 = [ nCp + (nCp )Ammonia + (nCp )Oxygen + (nCp )Nitrogen ]  T
Propylene

=[ 0.086944 𝑥 0.05 + 0.1043 𝑥 0.03 + 0.17345 𝑥 0.03 +

0.6525 𝑥 0.03] (400 − 25)

= 0.032255 𝑥 375

= 𝟏𝟐. 𝟎𝟗𝟓𝟕 𝒌𝑱/𝒔

Enthalpy of products:

 Products leave at 130 o C.

∆𝐻𝑃 = nCp + nCp + nCp + nCp + nCp +

C 3𝐻6 NH 3 O2 N 2 unreacted AN

nCpACN +nCpHCN +nCpCO2+nCp𝑤𝑎𝑡𝑒𝑟  T

= {[8.6944𝑥10 − 4 𝑥 0.05 + 0.0430375 𝑥 0.03 + 0.6525 𝑥 0.03 + 0.0226 𝑥 0.03]

+ [0.0739 𝑥 1.204 + 0.00026 𝑥 0.06 + 0.0005216 𝑥 0.035
+ 0.02608 𝑥 0.039 + 0.2608 𝑥 2.013]} (130 − 25)

= 𝟔𝟔. 𝟖𝟓𝟔𝟎 𝒌𝑱/𝒔

25
Enthalpy of reaction:

∆𝐻𝑡𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = ∆𝐻𝑃 − ∆𝐻𝑅 + ∆𝐻𝑓 𝑜

= (−7159.6) + 12.0957 + 66.8560

= −𝟕𝟏𝟎𝟒. 𝟖𝟑𝟗𝟔𝟐 𝒌𝑱/𝒔

The negative sign in the above calculation ( ∆𝐻𝑡𝑒𝑎𝑐𝑡𝑖𝑜𝑛 indicates that the reaction is
exothermic. Hence cooling water is used for the removal of the heat

Assuming water enters at 25 𝑜 C and leaves at 80 𝑜 C

𝑄 = 𝑛 × 𝐶𝑝 × ∆𝑇

− 7104.83962 = 𝑛 × 4.184 × 25

𝑛 = 30.8745 𝑘𝑚𝑜𝑙/𝑠

Similarly energy balance is carried out for all the unit operations and represented in tabular
form as shown in appendix IV

26
EQUIPMENT
DESIGN

27
4.0 EQUIPMENT DESIGN

4.1 Fluidised Bed Reactor (FBR)

Assumptions:

ε𝑚 = 0.5

ε𝑚𝑓 = 0.55

ε𝑓 = 0.70

𝑇 = 400 𝑜 𝐶

𝑃 = 1 𝑎𝑡𝑚
Feed gas enters at bed temperature at composition

𝐶3 𝐻6 : 𝑁𝐻3 : 𝑎𝑖𝑟 = 1: 1.2: 9.5

Heat exchanger: Vertical tubes 0.08m OD,

𝑕𝑜𝑢𝑡𝑠𝑖𝑑𝑒 = 300 𝑊 𝑚2 𝐾

𝑕𝑖𝑛𝑠𝑖𝑑𝑒 = 1800 𝑊 𝑚2 𝐾

𝐷𝑝 = 60µ𝑚

𝑢𝑜 = 0.5 𝑚/𝑠

𝜏 = 8𝑠

4.1.1 Length of the reactor

𝑙𝑚 (1 − ε𝑚 )
𝜏 =
𝑢𝑜

0.5 ∗ 8
𝑙𝑚 = =8𝑚
0.5
𝑙𝑚 (1 − ε𝑚 ) 8 × 0.5
𝑙𝑓 = = = 𝟏𝟑. 𝟑𝟑 𝒎
(1 − ε𝑓 ) 1 − 0.7

With this bed height we choose length of heat exchanger tubes, 𝑙 to be 8 𝑚 long.

