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 MOHIT SHARMA DIVYANSHU PATEL SHASHWAT MITRA

10708004 10708035 10708017 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:

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

TABLE OF CONTENTS
Chapters 1.0 1.1 Contents Introduction Properties of Acrylonitrile 1.1.1 Physical Properties 1.1.2 Chemical Properties 1.1.3 Uses of Acrylonitrile Manufacture Methods of Production 2.1.1 Sohio Process Production from Ethylene 2.1.2 Cyanohydrin 2.1.3 Production from Acetylene and Hydrocyanic Acid 2.1.4 Future Processes 3.0 3.1 3.2 4.0 4.1 Process Description Material Balance Energy Balance Equipment Design Fluidized bed reactor 4.1.1 Height of the reactor 4.1.2 Diameter of the reactor Distillation column design 4.2.1 Number of Theoretical Plates 4.2.2 Height and Diameter of the column Cost Estimation Direct cost Indirect cost Estimation of total product cost Determination of pay-back period Plant Layout Plant location and site selection Plant layout Storage and Transportation Page. No. 7 9 9 10

2.0 2.1

13 13 13 14 16 20 23 28 28 28 29

4.2

30 32

5.0 5.1.1 5.1.2 5.1.3 5.1.4 6.0 6.1.0 6.1.1 7.0

34 34 35 37 39 39 43 45

Chapters 8.0 8.1.0 9.0 10.0 Appendix I Appendix II Appendix III Appendix IV Appendix V Appendix VI Appendix VII Appendix VIII 11.0

Contents Health Aspects Toxicology and Health Hazards Nomenclature Appendixes Process Block Diagram Process Flow Diagram Material Balance Diagram Energy Balance Equilibrium Curve Plant Layout Fluidized Bed Reactor Distillation Column Bibliography

Page. No. 47 47 49

52 53 54 55 56 57 58 59 60

INTRODUCTION

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 Sohiodeveloped 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.

PROPERTIES

1.1.1 Physical Properties Acrylonitrile (C3H3N, mol wt = 53.064) is an unsaturated molecule having a carboncarbon 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 dualphase 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 Boiling point, C At 101.3 kPa Critical pressure, kPa Critical temperature, C Density, g/L At 20 C At 25 C At 41 C Dielectric constant at 33.5 MHz Entropy, vapor at 25 C, 101.3 kPa, J/(molK) Explosive mixture with air at 25 C, vol% Lower limit Upper limit Flash point (tag open cup), C Freezing point, C Gibbs energy of formation, vapor at 25 C, kJ/mol Heat capacity, specic, liquid, kJ/(kgK) Heat capacity, specic, vapor, kJ/(kgK) At 50 C, 101.3 kPa Heat of combustion, liquid at 25 C, kJ/mol Heat of fusion, kJ/mol Heat of polymerization, kJ/mol Heat of polymerization at 74.5 C, kJ/mol Heat of vaporization at 101.3 kPa, kJ/mol Ignition temperature, C Molar refraction, D line Vapor density, relative Viscosity at 25 C, mPas(=cP)

53.06

77.3 3.535 103 246.0

806.0 800.4 783.9 38 273.9

3.05 17.0 0.5 5 83.55 0.05 195.4 2.094

1.204 1.7615 103 6.635 103 72.4 2.1 76.5 f 32.65 481.0 15.67 1.83 (air = 1.0) 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-CN + 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-CN CH2=CH-CN + 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-CC-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 and 400 510 (750 950). 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 (Oxygen) 2C3H3N (Acrylonitrile) + 6H2O (Water)

(Propylene) (Ammonia)

16

Side Reactions: 4C3H6 + 6NH3 + 3O2 6C2H3N (Acetonitrile) C3H6 + 3NH3 + 3O2 3HCN (Hydrogen Cyanide) 2C3H6 + 3O2 6CO2 (Carbon dioxide) + 6H2O + 6H2O + 6H2O

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 : 100000 / : 24 : 300 : 13889 / = 3.858 / = 0.07278 / Molar feed ratio = 3 = 1 1.2 9.5

Process Unit Fluidised Bed Reactor Absorber column Extractive distillation column Acetonitrile stripping column Lights fractionation column Product column

Acrylonitrile Recovery 85% 100% 99.5% 99% 99.9% 85%

Fluidised Bed Reactor

Acrylonitrile (C3H3N) Propylene Ammonia Air 1 2 3 FLUIDIZED BED REACTOR Conversion = 99 % 4 Acetonitrile (C2H3N) HCN H20 O2 CO2

