MANUFACTURE OF BUTADIENE

USING n-BUTANE

A PROJECT REPORT

Submitted by
ARVIND C.A. (41501203002)
PRAKASH RAO K.R. (41501203015)
SURYANARAYANAN K.S. (41501203018)


in partial fulfillment for the award of the degree
of
BACHELOR OF TECHNOLOGY
in
CHEMICAL ENGINEERING


S.R.M. ENGINEERING COLLEGE,
KATTANKULATHUR-603 203, KANCHEEPURAM DISTRICT.

ANNA UNIVERSITY : CHENNAI - 600 025

MAY 2005



BONAFIDE CERTIFICATE



Certified that this project report " MANUFACTURE OF BUTADIENE USING n-
BUTANE " is the bonafide work of " ARVIND C.A. (41501203002), PRAKASH
RAO K.R. (41501203015) and SURYANARAYANAN K.S. (41501203018)" who
carried out the project work under my supervision.




Dr. R. KARTHIKEYAN Dr. R. KARTHIKEYAN
HEAD OF THE DEPARTMENT SUPERVISOR
Professor
CHEMICAL ENGINEERING CHEMICAL ENGINEERING
S.R.M.Engineering College S.R.M.Engineering College
Kattankulathur - 603 203 Kattankulathur - 603 203
Kancheepuram District Kancheepuram District

iii

ACKNOWLEDGEMENT

We are extremely thankful to Prof. R. Venkataramani, Principal, S.R.M
Engineering College, for permitting to carry out this project and providing us with all
the facilities.

We take pride in expressing our deepest gratitude to our project guide,
Dr.R.Karthikeyan, Professor and Head, Department of Chemical Engineering, for
his invaluable guidance and encouragement at every stage of this project.

We extend our thanks to all the staff members of the Chemical Engineering
Department for their technical assistance and support.
iv

ABSTRACT
Butadiene is one of the most important industrial chemicals with applications ranging
from polymers and elastomers like SBR, NR, PBR, SBL, ABS, and CR to chemicals
like adiponitrile used in the manufacture of Nylon-66.

For a high yield requirement of butadiene, the Houdry Catadiene process of
dehydrogenation of n-butane has proven most economic. This project deals with the
material balance, energy balance, design, control, economics and safety aspects of the
process.
v
TABLE OF CONTENTS

CHAPTER TITLE PAGE NO
ABSTRACT iv
LIST OF TABLES vii
LIST OF FIGURES viii
LIST OF SYMBOLS, ABBREVIATIONS ix
1 INTRODUCTION 1
1.1 HISTORY 1
1.2 APPLICATIONS 1
1.3 PROPERTIES 3
1.3.1 PHYSICAL PROPERTIES 3
1.3.2 CHEMICAL PROPERTIES 4
1.4 LITERATURE REVIEW 6
1.4.1 METHODS OF PRODUCTION
OF BUTADIENE 6
1.4.2 SELECTION OF PROCESS 7
2 PROCESS 8
2.1 PROCESS DESCRIPTION 8
2.2 MATERIAL BALANCE 10
2.3 ENERGY BALANCE 17
2.4 DESIGN 24
2.5 PROCESS CONTROL AND INSTRUMENTATION 36
vi
2.6. PLANT LAYOUT 38
2.7 COST ESTIMATION 46
2.8 PROCESS SAFETY 55
2.9 MATERIALS OF CONSTRUCTION 62
2.10 STABILIZATION, STORAGE AND TRANSPORTATION
2.11 HEALTH, SAFETY AND TOXICOLOGY 64
CONCLUSION 66
REFERENCES 67
vii

LIST OF TABLES

Table.1. Uses of Butadiene 2
Table.2 Physical properties of butadiene 4
Table.3 Materials entering the absorber 12
Table.4 Required data for preheater 17
Table.5 Required data for reactor 18
Table.6. Required data for quench tower 19
Table.7 Required data for cooler 20
Table.8 Required data for reboiler 22
Table.9 Physical properties data for preheater 24
Table.10 Delivered cost of major equipment 47
Table.11 Direct cost factor 47
Table.12 Indirect cost factor 48
Table.13 Auxillary services cost factor 49
Table.14 Exposure limits 65
viii

LIST OF FIGURES

Fig.1 MANUFACTURE OF BUTADIENE 9
Fig.2 BUTADIENE - HEAVY ENDS SYSTEM 32
Fig.3 PLANT LAYOUT 38
ix
LIST OF SYMBOLS, ABBREVIATIONS

A
O
= surface area, m
2

B = Molar flow rate of residue, kmol/s
C
P
= specific heat, J / kg.K
D = Molar flow rate of distillate, kmol/s
d
e
= equivalent diameter, m
d
i
= inner diameter, m
d
o
= outer diameter, m
F = Molar flow rate of feed, kmol/s
G
MS
= Molar flow rate of inerts to the absorber, kmol/m
2
s
H.T.U. = Height of transfer unit, m
h
i
= tube side heat transfer coefficient, J / sm
2 0
C
h
o
= Shell side heat transfer coefficient, J / sm
2 0
C
K = thermal conductivity, J / sm
0
c
L = Tube length, m
L
MS
= Molar flow rate of solvent to the absorber, kmol/m
2
s
m = mass, kg
n = number of stages
N.T.U = Number of transfer units
Nu = Nusselt number
P = Pressure, atm
Pr = Prandtl number
P
T
= pitch, m
R = Universal gas constant, atm.m
3
/kmol.K
R
D
= Reflux ratio
Re = Reynolds number
TPD = tons per day
U
O
= overall heat transfer coefficient, J / sm
2 0
C
V = vapor flow rate in rectifying section kmol/s
v = Velocity, m/s
= vapor flow rate in stripping section kmol/s
X = Mole ratio in liquid phase
x =Mole fraction in liquid phase
x
y = Mole fraction in vapor phase
Y = Mole ratio in vapor phase
Z
T
= Total height of absorption column, m


GREEK SYMBOLS
= relative volatility
H
0
R
= Standard heat of reaction, kcal/kg
T = temperature difference,
0
C

T
L
= log mean temperature difference,
0
C
= Latent heat, kJ/kg
= viscosity, kg / m.s
= density, kg / m
3




1
1. INTRODUCTION
1.1. HISTORY
E.CAVENTOU was the first to isolate butadiene by means of pyrolysis of amyl
alcohol. M.BERTHELOT produced it by passing a mixture of acetylene and ethylene
through a red-hot iron tube. In 1885, G. CIAMICIAN and P.MAGNAGHI elucidated
the structure of butadiene. H.E.ARMSTRONG and A.K.MILLER, in 1886,discovered
butadiene in the products obtained on cracking petroleum.
Ever since S.LEBEDEW in 1910 discovered that butadiene forms rubber like
polymers, practical interest in this compound and its derivatives developed. Butadiene
was produced on a large scale in Germany prior to World War II and in the USA
during the war. Simultaneously, methods were developed for manufacture of useful
butadiene polymers. After the war, the work of K.ZIEGLER and G.NATTA, among
others, on polymerization with organometallic catalytic agents led to better quality of
rubber.
1.2. APPLICATIONS
Butadiene, the principal diolefin and four-carbon industrial chemical, is primarily
used as a monomer or a co-monomer in production of synthetic rubber. It is the main
component of the general-purpose rubber designated SBR (70% butadiene and
remainder styrene). The stereospecific polybutadiene rubber (PBR) and thermoplastic
rubbers containing polybutadiene and polystyrene blocks are growing in importance.
The third rubber involving butadiene as monomer, is Nitrile rubber (NBR), in which
butadiene and 20 60 % acrylonitrile are copolymerised. The fourth type is
chloroprene rubber (CR) where the monomer is 2- chlorobutadiene. A number of
latex materials are also produced from butadiene in conjunction with other monomers.
Nitrile latices, produced from acrylonitrile and butadiene are important. Another
important area of use for butadiene is in the field of plastics. The main product is the
copolymer of acrylonitrile, butadiene and styrene known as ABS resin, where 10-15%
butadiene is incorporated. It is also used in the raw material for production of
adiponitrile and hexamethylenediamine as intermediates for production of Nylon-66.
They are also included in the production of cyclododecatriene as a step toward
making Nylon-12 and in manufacture of hexabromocylododecane. A new elastomer
2
system based on carboxy-terminated butadiene acrylonitrile polymers (CBTN) is
being developed as an alternative to urethane technology e.g., car bumpers.
Table 1. Uses of Butadiene
END USE PERCENTAGE OF TOTAL
SYNTHETIC ELASTOMERS
Styrene-butadiene rubber(SBR)
Polybutadiene(BR)
Polychloroprene(neoprene)
Nitrile rubber
63.3
32.0
23.0
5.6
2.7
POLYMERS AND RESINS
Acrylonitrile-butadiene-styrene(ABS)
Styrene-butadiene copolymer(latex)
15.7
4.7
11.0
CHEMICALS AND OTHER USES
Adiponitrile
Others
21.0
13.0
8.0