28
4.1.2 Diameter of the reactor

Cross sectional area of reactor

Volumetric flow rate of propylene

𝑘𝑔 22.4 𝑚 3 673 𝐾 1 𝑏𝑎𝑟 1+1.2+9.5

= 3.65165
𝑠 42 𝑘𝑔 273 𝐾 1𝑏𝑎𝑟 1

= 56.1728 𝑚3

𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑝𝑟𝑜𝑝𝑦𝑙𝑒𝑛𝑒 56.1728

CSA of the reactor needed = =
𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑔𝑎𝑠 0.50

= 112.3456 𝑚3

𝜋𝑑 2
𝐶𝑆𝐴 𝑜𝑓 𝑡𝑕𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 =
4

112 .3456 ×4 𝟎.𝟓

Thus, diameter of the column, 𝑑 = = 𝟏𝟏. 𝟗𝟔 𝒎
𝜋

Heat Exchanger Calculations

𝑞 = 7104.83962 𝑘𝐽/𝑠

Overall heat transfer coefficient is

−1 −1
1 1 1 1
𝑈= + = + = 257.1 𝑊 𝑚2 𝐾
𝑕𝑖𝑛𝑠𝑖 𝑑𝑒 𝑕𝑜𝑢𝑡𝑠𝑖𝑑𝑒 300 1800

Hence the exchanger surface area needed to remove this heat is

𝑞 7104.83962 × 103
𝐴𝑤 = = = 110.5381 𝑚2
𝑈 ∆𝑇 257.1 × 400 − 150

The number of 2 𝑚 long tubes required is

𝐴𝑤 110.5381
𝑁𝑇 = = = 𝟓𝟒. 𝟗𝟕𝟕𝟏
𝜋 𝑑 𝑙 𝜋 0.08 8

29
4.2 Distillation Column

4.2.1 Number of Theoretical Plates (by McCabe–Thiele method)

𝐹𝑒𝑒𝑑, 𝐹 = 3.1556 𝑘𝑚𝑜𝑙/𝑠

𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒, 𝐷 = 0.1096 𝑘𝑚𝑜𝑙/𝑠

𝑅𝑒𝑠𝑖𝑑𝑢𝑒, 𝑊 = 3.0460 𝑘𝑚𝑜𝑙/𝑠

0.0739
Mol fraction of acrylonitrile in feed, 𝑥𝑓 =
3.1556

𝑥𝑓 = 0.02342

Similarly, 𝑥𝑑 = 0.67092

𝑥𝑤 = 0.0001213

Parameter of thermal state of feed:

𝑞 = 1 (Saturated liquid at its bubble point)

Reflux ratio
𝐿
𝑅 = = 2 × 𝑅𝑑
𝐷

Overall plate efficiency

𝐸 = 1
From equilibrium curve, at minimum reflux ratio (Rd), we get

𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = 0.01875

𝑥𝑑
𝑅𝑑 = –1
(Intercept)

0.67
= −1
0.03

= 21.33

Let reflux ratio, 𝑅 = 1.5 × 𝑅𝑑 = 42.66

30
 𝑥𝑑
Thus, 𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = (𝑅+1) = 0.01534

Thus from the equilibrium curve we get,

No of theoretical stages = 30

Position of feed tray = 8 tray

4.2.2 Height and Diameter of the column

Density of feed, 𝜌 = 𝜌𝑖 𝑥𝑖

0.000869 0.022605
x 0.04309 + x 0.04294 +
3.1556 3.1556

0.026083 0.005216
3.1556
x 0.0425 + 3.1556
x 0.02544 +
0.073900 0.002608
x 15.2075 + x 19.1951 +
3.1556 3.1556
3.024360
x 55.556
3.1556

= 53.6208 𝑘𝑚𝑜𝑙/𝑚3

Similarly, Density of liquid, 𝜌𝑙 = 166.3966 𝑘𝑚𝑜𝑙/𝑚3

Density of vapor, 𝜌𝑣 = 2.7987 𝑘𝑚𝑜𝑙/𝑚3

We chose the plate spacing, 𝑙 to be 0.5 m

Thus vapour velocity, 𝑢𝑣 , can be calculated:

2 𝜌 𝑙 − 𝜌 𝑣 0.5
𝑢𝑣 = (-0.171l + 0.271 l – 0.047)
𝜌𝑣

Thus, 𝑢𝑣 = 0.34598 m/s

The column diameter, 𝐷𝑐 , can be then calculated:

4𝑉
𝐷𝑐 = 𝜋 𝜌 𝑣 𝑢𝑣
Where, 𝑉 = vapour rate, 𝑘𝑚𝑜𝑙/𝑠

Thus, 𝐷𝑐 = 0.37968 𝑚
31
Height of the column = (𝑛𝑜 𝑜𝑓 𝑝𝑙𝑎𝑡𝑒𝑠 + 2) × 𝑃𝑙𝑎𝑡𝑒 𝑠𝑝𝑎𝑐𝑖𝑛𝑔

= 32 𝑥 0.5

= 𝟏𝟔 𝒎

Note: The drawing for the designed FBR and the Distillation column are given in Appendix
VII and VIII

32
Cost Estimation

33
5.0 Cost estimation

Number of working days per year = 300.00

Cost of 1000 kg of acrylonitrile = 85,000.00 `
Production of acrylonitrile = 100,000.00 ton
Gross sale for 1 year or total income = 8,50,00,00,000.00 `
, = 8,50,00,00,000.00 `

Turn Over Ratio

It is defined as the ratio of total income to the fixed capital investment

Total Income
i.e., TOR = Fixed Capital
Investment

For process industries turnover ratio is 1, thus,

Fixed Capital Investment (FCI) = Gross annual sales = 8,50,00,00,000.00 `
But, Fixed Capital Investment = Direct cost + Indirect Cost

5.1.1 Direct Cost

Direct cost is taken as 70% of fixed capital investment = 5,95,00,00,000.00 `

= 88, 06,24025.00 `

The cost involved are ,

i. Equipment cost 35% 2,08,25,00,000.00
ii. Installation and piping cost 6% 35,70,00,000.00
iii. Instrumentation cost 9% 53,55,00,000.00
iv. Electrical cost 10% 59,50,00,000.00
v. Piping cost 9% 53,55,00,000.00
vi. Building, process and auxiliary cost 7% 41,65,00,000.00
vii. Service facilities and yard improvement cost 4% 23,80,00,000.00
vii. Land cost 20% 1,19,00,00,000.00
Total 100% 5,95,00,00,000.00 `

5.1.2 Indirect cost

Indirect cost = Fixed Capital Investment - Direct Cost = 2,55,00,00,000.00 `

i.e., 2,55,00,00,000.00 `

Indirect cost consists of following items,

34
 i. Engineering and supervision cost
ii. Contingency
iii. Working capital

Engineering and supervision cost. i.e, 6% of

i. = 35,70,00,000.00
direct cost
i.e, 35,70,00,000.00 `

ii. Contingency is 2% of direct cost = 11,90,00,000.00

i.e, 11,90,00,000.00 `

iii. Working capital is 22% of direct cost = 1,30,90,00,000.00

1,30,90,000.00 `
Total = 1,78,50,00,000.00 `
, i.e., 1,78,50,00,000.00 `

Therefore, total working capital = fixed capital + working capital = 9,80,90,00,000.00 `

i.e., 9,80,90,00,000.00 `

5.1.3 Estimation of total product cost

Total Annual income = 8,50,00,00,000.00 `

Gross earning is 10% of annual income = 85,00,00,000.00 `
i.e., 85,00,00,000.00 `

Product cost = Total annula income - Gross earnings = 7,65,00,00,000.00 `

i.e., 7,65,00,00,000.00 `

Direct production Cost

It can be taken as 60% of total product cost = 4,59,00,00,000.00 `

Raw materials cost

It is 5% of toal product cost = 38,25,00,000.00 `

Operating labour cost

It can be taken as 15% of total product cost = 1,14,75,00,000.00 `

Direct supervisory and clinical labour cost

It is 20% of operating labour cost = 7,14,00,000.00 `

35
Utilities
It can be taken as 10% of total product cost = 76,50,00,000.00 `

Maintenance and repair cost

It is 3.6% of fixed capital investment cost = 8,50,00,00,000.00 `

= 30,60,00,000.00 `

Laboratory Charges

It is taken as 6.7% of operating labour cost = 35,70,00,000.00 `

= 2,39,19,000.00 `

Royalities

It can be taken as 1.5% of fixed capital cost = 8,50,00,00,000.00 `

= 12,75,00,000.00 `
Fixed Charges

It can be taken as 10% of product cost = 76,50,00,000.00 `

Plant overheads

This includes the cost of general house packaging, medical services, safety and protection
recreation, sewage, laboratories and storage facilities

