Ministry of Education

Higher Education and Scientific Research

University of Babylon

College of Engineering

chemical engineering

Butadiene production from butane

By:

Muhammad Abbas Saddam

Ali Dawood Said

Supervisor:

Dr. Falah Kifi Matlub

Dr.Sarmad Abdulrasol

2221-2222

1
 ‫ميحرلا نمحرلا هللا مسب‬
‫( وقل اعملوا فسريى اهلل عملكم ورسوله واملؤمنون )‬
‫صدق هللا العلي العظيم‬

‫الحمدللهىحمداًىكثوراىونذكرهُىرلىىنطمتهى‪...‬ى‬

‫نتقدمىبخالصىالذكرىواالمتنانىالهلناىالذونىداندوناىفيىالدراءىوالضراءىوالذونى‬
‫بفضلكمىاتممناىالرحلظىالدرادوظى‪.‬ى‬

‫والذكرىالكثورىالىىجموعىاداتذتناىفيىكلوظىالكنددظىقدمىالكومواويىوبالخصوصى‬
‫الدكتورى(ىفالحىكوفيىمطلوبى)ىالذيىداردناىبكلىخطوةىفيىاتمامىهذاىالمذروعى‪.‬ى‬

‫وامنىبفضلكمىىاتقدتىذمطظىالطلمىفيىرقولناىاطالىاللهىفيىارماركمىونتمنىىلكمى‬
‫دوامىالتوفوقىلبناءىاجوالىالطراق‬

‫‪2‬‬
 ‫هندي مرشوعنا هذا اىل شهداء العراق اكفة ‪....‬‬

‫اُهذي هزا العول اىل الشباب الزٌي اجربهتن ظشوف املعٍشت الصعبت واىل الفتٍاث اللواتً اصبحي ضحٍت اجملتوع املتخلف‬

‫وعاداث وتقالٍذ جاهلٍت هي ع ــذم اكوال الشحلت الذساسٍت‬

‫لعلنا ٌوهاً حني املتعلوني ًستطٍع اًقارهن‪.‬‬

‫اُهذي هزا هششوعً اىل كل هي علوين حشفاً واىل ابً الزي كاى يل عوًاً يف كل خطوة يف حٍاتً واىل مجٍع اساتزتً‬

‫يف سحليت الذساسٍت ومجٍع اصذقائً وال اًسى اٌضاً اهذاء هزا املششوع اىل وطين العشاق‪.‬‬

‫‪3‬‬
Chapter one

Introduction

4
1-1 what is butane
Butane: gas is sold in cylinders as a fuel source for cooking and camping, in
which case it is called liquefied petroleum gas, and in the UK it is called
"heating gas". It is also used as an ingredient in the petroleum industries for
the production of lower petrochemicals in steam cracking, as well as in
filling cigarette lighters, and as a propellant for spraying products using
aerosol method. Recent concerns about the risks to the ozone layer from
Freon have led to an increase in the use of butane gas in refrigeration
systems, especially refrigerators and freezers that are used in homes. When
used as a coolant, isobutane is called isobutane.

1-2 Physical and chemical Properties.

Table1-1 Physical and chemical Properties

Properties Values
Molecular formula C4H10
Molar mass 58.08 g/mol
Appearance Colorless gas
Density 2.52 g/l ,gas (15 Co ,1 atm)
Phase 0.584 g/cm3 ,liquid
Liquid Solubility in water 6.1 mg/100 ml (20 Co)
Melting point -138 Co
Boiling point -1.5 Co

1-3 Uses of Butane

1- Butane is used as a gasoline mixture, either alone or in a propane mixture.
2- Used as a feedstock for the production of ethylene and butadiene, butane,
like propane, comes from natural gas or petroleum refineries and the two
gases are usually found together. Butane is stored under pressure as a liquid,
when the device is turned on, butane is released and turns into a gas.
3- It is generally used for household purposes in cylinders painted red and sold
under various brand names.
4-It is used as a fuel gas and as a raw material in the production of ethylene and
butadiene.
5- It is used to produce methyl tert-butyl ether.
6- It is used in the catalytic dehydrogenation of butane or the cracking of raw
materials into n-butenes and higher and lower boiling fraction.

5
1-4 What is Butadiene ?