20

In the reactor the following reactions take place: Main Reaction: 2C3H6 + 2NH3 +. (Propylene) (Ammonia) 3O2 (Oxygen) 2C3H3N + (Acrylonitrile) 6H2O (Water) Conversion 0.85

Side Reactions: 4C3H6 + 6NH3 + 3O2 6C2H3N (Acetonitrile) + 6H2O 0.02

C3H6

3NH3

3O2

3HCN + (Hydrogen Cyanide) 6CO2 + (Carbon dioxide)

6H2O

0.02 0.100

2C3H6

3O2

6H2O

STREAM STREAM No. Temperature(oC) C3H6 O2 N2 NH3 CO2 HCN AN CAN H2 0 TOTAL 1 400 0.086944 ------------------------0.086944

INPUT (kmol/s) 2 400 ---------0.104333 ---------------0.104333 3 400 ---0.173450 0.652518 ------------------0.825968

OUTPUT (kmol/s) 4 130 0.000869 0.043312 0.652080 0.022600 0.026080 0.005216 0.073900 0.002608 0.260800 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 Ammonia Air 1 2 3 FLUIDIZED BED REACTOR Conversion = 99 % 4 Acetonitrile (C2H3N) HCN H20 O2 CO2

In the reactor the following reactions take place Main Reaction: 2 C3H6 + 2 NH3 +. 3 O2 (Propylene) (Ammonia) (Oxygen) Side Reactions: 4C3H6 + 6NH3 + 3O2 6C2H3N (Acetonitrile) + 6H2O (1) (2) (3) 2C3H3N + (Acrylonitrile) 6H2O (Water)

C3H6

3NH3

3O2

3HCN + (Hydrogen Cyanide) 6CO2 (Carbon dioxide) +

6H2O

2C3H6

3O2

6H2O

23

Table 2 Heat capacity and Enthalpy data

H
0 f 298

COMPONENT Propylene Ammonia Oxygen Nitrogen Acrylonitrile Acetonitrile HCN CO2 H2O(g) H2O(l)

kJ mol

kJ Cp mol
0.05 0.03 0.03 0.03 1.204 0.06 0.035 0.039 2.013 4.184

+20.41 -46.19
-------

+184.93 +74.56 +130.5 -393.50 241.83 285.83

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

Fluidised Bed Reactor

Enthalpy of formation of reaction: For main reaction

=
= (2 184.93 + 6 285.83 2 46.19 2 20.41) = 1293.36 / For reaction 1

=
= 6 74.56 + 6 285.83 4 20.41 6 (46.19) = 1072.12 /

24

 For side reaction 2

=
= 6 241.83 + 3 x 130.5 3 (46.19) 20.41 = 941.32 / For side reaction 3

=
= 6 (241.83) + 6 (393.5) 2 x 20.41 = 3852.8 / Total enthalpy of formation = (. . . . ) = . / Enthalpy of reactants: Reactants are added at 400oC. = [ nCp
Propylene

+ (nCp )Ammonia + (nCp )Oxygen + (nCp )Nitrogen ] T

=[ 0.086944 0.05 + 0.1043 0.03 + 0.17345 0.03 + 0.6525 0.03] (400 25) = 0.032255 375 = . / Enthalpy of products: Products leave at 130 o C. = nCp
C 3 6

+ nCp

NH 3

+ nCp

O2

+ nCp

N 2 unreacted

nCp

AN

nCpACN +nCpHCN +nCpCO2+nCp T = {[8.694410 4 0.05 + 0.0430375 0.03 + 0.6525 0.03 + 0.0226 0.03] + [0.0739 1.204 + 0.00026 0.06 + 0.0005216 0.035 + 0.02608 0.039 + 0.2608 2.013]} (130 25) = . /
25

Enthalpy of reaction: = + = (7159.6) + 12.0957 + 66.8560 = . / The negative sign in the above calculation ( indicates that the reaction is

exothermic. Hence cooling water is used for the removal of the heat Assuming water enters at 25 C and leaves at 80 C = 7104.83962 = 4.184 25 = 30.8745 / 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:
= 0.5 = 0.55 = 0.70 = 400 = 1 Feed gas enters at bed temperature at composition 3 6 : 3 : = 1: 1.2: 9.5 Heat exchanger: Vertical tubes 0.08m OD, = 300 2 = 1800 2 = 60 = 0.5 /

= 8

4.1.1 Length of the reactor = 0.5 8 = 8 0.5 = (1 ) 8 0.5 = = . (1 ) 1 0.7 (1 )

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

28

4.1.2 Diameter of the reactor Cross sectional area of reactor Volumetric flow rate of propylene = 3.65165
22.4 3 42 673 273 1 1 1+1.2+9.5 1

= 56.1728 3 CSA of the reactor needed =

56.1728 0.50

= 112.3456 3 = 2 4
112 .3456 4 .