It is 5% of total product cost = 38,25,00,000.00 `

Depreciation

Depreciation for machinery is 10% of fixed capital cost = 8,50,00,00,000.00 `

= 85,00,00,000.00 `

Depreciation of building is 3% of the land cost = 1,19,00,00,000.00 `

= 3,57,00,000.00 `
Total depreciation value is 13% = 88,57,00,000.00 `
Depreciable capital investment is = 88,57,00,000.00 `

Insurance

It is 1% of the fixed capital cost = 8,50,00,00,000.00 `

= 8,50,00,000.00 `
36
Rent value
It is 2% of the total product cost = 15,30,00,000.00 `

General expenses

Administrative cost includes cost of officers, legal fees, office supplier and communications.

It is 4% of the total product cost = 30,60,00,000.00 `

Distribution and selling cost

It accounts for 6% of total product cost = 45,90,00,000.00 `

Research and development cost

It is 1% of total product cost = 7,65,00,000.00 `

Financing

It is 2% of the total product cost = 15,30,00,000.00 `

Net Profit

It is obtained after deduction of taxes from the gross earnings.

Net Profit is 40% of gross earnings = 8,50,00,00,000.00 `

= 3,40,00,00,000.00 `

5.1.4 Determination of Pay-Back Period

Depreciable fixed capital investment

Pay-back period =
(Average profit + Average depreciation)

Pay-back period = 1
1 year

37
 PLANT
LAYOUT

38
6.0 PLANT LAYOUT
A suitable site must be found for a new project, and the site and equipment layout
planned. Provision must be made for the ancillary buildings and services needed for plant
operation and for the environmentally acceptable disposal of effluent. Plant layout refers to
the arrangement of physical facilities such as machinery, equipment, furniture etc. within the
factory building in such a manner so as to have quickest flow of material at the lowest cost
and with the least amount of handling in processing the product from the receipt of material
to the shipment of the finished product.

According to Riggs, “the overall objective of plant layout is to design a physical

arrangement that most economically meets the required output – quantity and quality.”

According to J. L. Zundi, “Plant layout ideally involves allocation of space and

arrangement of equipment in such a manner that overall operating costs are minimized. A
sample plant layout for our designed project is given in appendix V

6.1.0 SITE SELECTION

The location of the plant can have a crucial effect on the profitability of a project, and
the scope for future expansion. An ideal location is one where the cost of the product is kept
to minimum, with a large market share, the least risk and the maximum social gain. It is the
place of maximum net advantage or which gives lowest unit cost of production and
distribution. For achieving this objective, small-scale entrepreneur can make use of location
analysis for this purpose. Many factors must be considered when selecting a suitable site, and
only a brief review of the principle factors are given below.

The principle factors to consider are:

1. Location, with respect to the marketing area.

2. Raw material supply.
3. Transport facility.
4. Availability of labour.
5. Availability of utilities: water, fuel, power.
6. Availability of suitable land.
7. Environmental impact and effluent disposal.
8. Local community considerations.
9. Climate.
10. Political and strategic considerations.

39
Location with respect to the Marketing area

For materials that are produced in bulk quantities where the cost of the
product per tonne is relatively low and the cost of transport a significant fraction of the sales
price, the plant should be located close to the primary market. This consideration will be less
important for low volume production, high-priced products.

In an international market, there may be an advantage to be gained by locating the

plant within an area with preferential tariff agreements.

Raw Materials

The availability and price of suitable raw materials will often determine the site
location. Plants producing bulk chemicals are best located close to the source of the major
raw material where this is also close to the marketing area.

Transport

The transport of materials and products to and from the plant will be an overriding
consideration in site selection. If practicable, a site should be selected that is close to at least
two major forms of transport: road, rail, waterway (canal or river), or a sea port. Road
transport is being increasingly used, and is suitable for long- distance transport of bulk
chemicals.

Air transport is convenient and efficient for the movement personnel and essential
equipment and supplies, and the proximity of the site to a major airport should be considered.