Butadiene: a colorless gas with a light aromatic smell similar to that of gasoline,
highly reactive and flammable, insoluble in water and soluble in alcohol and
ether, and polymerizes easily, especially if oxygen is present. It was discovered in
the nineteenth century and one of its main uses is in the rubber industry, as well
as in the development of rubberlike polymers and in the manufacture of plastics.
Mass production began in World War II in the United States of America. The
first to polymerize butadiene was the Russian
chemist Sergei Lebedev in 1910, and in 1926 he invented the first process for the
manufacture of butadiene from ethanol, and in 1928 he developed a method for
producing butadiene using sodium as a catalyst.

Table 1-2 Physical and chemical Properties

Properties Values
Physical state at 20 °C Liquefied gas.
Colour Colorless gas.
Odour Poor warning properties at low
concentrations.
Molecular weight 54
Melting point [°C] -109
Boiling point [°C] -4.5
Critical temperature [°C] 152
Vapour pressure, 20°C 2.4 bar
Relative density, gas (air=1) 1.9
Relative density, liquid (water=1) 0.65
Solubility in water [mg/l] 1025
Flammability range [vol% in air] 1.4 to 16.3
Auto-ignition temperature [°C] 415
Other data Gas/vapour heavier than air. May accumulate
in confined spaces, particularly at or below
ground level

6
1-5 Butadiene is produced commercially by three processes

1- Steam Cracking of Paraffinic Hydrocarbons: In this process, butadiene is

a co- product in the manufacture of ethylene (the ethylene co-product
process)
2- Catalytic Dehydrogenation of n-Butane and n-Butene (the Houdry
process).
3- Oxidative Dehydrogenation of n-Butene (the Oxo-D or O-X-D process).

7
Chapter Two

Process Description

8
2-1 Butadiene Production via Oxidative Dehydrogenation of n-
Butenes (the Oxo-D or O-X-D process):

Oxidative dehydrogenation of n-butenes has replaced many older processes

for commercial (onpurpose) production of butadiene. Several processes and
many catalyst systems have been developed for the oxydehydrogenation of
either n-butane or of n-butene feedstocks. Butenes are much more reactive,
however, and they require less severe operating conditions than that of
nbutane to produce an equivalent amount of product. Therefore, the use of
n-butane as a feedstock in this process may not be practical. In general, in an
oxydehydrogenation process, a mixture of n-butenes, air and steam is passed
over a catalyst bed generally at low pressure and approximately 930-1110 °F
(500-600 °C). The heat from the exothermic reaction can be removed by
circulating molten heat transfer salt, or by using the stream externally for
steam generation. An alternate method is to add steam to the feed to act as a
heat sink. The heat can then be recovered from the reactor effluent.Reaction
yields and selectives can range from 70-90%, making it unnecessary to
recover and recycle feedstock.

In the Oxo-D process shown in Figure, a mixture of air, steam, and n-

butenes is passed over the dehydrogenation catalyst in a continuous process.
9
The air feed rate is such that an oxygen/butene molar ratio of approximately
0.55 is maintained, and the oxygen is totally consumed. A steam to butene
ratio of 10:1 has been reported as necessary to absorb the heat of reaction
and to limit the temperature rise.
The reactor effluent is cooled and the C4 components are recovered in an
absorber/degasser/ stripper column combination. The lean oil flows from the
bottom of the stripper back to the absorber, with a small amount passing
through a solvent purification area. Crude butadiene is stripped from the oil,
recovered in the overhead of the stripper, then it is sent to a purification
system to recover the butadiene product.

2-2 Preprocess Purification – Deisobutanizer :

The main objective of this pre-treatment unit is to extract n-butane from the feed.
The extracted n-butane will be used as the reactant for the dehydrogenation
process in order to produce butadiene.

11
Component Formula Mole %
Propane C3H8 0.9
i-Butane (isobutene) C4H10 25.9
n-Butane C4H10 72.2
Other Hydrocarbon C5 + 1

From the table, it can be seen that the feed also contains significant amount of i-
butane which is 25.90 %. In order to fully utilize the feed, the separated i-butane
will be sent to isomerization section to undergo the isomerization process that
will convert i-butane to n-butane.
The distillation column, C-101 will recover i-butane as the top product. The
overhead product of the column also consists of significant amount of n-butane.
For the sake of purity, the overhead product will enter the vapor recovery system
which is the condenser (E-102). The operating temperature and pressure of E-102
are 40.71oC and 300 kPa. The condensed product which is mainly n-butane will
be recycled back to C-101 while the vapor product which is mainly ibutane will
be sent to the Alkylation Section. N-butane is extracted as the side product. This
nbutane will enter the Reaction Section to undergo the dehydrogenation process.
The bottom product of this column consists of the heavier product which is the
condensate (C5+) together with considerable amount of n-butane. The bottom
stream of column will then enter the reboiler (E-101) to recover the n-butane.