Thus, diameter of the column, = Heat Exchanger Calculations = 7104.83962 / Overall heat transfer coefficient is = 1 + 1
1

= .

1 1 + 300 1800

= 257.1 2

Hence the exchanger surface area needed to remove this heat is = 7104.83962 103 = = 110.5381 2 257.1 400 150

The number of 2 long tubes required is = 110.5381 = = . 0.08 8

29

4.2 Distillation Column 4.2.1 Number of Theoretical Plates (by McCabeThiele method) , = 3.1556 /

, = 0.1096 / , = 3.0460 / Mol fraction of acrylonitrile in feed, =

0.0739 3.1556

= 0.02342
Similarly,

= 0.67092 = 0.0001213

Parameter of thermal state of feed: = 1 (Saturated liquid at its bubble point)

Reflux ratio = = 2

Overall plate efficiency = 1 From equilibrium curve, at minimum reflux ratio (Rd), we get = 0.01875 =
(Intercept)

0.67 1 0.03

= 21.33 Let reflux ratio, = 1.5 = 42.66

30

Thus,

= (+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, =
0.000869 0.022605 x 0.04309 + x 0.04294 + 3.1556 3.1556

0.026083
3.1556

x 0.0425 +

0.005216 x 0.02544 + 3.1556 0.002608 x 19.1951 + 3.1556

0.073900 x 15.2075 + 3.1556 3.024360 x 55.556 3.1556

= 53.6208 /3 Similarly, Density of liquid, = 166.3966 /3 Density of vapor, = 2.7987 /3 We chose the plate spacing, to be 0.5 m Thus vapour velocity, , can be calculated:

= (-0.171l + 0.271 l 0.047)

Thus, = 0.34598 m/s

0.5

The column diameter, , can be then calculated:

4

Where, = vapour rate, /

Thus, = 0.37968
31

Height of the column = ( + 2) = 32 0.5 = 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 Cost of 1000 kg of acrylonitrile Production of acrylonitrile Gross sale for 1 year or total income , Turn Over Ratio It is defined as the ratio of total income to the fixed capital investment Total Income Fixed Capital Investment = = = = = 300.00 85,000.00 100,000.00 8,50,00,00,000.00 8,50,00,00,000.00

` ton ` `

i.e., TOR

For process industries turnover ratio is 1, thus, Fixed Capital Investment (FCI) = Gross annual sales But, Fixed Capital Investment = Direct cost + Indirect Cost 5.1.1 Direct Cost Direct cost is taken as 70% of fixed capital investment

8,50,00,00,000.00

= =

5,95,00,00,000.00 88, 06,24025.00

` `

The cost involved are , i. Equipment cost ii. Installation and piping cost iii. Instrumentation cost iv. Electrical cost v. Piping cost vi. Building, process and auxiliary cost vii. Service facilities and yard improvement cost vii. Land cost Total 5.1.2 Indirect cost Indirect cost = Fixed Capital Investment - Direct Cost

35% 6% 9% 10% 9% 7% 4% 20% 100%

2,08,25,00,000.00 35,70,00,000.00 53,55,00,000.00 59,50,00,000.00 53,55,00,000.00 41,65,00,000.00 23,80,00,000.00 1,19,00,00,000.00 5,95,00,00,000.00

= i.e.,

2,55,00,00,000.00 2,55,00,00,000.00

` `

Indirect cost consists of following items,

34

i. ii. iii. i.

Engineering and supervision cost Contingency Working capital Engineering and supervision cost. i.e, 6% of direct cost = i.e, 35,70,00,000.00 35,70,00,000.00 11,90,00,000.00 11,90,00,000.00 1,30,90,00,000.00 1,30,90,000.00 1,78,50,00,000.00 1,78,50,00,000.00 9,80,90,00,000.00 9,80,90,00,000.00 `

ii.

Contingency is 2% of direct cost

= i.e, = Total = i.e.,

iii.