3
1.3. PROPERTIES
1.3.1. PHYSICAL PROPERTIES
1,3-Butadiene is a non-corrosive, colorless, flammable gas at room temperature and
atmospheric pressure. It has a mildly aromatic odor. It is sparingly soluble in water,
slightly soluble in methanol and ethanol, and soluble in organic solvents like diethyl
ether, benzene, and carbon tetrachloride. 1,2-butadiene is much less studied. It is a
flammable gas at ambient conditions. The conjugation of the double bonds makes it
15 kJ/mole, more thermodynamically stable than molecule with two isolated single
bonds. The s-trans isomer, often called the trans form, is more stable than the s-cis
form at room temperature. Although there is a 20kJ/mole rotational barrier, rapid
equilibrium allows reactions to take place with either the s-cis or s-trans form.
The double-bond length in 1,3-butadiene is .134 nm, and the single-bond, .148nm.
Since normal carbon-carbon single bonds are .154 nm, this indicates the extent of
double-bond character in the middle single-bond. Upon complexing with metal
carbonyl moieties like Fe(CO)
3
, the two terminal bonds lengthen to .141 nm, and the
middle bond shortens even more to .145 nm.
4
Table 2. Physical properties of butadiene
Property Value
Molecular formula C
4
H
6

Molecular weight 54.092
Boiling point at atm. pressure,
0
C -4.411
Freezing point,
0
C -108.902
Critical temperature,
0
C 152.0
Critical pressure,MPa 4.32
Critical volume, cm
3
/mole 221
Critical density,g/ml .245
Density (liquid),g/ml at
0
0
C
25
0
C

.6452
.6194
Density(gas) (air=1) 1.9
Heat capacity at 25
0
C,J/(mole.K) 79.538
Refractive Index, at -25
0
C 1.4292
Solubility in water at 25
0
C,ppm 735
Viscosity (liquid), mPa.s at 0
0
C .25
Heat of formation, gas, kJ/mole 110.165
Heat of formation, liquid, kJ/mole 88.7
Flash point,
0
C -85
Explosion limits in air, vol%
Lower
Upper

2.0
11.5

1.3.2. CHEMICAL PROPERTIES
Butadiene has two conjugated double bonds and, therefore, can take part in numerous
reactions, which includes 1,2- and 1,4- additions with itself (polymerization) and with
other reagents, linear dimerisation and trimerisation, and ring formation.
Polymerisation by means of 1,2- and 1,4- addition is the most important butadiene
reaction. On 1,2-addition, atactic polymers, in which the vinyl group has an arbitrary
steric position, can also be formed.
The manufacture of chloroprene (chlorinated hydrocarbons) requires the
chlorination of butadiene followed by isomerization and alkaline dehydrochlorination.
In the production of adipic acid according to a BASF procedure, butadiene reacts with
carbon monoxide and methanol in two steps under different reaction conditions. At a
higher temperature, approximately 185
0
C, and at a lower pressure pentene acid ester
5
reacts again with carbon monoxide and methanol to give adipic acid dimethyl ester.
Hydrolysis then leads to the formation of adipic acid.
Butadiene undergoes hydroformylation to give valeric aldehyde. In the production of
hexamethylenediamine, hydrogen cyanide reacts with butadiene in two steps and the
adiponitrile thus obtained is hydrogenated to give the diamine. Butadiene also reacts
in several ways to give 1,4-butanediol.
Linear dimerisation and trimerisation: Butadiene forms linear dimers or trimers in the
presence of Ni, Co, Pd, or Fe catalysts. Dimerisation of butadiene and simultaneous
reaction with carbon monoxide and alcohol leads to the synthesis of pelargonic acid,
which is a starting material in production of heat-resistant lubricants.
Cyclization, Diels-Alder Reaction: The Diels-Alder reaction is one of the best known
reactions of butadiene. Usually, a dienophile, i.e., an olefin with an activated double
bond, reacts with butadiene forming a cyclohexane ring. This addition reaction,
which is exclusively a 1,4-addition, can also take place with a second molecule of
butadiene as the dienophile component, forming 4-vinylcyclohexene-1.
Vinylcyclohexene, when subjected to dehydrogenation or oxidation, gives styrene.
In the synthesis of anthraquinone, butadiene undergoes a Diels-Alder reaction with
naphthaquinone to give tetrahydroanthraquinone, which in turn is oxidized to
anthraquinone.
Butadiene readily undergoes a 1,4-addition with sulfur dioxide forming a cyclic
sulfone, 2.5-dihydrothiophene-1,1-dioxide. This compound is converted into
sulfolan, a heat-stable and highly polar solvent, on catalytic hydrogenation.
Formation of Complexes: Butadiene reacts with numerous metal compounds to form
complexes, e.g., with Cu(I)salts, which are used in the extraction of butadiene from
C
4
-hydrocarbon mixtures. Complexes with iron, nickel, cobalt, palladium, and
platinum are also well known.
1.4. LITERATURE REVIEW
1.4.1. METHODS OF PRODUCTION OF BUTADIENE
6
Production from Acetylene: The large-scale industrial production of butadiene from
acetylene has been carried out in Germany using two processes. These methods are
no longer used as the production of acetylene requires a large amount of energy and is
very expensive.
Production from ethanol:
2CH
3
CH
2
OH CH
2
=CH-CH=CH
2
+ H
2
+ 2H
2
O
It is the method of choice in countries, which manufacture cheap ethanol from
carbohydrates or in the EEC with its enormous, subsidized agricultural surpluses.
Dehydrogenation of n-Butane: The best known one-step dehydrogenation is the
Houdry Catadiene process, which has been in operation on a commercial scale since
1943. If a high yield of Butadiene is required, this process has proven most economic.
Oxidative Dehydrogenation of n-Butenes: The conversion and the selectivity of the
dehydrogenation of n-butenes to butadiene can be significantly improved by removing
the hydrogen from the equilibrium. The addition of oxygen causes the oxidation of
hydrogen to water.
C
4
H
8
+ 1/2O
2
C
4
H
6
+ H
2
O
The addition of oxygen to the dehydrogenation reaction of butane is not meaningful
because at the high temperatures required,oxygen reacts with the reaction products,
giving rise to undesired byproducts.
Oxidative Dehydrogenation of Butane with Halogen: Shell has developed a one-step
dehydrogenation of butane to butadiene using iodine as the hydrogen acceptor. The
addition of iodine enables a high conversion and yield of butadiene, but has the
disadvantage of causing serious corrosion problems in the plant.
Steam Cracking: Steam cracking is a complex, highly endothermic pyrolysis reaction.
The main cracking feed stock is ethane, which yields only a little C
4
hydrocarbons
and is thus not suitable as a route to butadiene.
1.4.2 SELECTION OF PROCESS
7
If a high yield of Butadiene is required, the Houdry Catadiene process has proven
most economic.
2. PROCESS
2.1. PROCESS DESCRIPTION:
DEHYDROGENATION OF BUTANE:
CHEMICAL REACTIONS:
(a) Main reaction:
C
4
H
10
CH
2
=CH.CH=CH
2
+ 2H
2
; H = +32.2 Kcal
(b) Side reaction:
C
4
H
10
C
4
H
8
+ H
2

n-butylenes
A refinery gas of C4/C5 cut containing predominantly n-butane with some isopentane
is mixed with recycle gas and preheated to reaction temperature prior to contact with a
catalyst in a fixed bed, regenerative-heating system. A pair of reactors forms an
adiabatic cycle with the heat of reaction required during the 5-15 minutes make
period equal to that supplied by the combustion of carbon deposit on the catalyst
during the regenerative period. The temperature of reaction at the start of the make
period is 650
0
C, dropping to 550
0
C at the end before switching to regeneration. The
pressure is low, 120-150 mm absolute, to force the reaction to the right.
The product gases are oil-quenched, compressed, cooled and separated from the light
ends by absorption in naphtha following by stripping. The overhead is fractionated to
yield crude butadiene at the top, which is purified by (1) absorption using cuprous
ammonium acetate (CAA), (2) extractive distillation with furfural, (3) azeotropic
distillation with ammonia.
8

The more common absorption process involves contact of the close-boiling butadiene-
butene fraction with lean CAA solution, which dissolves butadiene. A desorption step
at higher temperature is followed by distillation, compression, and liquefaction of
butadiene to give 98-99% product purity. Mono-olefins may be required. Ammonia
is recovered in the distillation tower by water addition; it is then separated as
substantially anhydrous NH
3
by fractionation.
2.2. MATERIAL BALANCE
REACTOR:
BASIS: 62.1571 kg (from fresh feed) 1.0717 kmol 1-min operation
Following reactions are taking place in the reactor:
C
4
H
10
CH
2
=CH-CH=CH
2
+ 2H
2
----------- I
n-butane butadiene
C
4
H
10
C
4
H
8
+ H
2
------------- II
n-butane n-butylenes
9
Yield is taken as 60 %
n-butane reacted in reaction I = 0.643 kmol
n-butane reacted in other reactions = 0.4287 kmol
n-butane reacted in reaction II is taken as 0.2143 kmol
n-butane reacted for the production of light ends
is taken as 0.1072 kmol = 0.1072 x 58 = 6.2157 kg
n-butane reacted for the production of heavy ends
is taken as 0.1072 kmol = 0.1072 x 58 = 6.2157 kg
Butadiene produced in reaction I = 0.643 kmol
= 0.643 x 54
= 34.7222 kg
Butene produced in reaction II = 0.2143 kmol
= 0.2143 x 56
= 12.0027 kg
H
2
produced in reactions I and II = 0.643 x 4 + 0.2143 x 2
= 3.0007 kg
Conversion of butane is taken as 12 %
Butane entering into the reactor = (1/0.12)(0.643)
= 5.3584 kmol
= 5.3584 x 58 kg = 310.79 kg
Butane from recycle = 5.3584 1.0717 = 4.2867 kmol
= 248.63 kg