2-3 Dehydrogenation section

The third section of the plant is the dehydrogenation unit. The main
objective of the unit is to convert the n-butane to the product desired,
Butadiene. The section involves two steps of dehydrogenation processes
which are the non-oxidative dehydrogenation and oxidative
dehydrogenation. The processes are represented by Dehydrogenation
Reactor (R-301) and Oxidative Dehydrogenation Reactor (R-302)
respectively.

11
The process gas from Section 1, the preprocess unit enters the furnace
(F301) at 42.92Co. The furnace will heat up the process gas up to 600Co. The
heated process gas will enter the Dehydrogenation Reactor (R301) where the
n-butane will be converted in to butenes. Hydrogen and other byproduct
such as C1 – C3 will also form.The Dehydrogenation Reactor (R301) is a
fixed bed tubular reactor operating at temperature of 500Co and pressure of
3 bar. The reaction is an exothermic reaction and the temperature is
maintained using molten salt at the shell side of the reactor. The catalyst
used in the reactor is the Pt0.3 Sn 0.6 Cs 0.5 K 0.5 La 3.0 which gives the
conversion of 32.9 % and selectivity of 96%.
The butenes from R301 will be cooled down from 600Co to 420Co by
Dehydrogenation Intercooler (E301) before further supplied to Oxidative
Dehydrogenation Reactor (R302). The R302 is also a fixed bed tubular
reactor and is operating at temperature of 330Co and pressure of 3 bar.
The reaction is an exothermic reaction and the temperature is maintained by
molten salt. The catalyst used in the reactor is the Mo12Bi1Cr3Ni8Zr1Fe0.1 K 0.2
which gives the conversion of 99 % and selectivity of 96%.

12
 The Oxidative Dehydrogenation Reaction in R302 will convert the butenes to
butadiene and also byproducts such as C1-C3, Carbon Oxide, Carbon Dioxide
(CO2 ), water (H20) , and Hydrogen (H2 ). The product gases from the reactor
need to be cooled down to 24.48Co by two Dehydrogenation Reactor Coolers
which are the E302 and also E303 before can be sent to Section 3, the
purification section.

2-4 Purification Section:

The purity of 1,3-butadiene produced is demanded to be at least 99.6%. To

achieve the high purity, purification section is employed to separate 1,3-
butadiene from any impurities.

13
The product stream which comes from reactor section contains component
as heavy as water and as light as hydrogen.

Table 2-2 product stream from reactor

o
Component NBP (C ) Mole Fraction
Hydrogen -252.6 0.0099
CO -191.45 0.00018
Oxygen -182.95 0.0329
CO2 -78.55 0.00028
butenes -6.25 0.0029
1,3-butadiene -4.45 0.3487
n-butane -0.5 0.5815
H2 O 100 0.233
Total 1

Due to wide array of component‟s boiling point, different method of separation is

utilized. First is by cooling the stream to achieve partial condensation which is
happened in the previous section. The stream is then introduced to flash drum V-
401 to separate the liquid phase which is essentially water from the gaseous
phase. The liquid phase is sent to water treatment section while the gas is fed into
compressor K-401 to do partial condensation by compression. The K401 outlet
stream is sent to a flash drum V-402 to separate off-gas from C4 which is the
liquid phase.
Afterward, liquid C4 stream enter a distillation column C-401. Since the relative
volatility is very low, thus extractive distillation is employed where solvent is
introduced at the upper trays and feed enters the column at lower tray of C-401.
The column is equipped with a condenser E-402 at 30Co and 304kPa of operating
condition and a reboiler E-403 to supply heat at 70Co and 354kPa of operating
condition. The overhead product consists of all the feed but solvent and 1,3-
butadiene. Overhead product is sent back to C-101 Pretreatment Section. On the
other hand, solvent extracts 1,3-butadiene from the feed stream and leave the
column as bottom product to solvent recovery column, C-402.
The C-401 bottom product enters solvent recovery column, C-402. The purpose
of C-402 column is to recover solvent and produce 99.7% purity of 1,3-
butadiene. The heat to column C402 is supplied by a reboiler E-403. The
operating condition of E-403 is at temperature 208Co and pressure 355kPa. The
bottom product is the solvent which will be recycled to column C401, while
overhead of the column is cooled down in a condenser with operating condition is
at 27.45Co and 304kPa and collected in a reflux drum. Eventually, final product
of 1,3-butadiene flows from the reflux drum to storage.