Availability of labour

Labour will be needed for construction of the plant and its operation. Skilled
construction workers will usually be brought in from outside the site area, but there should be
an adequate pool of unskilled labour availability locally and labour suitable for training to
operate the plant. Skilled tradesmen will be needed for plant maintenance. Local trade union
customs and restrictive practices will have to be considered when assessing the availability
and suitability of the local labour for recruitment and training.

40
Utilities (Services)

Chemical processes invariably require large quantities of water for cooling and
general process use, and the plant must be located near a source of water of suitable quality.
Process water may be drawn from a river, from wells, or purchased from a local authority. At
some sites, the cooling water required can be taken from a river or lake, or from the sea at
other locations cooling towers will be needed.

Electrical power will be needed at all sites. Electrochemical processes that require
large quantities of power need to be located close to a cheap source of power. A
competitively priced fuel must be available on site for steam and power generation.

Environmental impact and effluent disposal

All industrial processes produce waste products, and full consideration must be given
to the difficulties and cost of their disposal. The disposal of toxic and harmful effluents will
be covered by local regulations, and the appropriate authorities must be consulted during the
initial site survey to determine he standards that must be met. An environmental impact
assessment should be made for each new project or major modification or addition or an
existing process.

Local community considerations

The proposed plant must be fit in with and be acceptable to the local community. Full
consideration must be given to the safe location of the plant so that it does not impose a
significant additional risk to the community.

On a new site, the local community must be able to provide adequate facilities for the
plant personnel: schools, banks, housing, and recreational and cultural facilities.

Land (site considerations)

Sufficient suitable land must be available for the proposed plant and for future
expansion. The land should ideally be flat, well drained and have suitable load-bearing
characteristics. A full site evaluation would be made to determine the need for piling or other
special foundations.

41
Climate

Adverse climatic conditions at a site will increase costs. Abnormally low

temperatures will require the provision of additional insulation and special heating for
equipment and pipe runs. Stronger structures will be needed at locations subject to high
winds (cyclone/hurricane) or earthquakes.

Political and strategic considerations

Capital grants, tax concessions, and other inducements are often given by
governments to direct new investment to preferred locations. such as areas of high
unemployment. The overriding of such grants can be the overriding considerations in site
selection.

Site layout

The process units and ancillary buildings should be laid out to give the most
economical flow of materials and personnel around the site. Hazardous processes must be
located at a safe distance from other buildings. Consideration must be given to the future
expansion of the site. The ancillary buildings and services required on a site, in addition to
the main processing units (buildings), will include:

1. Storages for raw materials and products: tank farms and warehouses.
2. Maintenance workshops.
3. Stores, for maintenance and operating supplies.
4. Laboratories for process control.
5. Fire stations and other emergency services.
6. Utilities: Steam boilers, compressed air, power generation, refrigeration,
transformer station
7. Effluent disposal plant.
8. Offices for general administration.
9. Canteens and other amenity buildings, such as medical centre.
10. Car parks.

When roughing out the preliminary site layout, the process units will normally be sited first
and arranged to give a smooth flow of materials through the various processing steps, from

42
raw materials to final product storage. Products units are normally spaced at least 30 m apart.
Grater spacing may be needed for hazardous processes.

The location of the principal ancillary buildings should then be decided. They should
be arranged so as to minimize the time spent by personnel in travelling between buildings.

Administration offices and laboratories, in which a relatively large number of people

will be working, should be located well away from potentially hazardous processes. Control
rooms will normally be located adjacent to the processing units, but with potentially
hazardous processes may have to be sited at a safer distance.

The sitting of the main process units will determine the layout of the plant roads, pipe
alleys and drains. Access roads will be needed to each building for construction, and for
operation and maintenance.

Utility buildings should be sited to give the most economical run of pipes to and from
the process units. Cooling towers should be sited so that under the prevailing winds the
plume of condensate spray drifts away from the plant area and adjacent properties.

The main storage area should be placed between the loading and unloading facilities
and the process units they serve. Storage tanks containing hazardous materials should be
sited at least 70 m (200 ft.) from the site boundary.

6.1.1 OTHER CONSIDERATION

The economic construction and efficient operation of the process unit will
depend on how well the plant and equipment specified on the process flow-sheet is laid out.