REACTOR
C
4
H
10
: 310.79 C
4
H
10
: 248.63
INPUT OUTPUT
kg kg
10
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
H
2
: 3.0007
Light ends : 6.2157
Heavy ends : 6.2157
TOTAL: 310.79 kg TOTAL : 310.79kg
ABSORBER:
Table.3. Materials entering the absorber
Component Weight , kg Mol. Wt., kg/kmol No. of kmoles
C
4
H
10
248.63 58 4.2867
C
4
H
6
34.7222 54 0.643
C
4
H
8
12.0027 56 0.2143
H
2
3.0007 2 1.5003
Light ends 6.2157 45 (assumption) 0.1393
Heavy ends 6.2157 60 (assumption) 0.1072
Total 310.79 6.8909
Moles of inert (H
2
and Light ends) entering absorber through gas mixture (G
ms
) =
1.6396 kmol
Mole ratio of solute to inert in the entering gas mixture = Y
b
= 5.2513/1.6396
= 3.2026
Let 99.99 % of solute be removed in the absorber
Mole ratio of solute to inert in the leaving gas mixture = Y
a
= 3.2026x10
-3
Mole ratio of solute to solvent (naphtha) entering the reactor = X
a
= 0
(as pure naphtha is used)
Let L
ms
be pure solvent used & X
b
be mole ratio of solute to solvent leaving the rector
Material balance for solute in the absorber:
L
ms
(X
b
X
a
) = G
ms
(Y
b
Y
a
)
For minimum solvent rate, (L
ms
)
min
, X
b
= X
b
*
11
Let equilibrium relationship be given as Y = 0.5 X
X
b
* = Y
b
/ 0.5 = 3.2026 / 0.5 = 6.4052
(L
ms
)
min
( 6.4052 0) = 1.6396 ( 3.2026 3.2026x10
-3
)
(L
ms
)
min
= 0.8190 kmol
Let actual solvent rate be 1.2 times the minimum solvent rate
L
ms
= 0.8190 x 1.2 = 0.9828 kmol = 0.9828 x 128

= 125.8 kg
H
2
unabsorbed = 3.0007 x .999 = 2.9976 kg
H
2
absorbed

= 3.0007 2.9976 = 0.003 kg
Light ends unabsorbed = 6.2157 x 0.999 = 6.2095 kg
Light ends absorbed = 6.2157 6.2095 = 0.006 kg




ABSORBER
C
4
H
10
: 248.63
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
H
2
: 3.0007
Light ends : 6.2157
Heavy ends : 6.2157


TOTAL : 436.59 kg
REACTOR
EFFLUENT
VENT GAS
SOLUTION
kg
kg
NAPHTHA : 125.8
C
4
H
10
: 248.63
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
H
2
: 0.003
Light ends : 0.006
Heavy ends : 6.2157
TOTAL : 436.59 kg
NAPHTHA : 125.8
H
2
: 2.9976
Light ends : 6.2095

12
STRIPPER:
Let all naphtha be removed in the stripper
H
2
and Light ends are not taken into account, as they are negligible


STRIPPER




BUTADIENE TOWER:
Let heavy ends be completely removed in the butadiene tower
Material balance in the butadiene tower:


BUTADIENE TOWER



kg
Naphtha : 125.8
C
4
H
10
: 248.63
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
Heavy ends: 6.2157


kg
GAS MIXTURE
C
4
H
10
: 248.63
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
Heavy ends: 6.2157
Naphtha : 125.8
TOTAL : 427.3706 kg
TOTAL : 427.3706 kg
GAS
MIXTURE
CRUDE
BUTADIENE
Heavy ends : 6.2157
C
4
H
10
: 248.63
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
Heavy ends : 6.2157
kg
TOTAL : 301.5706 kg
C
4
H
10
: 248.63
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
kg
TOTAL : 301.5706 kg
13
MIXER SETTLER:
Crude butadiene is sent to mixer settler where cuprous ammonium acetate (CAA)
separates n-butane.
Material balance in the mixer settler:
Let 1 kg of CAA be used per kg of crude butadiene

MIXER
SETTLER



STRIPPER:
Let all CAA be removed in the stripper
Material balance around stripper:





CRUDE
BUTADIENE
C
4
H
10
: 248.63
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
TOTAL : 590.7098 kg
CAA : 295.3549
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
TOTAL : 590.7098 kg
kg
C
4
H
10
: 248.63
CAA : 295.3549
kg

STRIPPER
CAA : 295.3549
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027

kg
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
kg
CAA : 295.3549
TOTAL : 342.0798 kg TOTAL : 342.0798 kg
14
AZEOTROPIC DISTILLATION TOWER:
In the azeotropic distillation tower, ammonia is used to remove C
4
H
8

Material balance in the azeotropic distillation tower:
Let 0.2 kg of NH
3
be used per kg of C
4
H
6
, C
4
H
8
mixture
NH
3
required = 46.7249 x 0.2 = 9.3449 kg

AZEOTROPIC
DISTILLATION TOWER


BUTADIENE PURIFIER:
In the butadiene purifier NH
3
is removed by H
2
O
Let 0.2 kg of H
2
O be used per kg of C
4
H
6
, NH
3
mixture
H
2
O used = 0.2 x 44.0671 = 8.8134 kg
NH
3
: 9.3449
kg
C
4
H
6
: 34.7222
C
4
H
8
: 12.0027
NH
3
: 9.3449
C
4
H
6
: 34.7222
kg
C
4
H
8
: 12.0027
TOTAL : 56.0698 kg TOTAL : 56.0698 kg
15
Material balance in the butadiene purifier:





BUTADIENE PRODUCED = 34.7222 kg

2.3. ENERGY BALANCE:
PREHEATER:
Table.4. Required data for preheater
Required data COLD FLUID
(C
4
H
10
)
HOT FLUID(FUEL
GAS)
Mass,m(kg) 310.79 ???
Specific heat,C
p
(J/kgK) 1.6164 x 10
3
1.1 x 10
3

Outlet temperature(
0
C) 650 200
Inlet temperature (
0
C) 25 900
Temperature difference,T
(
0
C)

625

700

( m x c
p
x

T )
cold fluid
= ( m x c
p
x T )
hot fluid

310.79 x 1.6164 x 10
3
x 625 = m x 1.1 x 10
3
x 700

m = 407.75 kg
Mass of fuel gas required = 407.75 kg




BUTADIENE
PURIFIER
H
2
O : 8.8134
NH
3
: 9.3449
C
4
H
6
: 34.7222
BUTADIENE : 34.7222
kg
H2O : 8.8134
NH
3
: 9.3449
TOTAL : 52.8805 kg TOTAL : 52.8805 kg
kg
16












REACTOR:
Table.5. Required data for reactor
Required data Reactants Products
Mass, m(kg) 310.79 310.79
Specific heat,C
p
(J/kgK) 1.6164 x 10
3
1.94 x 10
3


Inlet temperature of reactant = 650
0
C
Standard heat of reaction H
0
R
= 32.2 Kcal
Datum temp: 25
0
C
Temperature of products leaving the reactor =?
Heat of reaction (H)= (mC
p
T)
products
+ H
0
R
- (mC
p
T)
reactants

For adiabatic process: H=0
0 = (mC
p
T)
products
+ H
0
R
- (mC
p
T)
reactants
0 = 301.79 x 1.94 x 10
3
x (T-25) + 32.2 x 4.187 x 1000
310.79 x 1.6164 x 10
3
x (650-25)
FUEL GAS: 407.75 kg
Outlet temp: 200
0
c
C
4
H
10
(gas): 310.79 kg
Outlet temp: 650
0
C
FUEL GAS: 407.75 kg
Inlet temp: 900
0
C
C
4
H
10
(gas): 310.79 kg
Inlet temp: 25
0
C


PREHEATER
17
T 25 = 520.52
0
C
T = 545.5
0
C
Outlet temperature of products = 545.5
0
C


REACTOR



QUENCH TOWER:
Table.6. Required data for quench tower
Required data Cold fluid (oil) Hot fluid(Products from reactor)
Mass, m(kg) ??? 310.79
Specific heat,C
p
(J/kgK) 2.1 x 10
3
1.6164 x 10
3

Inlet temperature(
0
C) 25 545.5
Outlet temperature (
0
C) 300 55
Temperature difference, T
(
0
C)

275

490.5

( m c
p
T )
cold fluid
= ( m c
p
T )
hot fluid
m x 2.1 x 10
3
x 275 = 310.79 x 1.6164 x 10
3
x 490.5
m = 426.67 kg
Mass of oil required = 426.67 kg

C
4
H
10
: 310.79 kg C
4
H
10
: 248.63
C
4
H
6
: 34.72
C
4
H
8
:

12.00

H
2
: 3.00
Light ends: 6.22
Heavy ends: 6.22
Total: 310.79 kg
kg
Outlet temp:
545.5
0
C
Inlet temp: 650
0
C
18