14
Chapter Three

Material and Energy Balance

15
3-1 Material Balance

3-1-1Distillation column :

Light Key Component : i-C4

Heavy Key Component : n-C4
Feed = 3000 kmol/hr
Feed Distillate Bottoms
Components XF Mole % Xd Mole% Xb Mole%
C3 27 0.009 27 0.03710499 0 0
i-C4 777 0.259 693.084 0.95247676 83.916 0.036929
n-C4 2166 0.722 7.581 0.01041826 2158.419 0.949868
C5+ 30 0.01 0 0 30 0.013202
Total 3000 1 727.665 1 2272.335 1

Split Fractions of LK = 0.892

16
3-1-2 For Distillat :

C3 : In = Out = 27 kmol/hr
i-C4 : 777*0.892 = 693.084 kmol/hr
n-C4 : (1 – 0.9965)*2166 = 7.581 kmol/hr
Total : 727.665 kmol/hr

3-1-3 For Bottoms :

i-C4 : 777-693.084 = 83.916 kmol/hr

n-C4 : 2166-7.581 = 2158.419 kmol /hr
C5+ : 30 kmol/hr

3-1-4 Non-Oxidative Dehydrogenation Reactor :

Assumption : 35% conversion of n-Butane to (1,cis,trans) Butenes

17
Components Feed(Kmol/hr) (KJ/hr) Product(Kmol/hr) Kg/hr
n-C4 2158.419 131339.7962 1402.97235 81544.9619
Butenes 0 0 863.3676 48440.9659
H2 0 0 671.5081333 1353.7604
131339.7962 2937.848083 131339.688

n-C4 : 2158.419-(2158.419*0.35) = 1402.9723 kmol/hr

Butenes : ( 2158.419*0.35)*(4/3.5) = 863.36 kmol /hr
H2 : (2158.419*0.35)*(4/4.5) = 671.50 kmol/hr

Amount of O2 added : (863.3676*3/10)*(1.07) = 277.1409996 Conversion :

99.16 % of reacted of Butenes for Butadiene & 50% O2 is reacted.

18
Components Feed(Kmol/hr) (Kg/hr) Product(Kmole/hr) Kg/hr

n-C4 1402.97235 81372.3963 1402.97235 81372.3963

Butadiene 0 0 856.113122 48798.5728

Butenes 863.367 48348.5856 7.25228784 413.380407

H2 671.5081333 1343.016267 671.5081333 1399.28865

O2 277.1409996 8868.511987 138.5704998 4614.39764

H2 O 0 0 173.2131248 3268.53166
CO 0 0 0.90653598 26.1082362
CO2 0 0 0.90653598 40.0054328
139932.5102 139932.681

n-C4 : In = out = 1402.97235

Butadiene : 863.3676*0.9916 = 856.1153122
Butenes : 863.3676 - (863.3676*0.9916) = 7.25228784
H2 : In = Out = 671.5081333
O2 : (277.1409996*0.50) = 138.5704998
H2O : (277.1409996*0.50)*(10/8) = 173.2131248
CO : ((863.3676 - (863.3676*0.9916)) / 2) = 0.90653598
CO2 : ((863.3676 - (863.3676*0.9916)) / 2) = 0.90653598

19
3-2 Energy Balace

3-2-1 Distillation Unit

Inlet Temperature = 313k

Overhead Temperature = 510 K
Temperature Difference = 197 K
Distillate Flow Rate CP Enthalpy
Component Xd Mole% In Kg/hr KJ/kmole K H(Kj/hr)
C3 27 0.03710498 1188 76.701 407972.619
i-C4 693.084 0.952476758 40198.872 101.475 13855147.68
n-C4 7.581 0.010418256 439.698 101.475 151548.5491
C5+ 0 0 0 114..002 0
Total 688.37109 1 41826.57 14414668.85

Q = mCpΔT
Condenser Duty Qc = (Qv- QD-QL)
V = 1.408836 kmol/sec
Cp = 89.72 J/kmol K
)Qv = 14.4088*3600*89.72*( 510-273
Qv = 107845163 KJ/hr
L = 1.206707 kmol/sec
Cp = 119 J/kmol K
)QL = 1.206*119*(298-273
QL = 12916260 KJ/hr
Similarly we can find the QD for distillate in which temperature difference is
taken as
(773-273)K
Reference Temperature is 273 K
QD = 25361268.33 KJ/hr
Hence Condenser Duty Qc = 107845163 – 12916260 - 25361268.33
Qc = 69567634 KJ /hr