Working capital is 22% of direct cost

` ` ` ` `

Therefore, total working capital = fixed capital + working capital = i.e., 5.1.3 Estimation of total product cost Total Annual income Gross earning is 10% of annual income = = i.e., = i.e.,

8,50,00,00,000.00 85,00,00,000.00 85,00,00,000.00 7,65,00,00,000.00 7,65,00,00,000.00

` ` ` ` `

Product cost = Total annula income - Gross earnings

Direct production Cost It can be taken as 60% of total product cost Raw materials cost It is 5% of toal product cost Operating labour cost It can be taken as 15% of total product cost = 38,25,00,000.00 ` = 4,59,00,00,000.00 `

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 Maintenance and repair cost It is 3.6% of fixed capital investment cost

76,50,00,000.00

= =

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 Fixed Charges It can be taken as 10% of product cost 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 Depreciation Depreciation for machinery is 10% of fixed capital cost = = = = = = 8,50,00,00,000.00 85,00,00,000.00 1,19,00,00,000.00 3,57,00,000.00 88,57,00,000.00 88,57,00,000.00 ` ` ` ` ` ` = 38,25,00,000.00 ` = 76,50,00,000.00 ` = = 8,50,00,00,000.00 12,75,00,000.00 ` `

Depreciation of building is 3% of the land cost Total depreciation value is 13% Depreciable capital investment is

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 General expenses

15,30,00,000.00

Administrative cost includes cost of officers, legal fees, office supplier and communications. It is 4% of the total product cost Distribution and selling cost It accounts for 6% of total product cost Research and development cost It is 1% of total product cost Financing It is 2% of the total product cost 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 ` ` = 15,30,00,000.00 ` = 7,65,00,000.00 ` = 45,90,00,000.00 ` = 30,60,00,000.00 `

5.1.4 Determination of Pay-Back Period Pay-back period Pay-back period = = Depreciable fixed capital investment (Average profit + Average depreciation) 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.
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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.

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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.

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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

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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.

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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.

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7. Modular construction In recent years, there has been a move to assemble sections of plant at the plant manufacturers 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.

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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.
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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.

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9.0 Nomenclature
Symbol/Acronym ACN AN , , , , , , , , Sohio , , , , Key Exchanger Surface Area Acrylonitrile Acetonitrile Specific Heat Diameter of the Column Distillate Diameter of the Catalyst Particle Plate Efficiency void fraction in a fixed bed, at minimum fluidisation, in the fluidised bed as a whole Fixed Capital Investment heat transfer coefficient ouside, inside Standard Heat of formation, of products, of reactants gas velocity space time length of fluidising bed, of reactor molar flow rate flow rate of heat overall heat transfer coefficient Standard Oil of Ohio temperature difference number of tubes mole fraction of ith component, in feed, in distillate, in residue Reflux ratio, minimum reflux ratio Overflow Temperature Pressure 49

, , ,

Density, of ith component, of liquid, of vapor Vapor flow rate 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 Stream # Temperature(oC) 1 400

Inlet 2 400 3 400

Outlet 4 130

Inlet 7 90 8 70

Outlet 9 120

Inlet 8 90 10 80

Outlet 11 110

Inlet 11 100 12 80

Outlet 13 110

Inlet 9 100 14 90

Outlet 15 110

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 Enthalpy(KJ/s) Enthalpy of Formation (kJ/s) Enthalpy of Reaction (kJ/s) Cooling water required (kmol/s)

12.0955

66.856

32.843

-146.4733

19.615

19.515

6.3595

16.7695

-860.79

-222.77962

-7159.6

-113.6268

-0.1

10.41005

638.0133

-7104.83962

30.8745

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

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Appendix V VLE Data for Acrylonitrile Water System:

x Y 0.1

0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1

0.18 0.26 0.33 0.4 0.46 0.52 0.57 0.62 0.67 0.71 0.75 0.79 0.82 0.86 0.89 0.92 0.95 0.97 1

= = =

0.02342 0.67092 0.0001213

Appendix VI Plant Layout

Appendix VII Fluidized Bed Reactor

Appendix VIII Distillation Column

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11.0 Bibliography
Process Description Kirk-Othmer Encyclopedia of Chemical Technology Perry R.H., Green D., Perrys Chemical Engineers Handbook, McGraw -Hill. Ullmanns Encyclopedia of Industrial Chemistry, VCH. C. Dimian Alexandre, Bildea Costin Sorin, Chemical Process Design- ComputerAided 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.

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