COOLER:
Table.7. Required data for cooler
Required data Hot fluid(products from the
compressor)
cold fluid (water)
Mass, m(Kg) 310.79 ???
Specific heat, C
p
(J/Kg K) 1.6164 X 10
3
4.187 X 10
3

Inlet temperature(
0
C) 75 25
Outlet temperature(
0
C) 35 85
Temp. difference,T (
0
C) 75-35 = 40 85-25=60

( m C
p
T)
cold fluid
= (m c
p
T)
hot fluid
m X 4.187 X 10
3
x (85-25) = 310.79 X 1.6164 X 10
3
x

(75-35)
m = 79.98 kg
Mass of water required = 79.98 kg



QUENCH TOWER
Oil: 426.67 kg
Inlet temp: 25
0
C
Oil: 426.67 kg
Outlet temp: 300
0
C
C
4
H
10
: 248.63
C
4
H
6
: 34.72
C
4
H
8
:

12.00

H
2
: 3.00
Light ends: 6.22
Heavy ends: 6.22
Total: 310.79 kg

kg
Inlet temp: 545.5
0
C
C
4
H
10
: 248.63
C
4
H
6
: 34.72
C
4
H
8
:

12.00

H
2
: 3.00
Light ends: 6.22
Heavy ends: 6.22
Total: 310.79 kg
kg
Outlet temp: 55
0
C
Water: 79.98 kg
Inlet temp: 25
0
C
19






COOLER








BUTADIENE TOWER:
Condenser:
V = (mC
p
T)
cooling medium

V= Amount of vapor leaving the tower = D (R
D
+1)
Let R
D
(reflux ratio)

= 2.5
D = amount of distillate = F[(x
F
x
B
) / (x
D
x
B
)]
F = 5.25 kmoles
x
F
= 0.9796
x
B
= 0.001
x
D
= 0.9999
Substituting the above values, we get
D = 5.14 kmoles
Amount of vapor = V = 5.14 x (2.5 + 1) = 18 kmoles
= 295.35 Kg.
= 494.6 x 10
3
J/kg
m = mass of cooling medium =?
C
p
of cooling medium = 3 X 10
3
J/kgK
Products (gas)
Mass : 310.79 kg
Inlet temp: 75
0
C
Water: 79.98 kg
Outlet temp: 85
0
C
Products (gas)
Mass : 310.79 kg
Outlet temp: 35
0
C
20
Let T = 15
0
C
V = (mC
p
T)
cooling medium
295.35 X 494.6 X 10
3
= m X 3 X 10
3
X 15
m = 3246.26 Kg
= vapor flow rate at bottom of the tower.
= V - F (1-q)
q = 1(for saturated liquid feed)
= V = 295.35 Kg
Reboiler:
Table.8. Required data for reboiler
Required data Hot fluid Cold fluid (water)
Vapor, (Kg) 295.35 --
Latent heat, (J/Kg ) 2321.5 X 10
3
515 X 10
3


()
cold fluid
= (m)
hot fluid
295.35 X 515 X 10
3
= 2321.5 X 10
3
X m
21
m = 65.52 Kg
mass of heating medium required for reboiler = 65.52 Kg



CONDENSER
REBOILER
kmoles
C
4
H
10
: 4.29
C
4
H
6
: 0.64
C
4
H
8
: 0.21
Heavy ends: 0.11

5.25

x
F
= 0.9796
FEED, F
kmoles
C
4
H
10
: 4.29
C
4
H
6
: 0.64
C
4
H
8
: 0.21

5.14
DISTILLATE
X
D
= 0.9999
HEAVY ENDS: 0.11 kmoles
RESIDUE
X
B
= 0.001



BUTADIENE
TOWER
22
2.4. DESIGN

PREHEATER:

U
O
A
O
T
L
= (m Cp T)
cold fluid
= (m Cp T)
hot fluid


U
O =
Overall heat transfer coefficient
= 1 / [(1/ho)+(a
o
/a
i
)(1/hi)]
Where h
o
= shell side heat transfer coefficient
h
i
= tube side heat transfer coefficient
A
o
= surface area = 2 x x r
o
x L x n
Where, r
o
= outside radius
L = Length of the tube
n = no.of tubes
T
L
= log mean temperature difference = (T
1
-

T
2
) / ln[(T
1
/

T
2
)]
U
O
A
O
T
L
= (m Cp T)
cold fluid

1 / [(1/ho)+(a
o
/a
i
)(1/h
i
)] x 2 x x r
o
x L x n x T
L =
(m Cp T)
cold fluid

Table.9. Physical properties data for preheater
PHYSICAL PROPERTIES FUEL GAS(SHELL SIDE
FLUID)
BUTANE(TUBE SIDE
FLUID)
C
p
(J/KgK) 1.1 x 10
3
1.6164 x 10
3

(kg/m
3
) 1.8

2.5
(J/sm
o
C) 0.0339 0.0198
(kg/ms) 2 x 10
-5
7.35x10
6
kg/ms

Let velocity of flow V = 30 m/s
Assume inch outside diameter tubes of BWG 16
d
o
= 0.0191 m
d
i
= 0.0157 m
Tube side heat transfer coefficient h
i
:
Using Nusselt equation,
Nu = 0.023 (Re)
0.8
(Pr)
0.4
Re = (d
i
v )/ = (0.0157 x 30 x 2.5)/ 7.35 x 10
-6
= 160204 (>10000)
Pr = C
p
/ K = (1.6164 x 10
3
x 7.35 x 10
6
)/ 1.98 x 10
2
= 0.6
23
Nu = h
i
d
i
/K = 0.023 (Re)
0.8
(Pr)
0.4

= 0.023 (160204)
0.8
(0.6)
0.4

= 273.3551
h
i
= 273.3551 x 1.98 x 10
-2
/0.0157 = 344.7408 J/sm
2

o
C

Shell side heat transfer coefficient h
o
:
Using Nusselt equation,
N
u
= 0.023 (Re)
0.8
(Pr)
0.3

h
o
d
e
/ K = 0.023 (Re)
0.8
(Pr)
0.3

d
e
= equivalent diameter
d
e
for a triangular pitch is given by
d
e
= 4 x ( P
t
x 0.86 P
t
x d
o
2
/4)/( x d
o
)
Assume 1-inch triangular pitch
d
e
= 0.018 m
R
e
= d
e
v / = (0.018 x 30 x 1.8 )/ 2 x 10
-5
= 48600 (>10000)
Pr = Cp /k = 1.1 x 10
3
x 2 x 10
-5
/ (0.0339) = 0.6489
h
o
d
e
/ K =0.023 (48600)
0.8
(0.6489)
0.3

h
o
= 213.6079 J/sm
2o
C
U
o
= overall heat transfer coefficient
= 1/[(1/h
o
)+(a
o
/a
i
)(1/h
i
)]
h
o
= 213.6079 J/sm
2o
C
h
i
= 344.7408 J/sm
2o
C
a
i
= x d
i
2
/4 = 1.9359 x 10
-4
m
2
a
o
= x d
o
2
/4 = 2.8652 x 10
-4
m
2
U
O
= 1/[(1/213.6079) + (2.8652/1.9359)(1/344.7408)]
= 111.4254 J/sm
2o
C
T
L
= log mean temperature difference = (T
1
-

T
2
) / ln[(T
1/
T
2
)]
24
= [(900-650)-(200-25)] / ln(900-650/200-25)
= 210.2755
o
C

U
O
A
O
T
L
= (m Cp T)
cold fluid

m = mass flow rate of C
4
H
10
= 310.79 kg/min = 5.1797 kg/sec
T = 650 25 = 625
0
C
U
O
x x d
o
x L x n x T
L
= (m x C
P
x T)
cold

Assume length of tube L as 10 ft = 3.048 m
n = 1205
No. of tubes used = 1205
Shell inner diameter = 39 in. = 0.9906 m
DESIGN SUMMARY:
Length of each tube = 10 ft = 3.048 m
Outer dia of each tube

= inch = 0.0191 m
Inner dia of each tube = 0.0157 m
No. of tubes = 1205
Shell inner diameter = 39 in. = 0.9906 m
REACTOR:
Volume of gas charged = nRT / P
n = 5.3584 kmol/min = 321.5021 kmol/hr
R = 0.08206 atm m
3
/kmol K
T = 298 K
P = 1 atm
Volume of gas charged per hour = 7861.9727 m
3
gas charged / hr
Space velocity = 2 m
3
gas charged / hr m
3
of catalyst
Volume of catalyst = 7861.9727 / 2 = 3930.9864 m
3
of catalyst
Let porosity = 0.35
Volume of bed = 3931/(1 - 0.35) = 6047.6713 m
3
of bed
Assume D = 3m & L/D = 7
25
L = 21 m
Volume of one reactor = D
2
L/ 4 = 148.44 m
3
No of reactors required in parallel = 6048 / 148.44 = 41
DESIGN SUMMARY:
Diameter of each reactor = 3 m
Length of each reactor = 21 m
No. of reactors required in parallel = 41
ABSORBER:















No. of transfer units N
OY
= (y
b
y
a
) / y
L
----------- I
y
L
= [(y
b
y
b
*) (y
a
y
a
*)] / ln {( y
b
y
b
*) / (y
a
y
a
*)} ------ II
y* = 0.5 x (equilibrium relationship)
y
b
* = 0.5 x
b
= 0.5 x 0.8421 = 0.4211
y
a
* = 0.5 x
a
= 0.5 x 0 = 0
y
a
= 0.0032 ; y
a
* = 0
y
b
= 0.7621 ; y
b
* = 0.4211