21
 For Bottom:

Inlet Temperature = 313 K

Bottom Temperature = 773 K
Temperature Difference = 448 K

Bottoms Cp Flow Rate Enthalpy

Components Xb Mole% Kg/kmol K KJ/hr H(KJ/hr)
C3 0 0 68.318 0 0
i-C4 83.916 0.03692941 104.766 4867.128 3938611.6
n-C4 2158.419 0.094986831 104.766 125188.3 101305758.5
C5+ 30 0.01320228 117.592 2100 1580436.5
Total 2149.629 1 132155.4 106824806

Reboiler Duty QB = QW+QD+QC-QF-QL

Reference Temperature = 273K
For Qw temperature difference = 773-273=500 K
QW = 224598914 KJ/hr

For feed stream Temperature difference = 313-273= 40 K

Qf = 16100760 KJ/hr
Hence Reboiler Duty QB
QB = 224598914 +25361268.33 +69567634 -16100760 – 12916260
QB = 290510796 KJ/hr

3-2-2 Non-Oxidative Dehydrogenation Reactor:

Inlet Temperature : 773 K

Outlet temperature : 603 K
Temperature Difference : 170 K

21
Components Product(Kmol/hr) Cp(KJ/Kmol k) Enthalpy (KJ/hr)

n-C4 1402.97235 197.955 47213338.95

Butenes 863.3676 169.333 24853494.41
H2 671.5081333 30.043 3429600.204
Total 2937.848083 75496433.56

Enthalpy of outlet stream of Non-oxidative dehydrogenation

= 75496433.56 KJ/hr

3-2-3 Oxidative Dehydrogenation Reactor:

Inlet Temperature : 603 K

Outlet Temperature : 295 K
Temperature Difference : 308 K

Component Product(Kmole/hr) Cp(KJ/Kmol k) Enthalpy (KJ/hr)

n-C4 1402.97235 168.927 72995994.71
Butadiene 865.1153122 133.674 35247652.81
Butenes 7.25228784 144.458 322744.527
H2 761.5081333 29.381 6076710.783
O2 138.5704998 31.692 1352605.494
H2 O 173.2131248 36.424 1943207.376
CO 0.90653598 31.425 8774.271097
CO2 0.90653598 45.468 12695.26041
Total 3251.44478 117960385.2

Enthalpy of outlet stream of Oxidative Dehydrogenation Reactor = 117960385.2

KJ/hr

22
Chapter Four

Dedign of Equipments

23
4-1 Design of Heat Exchanger :

Mass flow Rate(Kg/hr) T in (Co) T out (Co)

Hot Fluid 131339.7 500 330
Cold Fluid 80973.67 160 280
Difference 340 50

)Q= 75496433.56 KJ/hr (From Non Oxidtive Rector Energy Balance

LMTD = ((340-50)/ ln (340/50)) = 151.9269 Co
Assumption : Overall Heat Transfer Co-efficient Uf
= 900 W/M2 Co
A= Q/ U T

Area = 75496433.56 / 900*151.9269

= 154.0239 m2

Assumptions :
Two pass Heat Exchanger with Square pitch Lay out with tube I.D. 0.016 m &
the length of the
.Heat Exhanger is assumed to be 11 ft
CTP= 0.9
CL= 1.0
Pitch Ratio (PR)= P/do
PR= 1.25
do= 0.019 m
P=0.02375
L=3.35 m
A = 154.0239 m2
=0.637( )0.5 ( ) 0.5

Dia. Of Shell (Ds)

= 0.637 *(1/0.9)0.5 *(154.0239 * (1.25)2 *0.019/3.35)
= 0.7447M = 0.8M

No. of Tubes

24
Nt = 0.785 ( )
=0.785*(0.9/1.0)*(0.82/1.252 *0.0192)
=800 For two pass
=400 per pass
Baffle Spacing is 60
B=0.6×0.8=0.48m
Shell Side :Feed from Non-Oxidative Reactor Unit

T=415℃
P=750Kg/m3,Cp=1920 J/Kg K, µ=4.67×10-4k g/m s
K=0.652W/m K ,µw = 6.04×10-4kg/m s
Tube Side: Water
T = 220℃
P=1000 Kg/m3 , Cp = 4160 J/Kg K ,µ= 4.2×10-4 , K = 0.61 W/m K

0.55

Equivalent Diameter (De)