The principal factors to be considered are:

1. Economic considerations: construction and operating costs.

2. The process requirements.
3. Convenience of operation.
4. Convenience of maintenance
5. Safety.
6. Future expansion.
7. Modular construction.

43
 1. Costs

The cost of construction can be minimized by adopting a layout that gives the shortest
run of connecting pipe between equipment, and the least amount of structural steel work.
However, this will not necessarily be the best arrangement for operation and maintenance.

2. Process requirements

An example of the need to take into account process considerations is the need to
elevate the base of columns to provide the necessary net positive head to a pump or the
operating head for a thermo-syphon reboiler.

3. Operation

Equipment that needs to have frequent operator attention should be located

convenient to the control room. Valves, sample points and instruments should be located at
convenient positions and heights. Sufficient working space and headroom must be provided
to allow an easy access to equipment.

4. Maintenance

Heat exchangers need to be sited so that the tube bundles can be easily withdrawn for
cleaning and tube replacement. Vessels that require frequent replacement of catalyst or
packing should be located on the outside of buildings. Equipment that requires dismantling
for maintenance, such as compressors and large pumps, should be placed undercover.

5. Safety

Blast walls may be needed to isolate potentially hazardous equipment, and confine
the effects of an explosion. At least two escape routes for operators must be provided from
each level in process buildings.

6. Plant expansion

Equipment should be located so that it can be conveniently tied in, with any future
expansion of the process. Space should be left on pipe alleys for future needs, and service
pipes over-sized to allow for future requirements.

44
 7. Modular construction

In recent years, there has been a move to assemble sections of plant at the plant
manufacturer’s site. These modules will include the equipment, structural steel, piping and
instrumentation. The modules are then transported to the plant site, by road or sea.

7.0 Storage and Transportation

Acrylonitrile may be fatal if absorbed through the skin and can be harmful if inhaled
or ingested. In addition, acrylonitrile also is a flammable liquid and its vapors can form
explosive mixtures with air under ambient conditions. The toxicity, flammability, and vapor
pressure of acrylonitrile dictate that it be stored in closed systems.
Storage vessels and piping for use at ambient temperature and pressure may be
constructed from carbon steel. Stainless steel is recommended for more severe conditions.
Tanks should be electrically grounded and equipped with scrubbers or vent condensers to
prevent vapor leaks to the atmosphere. Other storage considerations include preserving
product quality and minimizing the potential for polymerization.
Acrylonitrile is transported in tank cars, barges, steel drums, and via pipeline.
International transportation of acrylonitrile is governed by the International Maritime
Dangerous Goods (IMDG) code published by the Intergovernmental Maritime Consultative
Organization (IMO): IMDG code no. 3105, class 3.1, UN no. 1093. In the United States,
acrylonitrile is classified as a flammable liquid and as a poison, and its transportation is
governed by the U.S. Department of Transportation (DOT) Safety Act, title CFR 172.101 et
seq. The DOT freight classification is RQ/Acrylonitrile/Flammable Liquid/UN 1093/ Poison.
Transportation in Europe is regulated by RID, ADR, and ADRN: class 6.1, no. 2 a (from
1985: class 3, no. 11a), RN 601, 2601, and 6601 resp. Blue Book (UK): flammable liquid,
IMDG E 3022.