Substituting the above values in equations I and II,
N
OY
= 11
NAPHTHA
x
a
= 0
NAPHTHA
C
4
H
10

C
4
H
6

C
4
H
8

x
b
= 0.8421
H
2

Light ends
y
a
= 0.0032
y
b
= 0.7621
A
B
S
O
R
B
E
R
G
M
= 0.0273 kmol/s
C
4
H
10

C
4
H
6

C
4
H
8
H
2

Light ends
Heavy ends

26
No. of transfer units = 11

HEIGHT OF TRANSFER UNIT (H.T.U):
Height of transfer unit, H
OY
= G
m
/ K
Y
a
Let K
Y
a (overall mass transfer coefficient) = 0.046 kmol / m
3
.sec
G
m
= Molar flow rate / column area
Gas flow rate = 310.79 kg / min = 5.1797 kg / sec
Liquid flow rate = 427.59 kg / min = 7.1266 kg / sec
Assuming 38 mm Intalox saddles packing; F
P
= 170 m
-1

Gas density (at 35
0
C) = P / RT = 1 / (0.08206 x 308) = 0.0396 kmol/m
3

= 2.29 kg/m
3

Liquid density = 960 kg/m
3

= 1.9 x 10
-3
kg/m.s
(L
W
/V
W
){(
V
/
L
)} = (7.1266/5.1797){(2.29/960)} = 0.067
Assume pressure drop of 20 mm H
2
O/m packing
K
4
= 0.9; At flooding K
4
= 3.2
% flooding = {(0.9/3.2)} x 100 = 53 %, satisfactory
V
W
= [{K
4
x
V
x (
L
-
V
)} / {13.1 x F
P
x (
L
/
L
)^0.1}]^(1/2)
= 1.82 kg/m
2
.s
column area = 5.1797 / 1.82 = 2.8460 m
2
= d
2
/4
column diameter = (4 x 2.8460)/ = 1.9 m
G
m
= 0.0273/2.8460 = 0.0096 kmol/m
2
s
H
oy
= G
m
/ k
y
a = 0.0096/0.046 = 0.21 m

Z
t
= H
oy
x N
oy
= 0.21 x 11 = 2.31 m
DESIGN SUMMARY:
Column diameter = 1.9 m
No. of transfer units = 11
27
Height of each transfer unit = 0.21 m
Total height of the column = 2.31 m

BUTADIENE TOWER:















DISTILLATE
X
D
= 0.9999

FEED, F
(SATURATED LIQUID)
kmoles
C
4
H
10
: 4.29
C
4
H
6
: 0.64
C
4
H
8
: 0.21
Heavy ends: 0.11

5.25

x
F
= 0.9796

B
U
T T
A O
D W
I E
E R
N
E
kmoles
C
4
H
10
: 4.29
C
4
H
6
: 0.64
C
4
H
8
: 0.21

5.14

RESIDUE
X
B
= 0.001
HEAVY ENDS: 0.11 kmoles
28
NO. OF STAGES:
Let relative volatility = 2.5
Equilibrium curve is given by
y = x/(1+[-1]x) = 2.5x/(1+1.5x)
For saturated liquid feed, q= 1
Slope of feed line = q/q-1 =
y - intercept of rectifying section operating line = x
D
/ R
D
+1
= 0.9999/3.5
= 0.2857
By Mccabe - thiele diagram,
No. of theoretical stages = 12 - 1( for reboiler) = 11

2
9
X
B

X
F
X
D

E
Q
U
L
I
B
R
I
U
M

C
U
R
V
E

R
E
C
T
I
F
I
C
A
T
I
O
N

O
P
E
R
A
T
I
N
G

L
I
N
E
q

-
-

L
I
N
E
S
T
R
I
P
P
I
N
G

O
P
E
R
A
T
I
N
G

L
I
N
E

X
:

M
O
L
E

F
R
A
C
T
I
O
N

O
F

L
I
Q
U
I
D

P
H
A
S
E

Y

M
O
L
E

F
R
A
C
T
I
O
N

O
F

V
A
P
O
U
R

P
H
A
S
E
X

y


F
i
g

2


B
U
T
A
D
I
E
N
E

H
E
A
V
Y

E
N
D
S

S
Y
S
T
E
M

30
COLUMN DIAMETER:
F
LV
bottom = (slope of bottom operating line )(
v
/
L
)

Assume tray spacing as 0.5 m

v
= 2.2 kg/m
3
;

L
= 750 kg / m
3
Slope of bottom operating line = 1.02
F
LV
bottom = 1.02 2.2/750 = 0.0552
Surface tension = 60 x 10
-3
N/m
Base K
1
= 8 x 10
-2
Correction for surface tension:
Base K
1
= (60/20)
0.2
x 8 x 10
-2
= 0.0996
Base U
f
= 0.0996 (750-2.2)/2.2 = 1.8374 m/s
Design for 85% flooding at maximum flow rate
Base U
V
= 0.85 x 1.8374 = 1.5618 m/s
Maximum volumetric flow rate:
Base : 295.35/(2.2 x 60) = 2.2375 m
3
/s
Net area required = 2.2375/1.518 = 1.4327 m
2

Taking downcomer area as 12% of total column cross sectional area,
Base area : 1.4327/0.88 = 1.6280 m
2

Column diameter = (4 x 1.6280)/() = 1.4398 m 1.44 m
Column height = 10 x 0.5 + 1 = 6 m
DESIGN SUMMARY:
No. of theoretical stages = 11
Tray spacing = 0.5 m
Column diameter = 1.44 m
Column height = 6 m

31
REBOILER:


REBOILER


U
O
A
O
T
L
= (m)
steam
U
O
= h
io
h
o
/ (h
io
+

h
o
)
A
O
= 2 r
o
L n
T
L
= 75 - 50 = 25
o
C
m
steam
= 65.52 kg

steam
= 2321.5 x 10
5
J/kg
h
o
= 8513.6 J/sm
2o
C
Re =d
i
v /
Assume inch outside dia, 16 BWG
d
i
= 0.0157 m (0.62 inch)
Let v = 30 m/s
= 1.9 x 10
4
kg/ms
= 39 kg/m
3

Re = 0.0157 x 30 x 39 /1.9 x 10
4
= 96679
j
H
= 250
C
p
= 1.5 x 10
3
J/Kg K
= 1.9 x 10
-4
kg/ms
K = 0.0174 W/m
o
C
d
i
= 0.0157 m
d
o
= 0.0191 m
Inlet temp. = 50
0
C
Heavy ends (lqd)
Outlet temp. = 50
0
C
Vapor
Steam: 65.52 kg
Inlet temp. = 75
0
C
Water: 65.52 kg
Outlet temp. = 75
0
C
32
K (Pr)
1/3
= 0.0442
h
i
= (j
H
K/D) (Pr )
1/3
= 703.6469 W/m
2o
C
h
io
= h
i
x d
i
/d
o
= 578.39 W/m
2o
C
Clean overall coefficient U
c
= h
io
h
o
/ (h
io
+

h
o
)
= (8513.6 x 578.39)/(8513.6 + 578.39)
= 541.5959 W/m
2o
C
U
C
A
O
T
L
= (m)
hot
Let L = 10 ft = 3.048 m
m = 65.52/60 = 1.092 kg/s
541.5959 x x 0.0191 x 3.048 x n x 25 = 1.092 x 2321.5 x 10
3
n = 1.092 x 2321.5 x 10
3
/(541.5959 x x 0.0191 x 3.048 x 25) 1024
Shell inner diameter = 37 inch = 0.9398 m
DESIGN SUMMARY:
Length of each tube = 10 ft = 3.048 m
Outer diameter of each tube

= inch = 0.0191 m
Inner diameter of each tube = 0.0157 m
No. of tubes = 1024
Shell inner diameter = 37 in. = 0.9398 m


2.5. PROCESS CONTROL AND INSTRUMENTATION
The primary objectives of the designer when specifying instrumentation and control
schemes are:
1. Safe plant operation:
a) To keep the process variables within known safe operating limits.
33
b) To detect dangerous situations as they develop and to provide alarms and
automatic shutdown systems.
c) To provide interlocks and alarms to prevent dangerous operating procedures.
2. Production rate:
To achieve the desired product output.
3. Product Quality:
To maintain the product composition within specified quality standards.
4. Cost:
To operate at the lowest production cost, commensurate with other Objects.
REACTOR CONTROL:
The schemes used for reactor control depend on the process and the type of reactor. If
a reliable on-line analyzer is available, and the reactor dynamics are suitable, the
product composition can be monitored continuously and the rector conditions and
feed flows controlled automatically to maintain the desired product composition and
yield. More often, the operator is the final link in the control loop, adjusting the
controller set points to maintain the product within specification, based on periodic
laboratory analysis.
Reactor temperature will normally be controlled by regulating the flow of heating or
cooling medium. Pressure is usually held constant. Material balance control will be
necessary to maintain the correct flow of reactants to the reactor and flow of products
and unreacted materials from the reactor.
Instrumentation:


34
Temperature Measurement:
The temperature-measuring element in a control system for a jacketed tank is
generally thermocouple. The five most commonly used thermocouple are copper-
constantan, iron-constantan, chromel-alumel, platinum-platinum 13% rhodium,
platinum-platinum 10% rhodium.
Flow rate Measurement:
The industrial devices for flow rate estimation are orifice meter, venturi meter, pitted
tube, and rotameter. The piping system must be made of special corrosion resistant
material meant for corrosive fluids.
Level Measurement:
The flow-shaft type is employed either in open vessels or in pressure vessels. This
method is suitable for a wide range of liquids and semi-liquids. Difficulties are
sometimes encountered when the liquid deposits on the floor and when the liquid
level is foaming or turbulent.
2.6. PLANT LAYOUT

35

The laying out of a plant is still an art rather than a science. It involves the placing
equipment so that the following are minimized:
Damage to persons and property in case of a fire, explosion, or toxic release
Maintenance costs
The number of people required to operate plant
Other operating costs
Construction costs
The cost of the planned future revision or expansion
The first thing that should be done is to determine the direction of the prevailing wind.
This can be done by consulting Weather Bureau records. Wind direction will
determine the general location of many things. All equipment that may spill
flammable materials should be located on the downwind side. Then if a spill occurs

RAW
MATERIAL
STORAGE

SCRAP AREA



FINISHED

PRODUCT

STORAGE
EFFULENT
TERATMENT

EXTENSION AREA

PROCESSING
AREA

ADMINISTRATIVE
OFFICE

BOILER
HOUSE
AND
WATER
PLANT
C
A
N
T
E
E
N
W
O
R
K

S
H
O
P
SECURITY
OFFICE
SAFETY
DEPT
HEALTH
CENTER
MAIN ROAD
Fig. 3. PLANT LAYOUT
36
the prevailing winds are not apart to carry any vapors over the plant, where they could
be ignited by an open flame, spark, or a hot surface.
Items that should be located Upwind of the plant:
Plant Offices
Central Laboratories
Mechanical and other shops
Office building
Cafeteria
Store house
Medical Building
Change house
Fire station
Boiler house
Electrical Power house
Electrical substation
Water treatment plant
Cooling tower
Air Compressors
Parking lot
Main water pumps
Warehouses that contain non-hazardous
Non-explosive and
Non-flammable materials
Fired heaters
All ignition sources

Items that should be located downwind of the plant
Equipments that may spill inflammable materials
Blown down tanks
Burning Flares
Setting ponds

For a similar reason the powerhouse, boilers, water pumping, and air supply facilities
should be located 250 ft (75 m) from the rest of the plant, and on the upwind side.
This is to minimize the possibility that these facilities will be damaged in case of a
major spill. This is especially important for the first two items, where there are
usually open flames.
37
Every precaution should be taken to prevent the disruption of utilities, since this could
mean the failure of pumps, agitators, and instrumentation. For this reason, it may also
be wise to separate the boilers and furnaces from the other utilities. Then, should
fired equipment explode, the other utilities will not be damaged.
Other facilities that are generally placed upwind of operating units are plant officers,
mechanical shops and central laboratories. All of these involve a number of people
who need to be protected. Also, shops and laboratories frequently that are used
primarily for quality control are sometimes located in the production area.
STORAGE FACILITIES
Tank farms and warehouses that contain non-hazardous, nonflammable, and non
explosive materials should be located upwind of the plant. Those that do not fit this
category should not be located downwind of the plant, where they could be damaged
and possibly destroyed by a major spill in the processing area. Nor should they be
located upwind of the plant where, if some of their contents are spilled. the processing
area might be damaged. They should be located atleast 250 ft (75 m) to the side of
any processing. Some authorities suggest this should be 500 ft. The same reasoning
applies to hazardous shipping and receiving areas.
Sometimes, storage tanks are located on a hill, in order to allow the gravity feeding of
tank cars. Care must be taken under these circumstances to see that any slop over
cannot flow into the processing, utilities, or services areas in case of a tank fir.
When liquefied petroleum gases are used, the areas for containing spills are always
below grade because the gases are denser than air. The gases will accumulate in the
low areas will also not be asphyxiated.
SPACING OF ITEMS
The OSHA has standards for hazardous materials that give the minimum distances
between containers and the distances between these items and the property line,
public roads and building. These depend on the characteristics of the material, the
type and size of the container, whether the tank is above ground or buried and the type
38
of protection provided. Specific details are provided for compressed gas equipment
containing acetylene-air, hydrogen-oxygen and nitrous oxide, as well as liquefied
petroleum gases. They also prohibit the storage and location of vessels containing
flammable and combustible materials inside buildings, unless special precautions are
taken.
Again, the major reason for including the layout in the preliminary plant design is that
the transporting equipment and buildings may be sized to make certain that no needed
equipment is omitted and that the chosen plant site will be large enough. At this
point, since most of the energy transfer equipment has not been sized, only its
approximate location can be given.
PROCESSING AREA
There are two ways of laying out a processing area. The grouped layout places all
similar pieces of equipment adjacent. This provides for ease of operation and
switching from one unit to another. For instance, if there are 10 batch reactors, these
would all be placed in the same general area and could be watched by minimum of
operators; if they were spread out over a wide area, more operators might be added.
This scheme is best for large plants. The flow line layout uses the train or line
system, which locates all the equipment in the order in which it occurs on the flow
sheet. This minimizes the length of transfer lines and therefore reduces the energy
needed to transport materials. In industries, it is used mainly for small volume
products. Often, instead of using the grouped or flow line layout exclusively, a
combination that best suits the specific situation is used.
PLACING OF EQUIPMENT
Once a general scheme is decided upon, the processing area is divided into unit areas.
The units should be grouped so that the number of operating personnel is minimized.
The maximum loss concept must also be considered. Some companies place a limit
in the maximum loss that can be expected if a fire or explosion occurs. This permits
those watching the controllers to quickly investigate and determine the cause of any
problems that might arise. It may be desirable to have two or more processes
controlled from one location, this could reduce the number of operations required. In
39
this case, the control room should be located in a relatively unexposed area near the
edge of the processing area, but away from fired heaters. This is to protect both the
employees and the equipment.
ELEVATION
If there is no special reason for elevating equipment it should be placed on the ground
level. The superstructure to support on elevated piece of equipment is expensive. It
can also be a hazard should there be an earthquake, fire or explosion. Then it might
collapse and destroy the equipment it is supporting as well as that nearby. Some
pieces of equipment will be elevated to simplify the plant operations. An example of
this is the gravity feed of reactors from elevated tanks. This eliminates the need for
some materials-handling equipment. This especially true for solids and slurry feed.
MAINTENANCE
Maintenance costs are very large in the chemical industry. In some cases, the cost of
maintenance exceeds the companys profit. The engineer must design to reduce these
costs. The easiest way to reduce maintenance costs is to allow lots of extra space and
to construct everything at ground level for easy access. However, this may increase
construction and operating expenses and the ease of operability. The engineer should
determine what type of equipment need to be serviced by mobile cranes. These
pieces of equipment will need to be located on the perimeters of the plant or on a
roadway. The roadways along which the crane will travel must have adequate
overhead and horizontal clearness. Adequate space must be left around all equipment
so that it can be easily serviced and operated. For instance, a floating-head heat
exchanger must have enough space so that the tube bundle can be removed from the
shell and taken elsewhere for repairs. For tanks containing coils and agitators, enough
headroom must be provided so that these can be removed.
CONSTRUCTION AND BUILDING
Proper placing of equipment can result in large savings during the construction of the
plant. For instance, large columns that are field-erected should be located at one end
40
of the site so that they can be built, welded, and tested without interfering with the
construction of the rest of the plant.
RAILROADS, ROADWAY AND PIPE RACKS
The main purpose of railroads is to provide an inexpensive means for obtaining raw
materials and for shipping products. This means that they should be close to raw
materials and or/ product storage. Buildings and loading docks should be set back 8 ft
(2.4m) from the center of the railroad track. Spurs and switches should be laid out
with a 100 ft (30m) radius. Roads are used not only for these purposes but to provide
access for fire fighting equipment and other emergency vehicles, and for maintenance
equipment. This means that there should be a road around the perimeter of the site.
No road should be dead-end. For safety there should be two ways to reach every
location. All major traffic should be kept away from the processing areas.
PLANNING FOR EXPANSION AND IMPREMENTS
Obviously, if the equipment has been over designed to meet the anticipated future
expansion, no extra space needs to be provided. If, however, additional equipment
will be required, space should be allocated for it. The net result will be an increase in
these initial costs of construction and some increase in material transfer costs, because
the transfer lines will be longer.
BUILDING
Building with the layout of the plant is the direction as to what types of buildings are
to be construction, and the size of teach. When laying out buildings, a standard size
bay (area in which there are no structural supports) is 20ft x 20ft (6m x 6m). Under
normal conditions a 20-ft (6m) span does not need any center supports. The extension
of bay in one direction can be done inexpensively. This only increases the amount of
steel in the long girders, and requires stronger supports. Lavatories, change rooms,
lunch rooms and medical facilities is dictated by OSHA. It depends on the number of
workers employed. Research laboratories and office buildings usually not included in
the preliminary cost estimate. However, if they are contemplated, their location
should be indicated on the pilot plan.
41
PROCESSING BUILDINGS
Quality control laboratories are necessary part of any plant, and must be included in
all cost estimates. Adequate space must be proved in them for performing all tests,
and for cleaning and storing laboratory sampling and testing containers.
Packaging equipment generally must be in enclosed buildings, and is often located at
one end of the warehouse. If the material being packaged is hazardous, either this
operation will be performed in a separate building, or a firewall will separate it from
any processing or storage areas.
WAREHOUSE
The engineer must decide whether warehouses should be at ground level or at dock
level. The latter facilitates loading trains and trucks, but costs 15-20 percent more
than one placed on the ground. It is usually difficult to justify the added expense of a
dock-high warehouse.
2.7. COST ESTIMATION
ESTIMATION OF THE TOTAL CAPITAL INVESTMENT:
The total capital investment I involves the following:
A. The fixed capital investment in the process area, IF.
B. The capital investment in the auxillary services, IA.
C. The capital investment as working capital, IW.
i.e., I = IF + IA + IW
A. FIXED CAPITAL INVESTMENT IN THE PROCESS AREA, IF.
This is the investment in all processing equipment within the processing area.
42
Fixed Capital Investment In The Process Area, If = Direct Plant Cost + Indirect Plant
Cost
The approximate delivered cost of major equipment used in the proposed Butadiene
manufacturing plant are furnished below:
Table.10. Delivered cost of major equipment
S.No. Equipment Units Cost in lakhs/unit Cost in lakhs
1 Furnace 1 2.4 x 10
6
2.4 x 10
6