De= 4*(P2-(π*Do/4)) /(π*Do) where P = Do * Pitch Ratio
2 2
=4 * (0.02375 - (π * 0.019 /4))/(π*0.019)t
0.018818m
C=p-Do
C=0.00475m
Area of Flow =(Ds*C*B/P)
=(0.8*0.00475*0.48/0.02375)
0.077285m
Gs=131339.688/(3600*0.077285)
=472.061Kg/sm2
Res=De*Gs/µ
=0.018818*472.061/4.67*10-4=19021.93
Ho=4091.83W/m2k
Now , calculations for hi
m = 80973.67 Kg/hr = 0.037488 m3/s
C/s area of Flow = (Nt * di2*π/8)=0.077449 m2
Um =0.037488/0.07744 = 0.48403m/s
R tube=10088.85

25
 0.4
As

Hi=1759.641W/m2
⁄ -1
Uf = ( +

Hence overall Heat Transfer Coefficient (Uf) = 899.6566 W/ m2 K

: Design Summary
Area = 154.0239 m2
Dia. Of Shell (Ds) = 0.8 m
No. of Tubes

(Nt) = 800 For two pass

per pass = 400
ho= 4283.297 W/m2 K
hi = 1759.641 W/m2 K
(Uf) = 899.6566 W/ m2 K

26
Chapter Five

Cost Estimation

27
5-1 Direct Cost:
Purchased Equipment :

Total Cost of Equipment = 372545281 Rs

Purchased Equipment Installation
Installation of all the equipment listed, structural supports, paints (Taken as 25%
of the purchased equipment cost )
=85685414Rs

28
Total Direct Cost (D) = 797246902 Rs
Indirect Cost (I)
Engineering and Supervision:
Total Engineering and Supervision Cost is taken as 8% of the Total Direct Cost
= 87697159.27 Rs
Construction Expenses:
Total Construction Expenses cost is taken as 7% of the Total Direct Cost
= 63779752.2 Rs
Contractor's Fee:
Total Contractor's fee is taken as 5% of the Total Direct Cost = 39,862,345.12Rs

Contingency :
Total Contingency cost is taken as 8% of the Total Direct and Indirect cost
= 55807283.17Rs

29
)of Total Direct Cost %(
Total Indirect Cost (I) = 247,146,539Rs
.Total Fixed Capital Investment (D + I) = 1,044,393,442 Rs
.Working Capital (WC), 15% of TCI = 184,304,725.10 Rs
Total Capital Investment (TCI) = 1,228,698,167.31 Rs

Total Product Cost:

Determination of the necessary Capital Investment is only one part of a complete
cost estimate .
Another equally important part is the estimation of costs for operating the plant
and selling the products .
These costs can be grouped under the general heading of Total Product Cost .

Basis :
1-Total cost calculated on The basis on the AnnualCost Basis
2-Number of days working per year is taken as 330 days
3-plant is running in three shifts i e 24 hrs per days
4-capacity of the plant per year =1512939600kg/yr manufacturing cost

31
Direct Production Costs

31
Total Direct Production Cost :

Total Direct Production Cost = 493273378Rs

Fixed Charges
a) Depreciation
i) Annual cost of Depreciation for Machinery and Equipment is assumed as 10%
of the Fixed Capital Investment = 10,443,934.42 Rs

ii) Annual cost of Depreciation for buildings is taken as 3% of the Initial Cost of
buildings = 1899980.94 Rs

iii) Annual cost of Depreciation for Instrumentation & Controls, piping,

Electrical equipment and Materials is assumed as 5% of FCI = 52,219,672.11 Rs

b) Taxes : Annual property taxes for plant is assumed as 1% of the Fixed Capital
investment = 10443934.42 Rs

c) Insurance : Annual cost of Insurance is assumed as 1% of the Fixed Capital

Investment = 10443934.42Rs

d) Rent Annual cost of Rent for Land and Buildings = 0.00 Rs

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. Total Fixed Charges = 85451456Rs

Plant Overhead Cost:

Annual Plant Overhead Costs is assumed as 30% of the total cost of operating
labor, supervision and maintenance = 2,038,193,918.38 Rs

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Total Manufacturing Cost = 49,408,069,365.70 Rs

General Expenses :

Administrative Expenses :
Annual cost of Administrative expenses is assumed as 25% of the total cost of
operating labor = 1,475,1161.10 Rs

Distribution and Marketing Expenses :

Annual cost of Distribution & Marketing expenses is assumed as 10% of the
Total Product Cost = 49,327,337.82 Rs

Research and Development :

Annual cost of Research and Development = 24,663,668.91 Rs

Financing (interest):
Annual cost of Financing (interest) = 0.00 Rs

Total Cost of General Expenses = 88,742,167.82 Rs

Total Product Cost (TPC), M + G = 691,176,512.14 Rs

34
Chapter Six

Material Safety and Hazard

35
Material, Safety and Chemical Hazard :

1-Distillation :

1-In a distillation column, among the potential accident that can happen is
flooding.
This circumstance occurs as a result of high pressure in the column. There are
also large inventories of boiling the liquid such as sometimes under pressure, in
the distillation column both in the base and held up .