45
Health Aspects

46
8.0 Toxicology and Occupational Health
The effects of human exposure to acrylonitrile have been a matter of public health
concern and speculation for some time, but a good under-standing of the toxic effects of
acrylonitrile has just evolved in the last decade. Because so vast a number of studies have
been directed at understanding the toxicity of acrylonitrile, only a general overview can be
given here.
Acrylonitrile is toxic to laboratory animals, regardless of the route of exposure.
Acrylonitrile exerts its toxic action by two simultaneous mechanisms: inhibition of the
activity of cyto chrome oxidase by liberation of cyanide, and the inhibition of sulfhydryl
dependent enzymes of intermediary metabolism by cyanoethylation of sulfhydryl groups.
Furthermore, there is some evidence that, contrary to past belief, cyanide plays little role in
acrylonitrile lethal effects. Coadministration of certain aromatic compounds has been
reported to increase the lethal effects of acrylonitrile. A wide range of acute LD50 values has
been found for different laboratory animals and for different routes of administration. Mice
(25 – 50 mg/kg) are more sensitive to acrylonitrile than are rats (78 – 150 mg/kg) and guinea
pigs (56 mg/kg). The consequences of human acrylonitrile exposure depend both on the route
and the degree of exposure. Acrylonitrile may cause death by ingestion, inhalation of vapor,
or absorption of the liquid through the skin. Nonfatal intoxication of people working with
acrylonitrile has been reported in several instances.
Acrylonitrile poisoning results in toxic symptoms characteristic of the cyanide ion.
Sequentially, one experiences irritation of eyes and nose, limb weakness, labored breathing,
dizziness and impaired judgement, nausea, collapse, irregular breathing, and convulsions,
possibly followed by cardiac arrest. Direct skin contact with acrylonitrile can cause severe
skin irritation and, in some cases, allergic dermatitis. Despite its large-scale use, no fatal
accidental poisonings from acrylonitrile are known in industry, although several deaths have
been reported following applications of fumigants containing acrylonitrile.
A description of protective clothing that should be worn when handling this
compound is given in reference. Chronic effects potentially can occur after prolonged,
excessive exposure to acrylonitrile. Complaints of headache, weakness, fatigue, nausea,
nosebleeds, and insomnia came from Japanese workers manufacturing acrylonitrile. Others
exposed to 5 – 20 ppm of acrylonitrile were found to have abnormal liver functions. Skin
irritation and allergic dermatitis also have been observed in workers after chronic exposure to
acrylonitrile. A number of long-term studies with laboratory animals have added significantly
to the understanding of acrylonitrile toxicity, particularly in relation to carcinogenicity.
47
Ingestion or inhalation of acrylonitrile has caused tumors of the central nervous system and
zymbal gland in rats. Acrylonitrile also appears to be mutagenic in certain bacterial and
mammalian test systems.
The results of laboratory experiments and an epidemiology study that suggested
above average cancer levels among workers at a Du Pont textile plant prompted OSHA to
regulate acrylonitrile as a carcinogen, and its use in the United States must be in strict
conformance to standards set forth in the Federal Register. These regulations set the
permissible exposure limit (PEL) to acrylonitrile at 2 ppm as an 8-h time-weighted-average
(TWA) concentration, with a ceiling level of 10 ppm for any 15-min period. In addition, the
standard established an action level of 1 ppm (8-h TWA) and included requirements for
employee training, medical surveillance, record keeping, and analytical procedures for
monitoring employee exposure (appendix D of the standard). Among other things, the
standard requires the employer to provide protective clothing and equipment, including
respirators, and to establish regulated areas where acrylonitrile concentrations may exceed the
permissible limits.
Legal actions have been taken in the United States against certain applications of
acrylonitrile. In 1977, the U. S. Federal Drug Administration declared acrylonitrile to be an
indirect food additive and banned use of beverage containers made from acrylonitrile. In
other food-packaging applications limits were established for allowable residual monomer
concentrations. The German MAK commission classifies acrylonitrile in group III A 2 for
compounds presenting a carcinogenic risk for humans.

48
9.0 Nomenclature
Symbol/Acronym Key

𝐴𝑤 Exchanger Surface Area

ACN Acrylonitrile

AN Acetonitrile

𝐶𝑝 Specific Heat

𝑑, 𝐷𝑐 Diameter of the Column

𝐷 Distillate

𝐷𝑝 Diameter of the Catalyst Particle

𝐸 Plate Efficiency

void fraction in a fixed bed, at minimum fluidisation, in the fluidised

𝜖𝑚 , 𝜖𝑚𝑓 , 𝜖𝑓
bed as a whole

𝐹𝐶𝐼 Fixed Capital Investment

𝑕𝑜𝑢𝑡𝑠𝑖𝑑𝑒 , 𝑕𝑖𝑛𝑠𝑖𝑑𝑒 heat transfer coefficient ouside, inside

∆𝐻𝑜 𝑓 , ∆𝐻𝑜 𝑓𝑃 , ∆𝐻𝑜 𝑓𝑅 Standard Heat of formation, of products, of reactants

𝑢𝑜 , 𝑢𝑣 gas velocity
𝜏 space time
𝑙𝑚 , 𝑙𝑓 length of fluidising bed, of reactor

𝑛 molar flow rate

𝑞 flow rate of heat

𝑈 overall heat transfer coefficient

Sohio Standard Oil of Ohio

∆𝑇 temperature difference

𝑁𝑇 number of tubes

𝑥𝑖 , 𝑥𝑓 , 𝑥𝑑 , 𝑥𝑤 mole fraction of ith component, in feed, in distillate, in residue