2 Reactor 41 2.6 x 10
6
1.066 x 10
8

3 Heat exchanger 5 7 x 10
5
35 x 10
5

4 Distillation column 3 8 x 10
5
24 x 10
5

5 Absorption column 1 6 x 10
5
6 x 10
5

6 Stripper 2 4 x 10
5
8 x 10
5

7 Mixer settler 1 5 x 10
5
5 x 10
5

8 Pump 1 10000 10000
9 Ejector 1 10000 10000
10 Compressor 1 10000 10000
11 Miscellaneous 3.17 x 10
6
3.17 x 10
6

TOTAL 1.2 x 10
8
lakhs

Table.11. Direct cost factor
S.No Items Direct cost factor
1 Delivered cost of major equipments 100
2 Equipment installation 15
3 Insulation 15
4 Instrumentation 15
5 Piping 75
6 Land & building 30
7 Foundation 10
8 Electrical 15
9 Clean up 5
Total direct cost factor 280
43

Direct plant cost = (Delivered cost of major equipments) (Total direct cost factor) /
100
Direct plant cost = (1.2 x 10
8
* 280) / 100
= 3.36 x 10
8
lakhs
Table.12. Indirect cost factor
S.No. Item Indirect cost factor
1 Overhead contractor etc. 30
2 Engineering fee 13
3 Contingency 13
Total indirect cost factor 56

Indirect plant cost = (Direct plant cost)(Total indirect cost factor) / 100
= (3.36 x 10
8
* 56) / 100
= 1.8816 x 10
8
lakhs
Fixed capital investment in the process area, IF = Direct plant cost + Indirect plant
cost
= 3.36 x 10
8
+ 1.8816 x 10
8

= 5.2416 x 10
8
lakhs
B. The capital investment in the auxiliary services, IA.
Such items as steam generators, fuel stations and fire protection facilities are
commonly stationed outside the process area and serve the system under
consideration.
44
Table.13. Auxillary services cost factor
S.No. Items Auxillary services cost factor
1 Auxillary buildings 5
2 Water supply 2
3 Electric Main Sub station 1.5
4 Process waste system 1
5 Raw material storage 1
6 Fire protection system 0.7
7 Roads 0.5
8 Sanitary and waste disposal 0.2
9 Communication 0.2
10 Yard and fence lighting 0.2
Total 12.3

Capital investment in the auxillary services = (Fixed capital investment in
the process area)( Auxillary services cost factor) / 100
= (5.2416 x 10
8
* 12.3) / 100
= 6.4471 x 10
7
lakhs
Installed cost= Fixed capital investment in the process area + Capital
investment in the auxillary services
= 5.2416 x 10
8
+ 6.4471 x 10
7

= 5.8863 x 10
8
lakhs
45
C. The capital investment as working capital, IW.
This is the capital invested in the form of cash to meet day-to-day operational
expenses, inventories of raw materials and products. The working capital may be
assumed as 15% of the total capital investment made in the plant ( I ).
Capital investment as working capital, IW = (5.8863 x 10
8
* 15) / 85
= 1.0387 x 10
8
lakhs
Total capital investment, I = IF+ IA+ IW
= 5.2416 x 10
8
+ 6.4471 x 10
7
+ 1.0387 x 10
8

= 6.9250 x 10
8
lakhs
ESTIMATION OF MANUFACTURING COST
The manufacturing cost may be divided into three items, as follows:
A. Cost Proportional to total investment
B. Cost proportional to production rate
C. Cost proportional to labour requirement
A. COST PROPORTIONAL TO TOTAL INVESTMENT
This includes the factors, which are independent of production rate and proportional
to the fixed investment such as
- Maintenance-labour and material
- Property taxes
- Insurance
- Safety expenses
- Protection, security and first aid
46
- General services, laboratory, roads, etc.
- Administrative services
For this purpose we shall charge 15% of the installed cost of the plant
= (Installed cost * 15) / 100
= (5.8863 x 10
8
* 15) / 100
= 8.8294 x 10
7
lakhs
B. COST PROPORTIONAL TO PRODUCTION RATE
The factors proportional to production rate are
- Raw material costs
- Utilities cost power, fuel, water. Steam, etc.
- Maintenance cost
- Chemical, warehouse, shipping expenses
Assuming that the cost proportional to production rate is nearly 60% of total capital
investment,
Cost proportional to production rate = (Total capital investment * 60) / 100
= (6.9250 x 10
8
* .6)
= 4.1550 x 10
8
lakhs
C. COST PROPORTIONAL TO LABOUR REQUIREMENT
The cost proportional to labour requirement might amount to 10% of total
manufacturing cost.
Cost proportional to labour requirement=(8.8294x10
7
+4.155x10
8
)(0.1)/(0.9)
47
= 5.5978 x 10
7
lakhs
Therefore, manufacturing cost = (8.8294x10
7
+4.155x10
8
+5.5978x10
7
)
= 5.5978 x 10
8
lakhs
SALES PRICE OF PRODUCT
Market price of Butadiene = Rs.45/kg
Production rate = 50

TPD
Total sales income = 45 x 50 x 1000 x 330
= 7.425 x 10
8
lakhs
PROFITABILITY ANALYSIS
A. DEPRECIATION
According to sinking fund method:
R = (V-VS) I / (1+ I)
n

R = Uniform annual payments made at the end of each year
V = Installed cost of the plant
VS = Salvage value of the plant after n years
N = life period (assumed to be 15 years)
I = Annual interest rate (taken as 15%)
R = (5.8863 x 10
8
* .15) / (1+0.15)
15
-1
= 1.2371 x 10
7
lakhs