2- To prevent the accident from happened, sequence that tends to minimize the
flow rate of nonkey component can be chose .
Dividing wall column can be used to reduce the inventories and also
number of items to lower the potential for leaks. In case of over pressurization,
the relief system can be installed .

2- Pressure and Temperature

1-High temperature condition in a plant can lead to possible rupture of tubes

carrying process fluids .
Thermal shock and leaking flanges also can occur due to the loss of cooling
medium .
Problem of fluids leaking can become more serious with high pressure operation
because when fluid is flashing, mass flow rate of liquid can increase which can
leak through holes .

2-In order to overcome the high temperature and pressure condition, relief
system must be installed.
Automatic shutdown system also must be installed to prevent overpressure and
temperature .
The system must always be operated at normal temperature and pressure
condition .

3- Heat Transfer Operation :

1-Generally, problems include in heat transfer operation involve tube rupture,

leaking polymerization and solidification.
36
These problems will influence the pressure and temperature
conditions in heater and also cooler.

2-Pressure relief can be used to overcome the overpressure consequences and

.also to protect against tube rupture.
To prevent thermal shock, the control valve (fail-to-open/fail-to-close) can be
used to control the flow rate of cooling or heating medium.

4- Chemical storage :
1-Chemicals which are highly flammable can lead to explosion. Leakage of
chemical from the storage tank can also cause the vapor cloud and toxic cloud to
occur. Failure of instrumentation especiciall Those which indicate the pressure
And temperature will also cause the explosion to happed .
Leaking of chemical into the sewage system also can happen in this area .

2-Prevention step can be taken to avoid all of these accidents from occurring. To
prevent explosion, the explosion proof motor and switches should be installed.
The use of non-sparking
tools and equipment is required. All storage areas must be clearly marked with
warning notices forbidding smoking and open fire. Pressure safety valve should
be installed to maintain the
pressure inside the storage tank. The storage area also should have no drain
without suitable cover or water seal to prevent the chemicals from entering the
sewage system.

5- Transportation:

1- Accident involves in this transportation factor involve spillage of toxic

chemicals and also risk of accident happened. Sometimes, the explosion can also
happen due to pressure and temperature change in the transportation tank.

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2- In handling the loading and unloading of the chemicals, the workers should
wear proper Personal Protection Environment (PPE).
Training should be provided to the driver of the vehicles so that
they can drive carefully and avoid the risk of road accident. To reduce the effect
caused by sudden changes of vehicle speed, baffles should be installed. Other
technical requirements such as gauges, thermometers, safety valve, indicator for
maximum and minimum filling and also device to remove static electricity should
be installed to make sure that the tanks are in normal condition. In case of
transportation by sea, tankers with heat-insulated reservoir should be used.

6- Materials for Construction:

Leakage, corrosion, crack and explosions can happen due to the poor materials
used for the construction purpose. Crack problem can also arise if high pressures
occur within the vessels.

To prevent such incident from happening, stainless steel is recommended to be

used for process stream to prevent corrosion. Electrical equipment used should
also be spark resistance to prevent explosions .

7- Toxicology and health hazard:

Most chemicals used in the plant either in process stream or product has contains
of several hazardous materials. When the toxic chemicals come into contact with
human being, it can cause a very bad impact to human‟s health. Human being
might expose to human mutagenic effect if they are exposed to the chemicals for
such long period.

In order to prevent all these bad consequences from happening, proper Personal
Protection Equipment (PPE) should be worn by workers when dealing with the
toxic chemicals.
Handling procedure of these hazardous materials should also be understood well
to avoid the accident Supervision from expert personnel during handling
chemicals also is useful to prevent any accident from occurring.

8- Flammability:

38
If the chemicals in reboiler or heater are overheated, explosion may occur. In
addition, spark can be produced from tools or vehicles used in the process area
which can lead to explosion or fire accident.

The vehicles and also the tools with spark resistance can only be used in the
process area. All
The vehicles and also the tools with spark resistance can only be used in the
process area. All activity which can lead to the production of sparks must be
)especially smoking(prohibited in the process area (especially smoking). .