𝑅, 𝑅𝑑 Reflux ratio, minimum reflux ratio

𝐿 Overflow

𝑇 Temperature

𝑃 Pressure
49
𝜌, 𝜌𝑖 , 𝜌𝑙 , 𝜌𝑣 Density, of ith component, of liquid, of vapor

𝑉 Vapor flow rate

𝑇𝑂𝑅 Turnover Ratio

50
Appendixes

51
10.0 Appendix I Block Diagram

53
Appendix II Process Flow Diagram

54
Appendix III Mass Balance
 Appendix IV Energy Balance *

Stream Inlet Outlet Inlet Outlet Inlet Outlet Inlet Outlet Inlet Outlet

Stream # 1 2 3 4 7 8 9 8 10 11 11 12 13 9 14 15

Temperature(oC) 400 400 400 130 90 70 120 90 80 110 100 80 110 100 90 110

-
Enthalpy (kJ/s) 1.6302 1.1734 9.2919 66.856
32.843
15.8066 -162.28 19.615 0.5005 19.0145 6.3595 15.6651 1.1044 -860.79 0.0037 -222.78

Total 12.0955 66.856

-
-146.4733 19.615 19.515 6.3595 16.7695 -860.79 -222.77962
Enthalpy(KJ/s) 32.843

Enthalpy of
-7159.6 -113.6268 -0.1 10.41005 638.0133
Formation (kJ/s)

Enthalpy of -7104.83962
Reaction (kJ/s)

Cooling water
required 30.8745
(kmol/s)

* With reference to the process flow diagram as shown in Appendix III

56
Appendix V

VLE Data for Acrylonitrile – Water System:

x Y
0.05 0.1
0.1 0.18
0.15 0.26
0.2 0.33
0.25 0.4
0.3 0.46
0.35 0.52
0.4 0.57
0.45 0.62
0.5 0.67
0.55 0.71
0.6 0.75
0.65 0.79
0.7 0.82
0.75 0.86
0.8 0.89
0.85 0.92
0.9 0.95 𝑥𝑓 = 0.02342
0.95 0.97 𝑥𝑑 = 0.67092
1 1 𝑥𝑤 = 0.0001213
Appendix VI

Plant Layout
Appendix VII Fluidized Bed Reactor
Appendix VIII Distillation Column

60
11.0 Bibliography

Process Description
• Kirk-Othmer Encyclopedia of Chemical Technology
• Perry R.H., Green D., “Perry’s Chemical Engineers’ Handbook”, McGraw-Hill.
• Ullmann’s Encyclopedia of Industrial Chemistry, VCH.
• C. Dimian Alexandre, Bildea Costin Sorin,“Chemical Process Design- Computer-
Aided Case Studies”, WILEY-VCH

Process Design
• Ulrich Gael, Vasudevan Palligarnai, “Chemical Engineering Process Design and
Economics – A Practical Guide”, Second Edition
• Biegler L.T., Grossmann I.E., and Westerberg A.W., “Systematic Methods of
Chemical Process Design.”, Prentice Hall.
• Douglas, J.M., “Conceptual Design of Chemical Processes”, McGraw Hill.
• Seider, W.D., J.D. Seader, and D.R. Lewin, “Process Design Principles.” Wiley.
• Smith, R., “Chemical Process Design.” McGraw Hill.

Process Economics
• Coulson & Richardson, “Chemical Engineering Design – by R.K. Sinnott”,
Pergamon Press.
• Peters M.S., Timmerhaus K.D., “Plant Design and Economics for Chemical
Engineers”, McGraw-Hill.

61