48
B. GROSS PROFIT
Gross profit = Total sales income - manufacturing cost
= 7.425 x 10
8
- 5.5978 x 10
8

= 1.8272 x 10
8
lakhs
C. NET PROFIT
It is defined as the annual return on the investment made after deducting depreciation
and taxes. Tax rate is assumed to be 40%.
Net profit = Gross profit Depreciation - (Gross profit*Tax rate)
= 1.8272 x 10
8
- 1.2371 x 10
7
- (1.8272 x 10
8
*0.4)
= 9.7262 x 10
7
lakhs
D. ANNUAL RATE OF RETURN
Rate of return = (100*Net profit/Installed cost)
= (100*9.7262 x 10
7
) / 5.8863 x 10
8
= 16.5235%
E. PAYOUT PERIOD
Payout period = Depreciable fixed investment / ((profit)+(depreciation))
= 5.8863 x 10
8
/ (9.7262 x 10
7
+ 1.2371 x 10
7
)
= 5.36908 years
2.8. PROCESS SAFETY
Introduction:
49
In recent years there has been an increased emphasis on process safety as a result of
number of serious accidents. This is due in part to the worldwide attention to issues in
the chemical industry brought on by several dramatic accidents involving gas releases,
major explosions and several environmental accidents. Public awareness and of these
and other accidents has provided a driving force for industry to improve its safety
record. Local and national governments are taking a hard look at safety in industry as
a whole and the chemical industry in particular. There has been an increasing amount
of government regulations.
For many reasons, the public often associates chemical industry with environmental
and safety problems. It is vital for the future of the chemical industry that process
safety has a higher priority in the design and operation of chemical process facilities.
Industrial accidents:
An accident has been defined as an unplanned or unexpected event, which causes or is
likely to cause an injury.
An accident occurs as a result of unsafe actions or exposure to an unsafe environment.
Unsafe actions or unsafe mechanical or physical conditions exist only because of
faults of a particular person.
Faults of persons are inherited from the environment and reasons for the faults are:
Improper attitude
Lack of knowledge or skill
Physical unsuitability
Improper mechanical or physical environment
Accident prevention:
Form the foregoing, it will be seen that the occurrence of an injury is the culmination
of a series of events or circumstances that invariably occur in a fused and logical
order.
50
Knowledge of the factors in the accident sequence guides and assists in selecting the
point of attack in prevention work. It permits simplification without sacrifice of
effectiveness. The most important point is that unsafe conditions or actions are the
immediate cause of accidents. The supervision and management can control the
actions of employed persons and so prevent unsafe acts and also guard or remove
unsafe conditions, even though previous events or circumstances in the sequence are
unfavorable.
The four factors that converge to cause accidents are:
Personal factor
Hazard factor
Unsafe factor
Proximate casual factor
The solution under the four factors would also lead to two steps. These are planning
and organizing to
1. Prevent unsafe mechanical or physical conditions.
2. Prevent unsafe action being committed.
Unsafe conditions examples:
Operating without securing, warning etc.
Operating or working at unsafe speed.
Making safety devices inoperative.
Using unsafe equipment.
Unsafe loading, placing, mixing etc.
Taking unsafe positions or posture.
Working on moving or dangerous equipment.
Unsafe mechanical and physical conditions-examples
51
Inadequately guarded.
Unguarded.
Defective condition (rough, delayed etc).
Unsafe design or construction.
Hazardous arrangement or process.
Inadequate or improperly distributed ventilation.
Unsafe dress or apparel.
Unsafe method, process, planning etc.
The most important means of accident prevention are:
Engineering revision.
Instruction.
Persuasion.
Appeal.
Personal adjustment.
Discipline.
Industrial ventilation and lighting
The main functions of ventilation in an industry are:
To prevent harmful concentration of aerosols.
To maintain reasonable condition of comfort for operators at workplace.
It maintains the body heat balance and to provide reasonable conditions of
comfort.
Ventilation should aim at
Keeping the air temperature of the workroom low enough to enable
52
1. body heat to be dissipated by convection.
2. preventing excessive humidity so as to assist body heat loss by
evaporation.
3. regulating the rate of air movement so that loss of body heat by
convection is facilitated.
The amount of ventilation generally depends on the following factors:
1. Size and type of room or building and its usage.
2. Duration and type of occupants and their activities.
3. Heat gains from sun, hot manufacturing.
4. Temperature conditions.
5. The operators of the ventilating system.
Types of ventilation
1. Natural ventilation
2. Mechanical ventilation
Natural ventilation
Forces, which operate to induce natural ventilation in building, are due to:
Pressures exerted by outside wind
The temperature differences of the air within and without the building.
Types of natural ventilation:
1. Cross ventilation.
2. Roofed ventilation.
3. Cool type roof ventilation.
53
Mechanical ventilation
It is brought out by either one or both of the following two methods:
Ventilation through windows or other openings owing to the suction created
by the exhaust of air
Positive ventilation by means of a fan or blower
Types of mechanical ventilation:
Exhaust ventilation
Combined plenum and extraction systems
Mechanical roof ventilators.
Personal protective devices:
Protective devices are required by regulation; the employers are required to provide it.
Free of cost and also should be responsible to ensure its usage maintenance and
renewal. Once it is decided to use personal protective devices, we must select the
proper type of device. Make sure that the employees use and maintain these correctly.
For selection of device, two criteria should be used:
1. The degree of protection.
2. The ease with which it may be used.
Protective devices are divided into two groups:
1. Respiratory devices
2. Non-respiratory devices
Safety appliances:
54
Helmets:
Every employee inside the factory should always wear the safety helmet to avoid
head injuries. No worker will be allowed to enter any plant without a helmet.
Safety goggles:
The goggles must be worn while entering the process areas. Special goggles must be
worn for gas welding and grinding operations.
Safety shoes:
All the employees working inside a factory should wear safety shoes and gumboots
should be used while handling acids and alkalis.
Hand gloves:
While operating any valve or equipment and also while executing any maintenance
work including electrical maintenance work, the employees should wear appropriate
type of safety gloves.
Dust mask:
While working in a dusty atmosphere, the employees must wear dust masks to prevent
dust and fumes from entering the sensitive respiratory organs, which can cause a lot
of irritation and in the long run painful and incurable diseases.
Plastic aprons:
This along with the hood gives protection to the operation and maintenance staff
while handling dangerous acids and other hazardous chemicals particularly when
there is possible leakage.
In spite of safety appliances, the companys medical center is equipped to meet any
emergency and any employee coming in contact with acids or any hazardous
chemicals must be treated at the medical center immediately.
55
2.9. MATERIALS OF CONSTRUCTION
Generally carbon steel is suitable for most plant equipment processing butadiene or
similar hydrocarbons. Brass or copper should be avoided because of the possible
formation of explosive acetylides from traces of acetylene. Special construction
materials may be essential in certain other circumstances. For example, in an n-
butene hydrogenation vessel, the surfaces are exposed to high temperatures and
steam; consequently carbon steels are not suitable. Nickel alloy steels are said to be
satisfactory provided that the catalyst is not calcium nickel phosphate. Heavy carbon
deposition is possible when this catalyst is used with nickel alloys. Chrome alloys are
(4 to 30%) are however, claimed to give good service.
Nickel steels are said also to be responsible for coke formation in n-butane
dehydrogenations. High chrome alloy steels are used for the construction of catalyst
support grids in Houdry plant. The internal surfaces of Houdry reactor are
alternatively exposed to high temperature hydrocarbons and air atmospheres.
Refractory linings are essential. Oxy halo dehydrogenation processes can give very
high corrosive conditions. In purification plants, carbon steel is regarded suitable.
Carbon steel is suitable in cuprous ammonium acetate extraction plant, but brass,
copper or bronze alloys must be avoided.
2.10. STABILIZATION, STORAGE, AND TRANSPORTATION
Stabilization involves protection against the action of oxygen and against
polymerization. Butadiene forms dangerous polymeric peroxides with oxygen, which
are viscous liquids sparingly soluble in liquid butadiene. They are deposited at the
bottom of butadiene containers. Hence, handling of butadiene requires complete
exclusion of oxygen. In addition, inhibitors, like TBC (p-tert-butylpyrocatechol) or
TBK (2,6-di-tert-butyl-p-cresol), are added because they are especially effective at
scavenging radicals. They also prevent a spontaneous polymerization of butadiene
and can easily be removed by washing with aqueous sodium hydroxide. An aqueous
sodium nitrite solution is also used as an antioxidant in the production of butadiene.
Butadiene can polymerize during its production, storage and transportation in three
different ways: First, it can dimerize to vinylcyclohexene. This reaction is dependent
56
on time and temperature and can be stopped by adding a potassium cyanide solution
to butadiene. Secondly, butadiene can polymerize under the influence of oxygen and
high temperatures, especially during its manufacture, to give rubber-like polymers
(fouling), Antioxidants, like TBC, exclusion of oxygen, low temperatures, and short
exposures to higher temperatures reduce this polymerization. Thirdly, butadiene can
polymerize, initiated by oxygen, high temperatures, and rust, to give a glassy,
granular, opalescent, and very hard polymer, the so-called Popcorn. It forms
preferentially in off-stream tubes. Its growth is favored when Popcorn seeds are
present in the plant. The formation of Popcorn in closed areas can lead to pressures of
> 1000 bar, causing the bursting of off-stream tubes or containers. It can be prevented
by the addition of TBC and by the careful elimination of all Popcorn seeds. Popcorn
is spontaneously
inflammable in air and, hence, must be kept moist during its removal. Liquefied
butadiene is stored at normal temperatures in liquid-gas containers or, today, for
safety reasons at a temperature of 4
0
C in almost pressureless containers. It is
transported at normal temperatures and raised pressures in tankers, railroad tank
wagons, and in ships. Especially in ships, temperatures of 4
0
C and pressure less
containers are required.
2.11. HEALTH, SAFETY AND TOXICOLOGY
Butadiene has been used widely in producing many important industrial polymers and
other products. Short-term exposure to high concentrations of butadiene may cause
irritation to the eyes, nose, and throat. Dermatitis and frostbite may result. Long-term
physiological reactions to 1,3-butadiene may vary individually.
Exposure studies have been made using mice and rats. These experiments have
demonstrated species differences in butadiene toxicity and carcinogenicity. Butadiene
was found to be a potent carcinogen in the mouse, but only a weak carcinogen in the
rat. The interpretations have focused on differences in toxification rates and
detoxification metabolisms as causative factors.

57
Butadiene is of low acute toxicity. Like some other hydrocarbons butadiene causes
narcotic effects after inhalation of high concentrations, some-times preceded by
excitation and hyperventilation.
Table.14. Exposure limits
Country Exposure Limit
Belgium 10 ppm
5 ppm before polymerization Germany
15ppm after polymerization
Italy 10 ppm (predicted)
Japan 10 ppm (voluntary adoption)
Latin America 1 ppm (predicted)
The Netherlands 50 ppm
United Kingdom 10 ppm
10ppm (ACGIH, 1982)
10ppm for 15 min (OSHA 1990)
United States
2ppm 8-h time weighted average (OSHA
1990)

CONCLUSION
Butadiene is one of the most important chemicals. Also with the major advancements
like production of a new elastomer system based on carboxy-terminated butadiene
acrylonitrile polymers (CBTN) as an alternative to urethane technology and its wide
applications, butadiene has become one of the most widely used chemicals in the
world.
This project has analyzed the salient features of the process of manufacture of
Butadiene. It has also dealt with the various design aspects of the important
equipments, cost estimation and project feasibility.
58
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