9- Explosion limit:
If the oxygen content in the reactor and other equipments exceed its normal limit,
explosions can occr.

To reduce the risk, total oxygen amount content in all these equipments should
always be less than its maximum limit. . A standard practice of ensuring oxygen
content less than 2% shall be employed prior to introduce flammable chemicals.

39
CONCLUSION

The design project of the Butadiene production plant has met its objectives of
producing 15,129,39600 tone / year of Butadiene with a purity of more than 99%
and is based on 330 working days and 7920 operating hours per year.

It has been proven conceptually that the setting up of a Butadiene plant in India
is feasible and crucial in order to meet the high demand of Butadiene in the Asian
region. From the feasibility research carried out, the Jamnagar or Hazira are
identified to be the best location for a Butadiene production plant. This is due to
the combination of attractive features, incentives and availability of raw material.
Basic utilities such as steam and raw water are obtained easily. Moreover heavy
machinery and raw materials, fuel and all equipments can be directly delivered to
Jamnagar Plant because of Arabian Sea. Furthermore, the product can also be
transported easily through marine.

The initial information of product and feed together with the reaction kinetics
has been vital in evaluating the feasibility of the chosen process route. The best
method to produce Butadiene so far has been the non-oxidative dehydrogenation
reaction of n-butane to butenes and followed by
oxidative dehydrogenation of butenes to butadiene.
The process is carried out in four stages. In distillation column, the height of
distillation column is 28 m. The no. of actual trays are 56. The diameter of
column is 3.5 m. In second stage n butane is dehydrogenated to butenes. The
butenes are further dehydrogenated in oxidative dehydrogenation reactor to 1,3
butadiene.In final stage the product 1,3 butadiene is separated
from unreacted n-butane by extractive distillation column.

As far as designing of the reactor is concerned the volume calculated for the
reactor is 2.4 m3 The diameter of the multitubular reactor is 1m. The no, of tubes
.are 1060.The catalyst used in

Non-oxidative dehydrogenation reactor is Pt0.3 Sn0.6Cs0.5K0.5 La3.0. While

the catalyst used in oxidative dehydrogenation reactor is
Mo12Bi1Cr3Ni8Zr1Fe0.1K0.2. The solvent used in extractive
distillation column is DMF (dimethyl formaldehyde).

41
Finally the cost of the butadiene production plant is also reasonable. The Total
Capital Investment is 1,228,698,167 Rs. The Total Production Cost of the plant is
691,176,512 Rs. The annual net profit after the income tax paid is 389899061.
The payback period of the project is 2.298084225 year & the rate of return of the
project is 56.41%.

Overall, as a conclusion, the project has achieved the overall objectives for
preliminary design stages of the Butadiene production plant. For accurate design
purposes, the recommendations should be taken into consideration and applied
into the design project of Butadiene production plant.

41
References :

[1] Biegler L.T, Grossmann I.E and Westerberg A.W, Systematic Methods of
Chemical Process Design, Prentice Hall, United States. (1997)

[2] Bhasin M.M et al, “Dehydrogenation and Oxydehydrogenation of Paraffins to

Olefins”, Applied Catalyst A: General 221, 397-419 (2001)

[3] Douglas J.M, Conceptual Design of Chemical Processes, Mc Graw Hill,

Singapore. (1988)

[4] Dow , Propylene Oxide, http://www.dow.com/propyleneoxide/app

/index.htm (2007)

[5] Geoff Wells, (1996) Hazard Identification and Risk Assessmen.

[6] Jackson S.D and Rugmini S., “Dehydrogenation of n-butane Over Vanadia
Catalysts Supported on θ Alumina”, Journal of Catalysts 251, 59-68 (2007)

[7] Peters M.S and Timmerhaus K.D., Plant Design and Economics for Chemical
Engineers, 4th Edition, Mc Graw Hill, Singapore.(1991)

[8] Wikipedia , http://en.wikipedia.org/wiki/Butane (2007)

[9] Schindler G.P, Walsdorff C., Harth K. Hibst H., Method for the production of
butadiene from n-butane, United States Patent.(2006)
[10] Chang J.(2006), http://www.icispricing.com/
[11] Introduction to Process Equipment Design By
Bhattacharya .

42
[12] Process Equipment Design By M.V. Joshi .

[13] Perry's Chemical Engineers' Handbook, Eighth Edition [Don Green, Robert
Perry] 8 th Edition.

43
Thank you

44