Project Report

Manufacturing of 1,3-Butadiene
Butadiene from ethanol
CHAPTER-1
INTRODUCTION
1.1 Butadiene Introduction:
Butadiene is a flammable, colorless gas with a mild aromatic odor and it is highly reactive. Its
physical Description - Colorless gas that has a mild gasoline-like
like odor. Its molecular weight is
54.1 & boiling/melting point 24F / -164F.
164F. Butadiene is soluble in alcohol and ether, insoluble
in water and polymerizes readily, particularly if oxygen is present. 1,3--Butadiene is a simple
conjugated
ugated diene. It is an important industrial chemical used as a monomer in the production of
synthetic rubber. When the word butadiene is used, most of the time it refers to 1,3-butadiene.
1,3
1.2 History:
1,3-Butadiene
Butadiene was discovered in the nineteenth century and its use in the development of rubberrubber
like polymers was explored during the early 1900s (Grub and Loser 2005; Sun and Wristers
2002). Large volume production of 1,3
1,3-butadiene
butadiene in the United States began during World War
II. The Russian chemist Sergei Vasilyevich Lebedev was the first to polyme
polymerize butadiene in
1910.In
In 1926 he invented a process for manufacturing butadiene from ethanol, and in 1928,
developed
method
for
producing
polybutadiene
using
sodium
sodium
as
catalyst.
There are two sources of butadiene in world: Extractive distillation from Crude C4 stream
produced as a co-product
product of ethylene production, and on-purpose
on purpose production by
dehydrogenation o n-Butane
Butane or nn-Butenes. Leading licensors of technology
ology for Butadiene are
Shell, Nippon-Zeon etc.
SCOE, Chemical Engineering
Page 1
Manufacturing of 1,3-Butadiene from ethanol
Table 1.1 Properties of 1, 3 Butadiene

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, 20C
2.4 bar
Relative density, gas (air=1)
1.9
Relative density, liquid (water=1)
0.65
Solubility in water [mg/l]
1025
1.3 Applications:
The largest single use for butadiene is in the production of styrene- butadiene rubber (SBR)
which in turn is principally used in the manufacture of tires. According to Huntsman (2006),
about half of all butadiene consumption in the United States is for styrene butadiene rubber
(SBR) and polybutadiene (PB), the primary feed to tires manufacturing. Approximately 14% of
the butadiene consumed in the US goes into the production of nylon 6, 6 which is used in making
carpet. About 13 % of the butadiene is used in the manufacture of styrene butadiene latex (SBL)
which is further processed into products such as adhesives and carpet backing. Another
Page 2
important use for butadiene is the production of acrylonitrile butadiene styrene (ABS) plastic
which is used for pipe, automotive components and housings for electronic equipment such as
telephones and computers.
1.4 Market:
According to CMAI (2007), global butadiene demand is expected to grow at just under
3.5%/year through 2014, slightly above the average of 3.2%/year growth of the past five years.
Demand in India will be the largest, growing nearly 15%/year for the next five years. Demand in
Asia is expected to exceed 5%/year, although demand in some countries, primarily China, will
be at more than 10%, analysts say. Demand in North America and Western Europe is expected to
rise at less than 1%.
Most of the capacity will be added in Asia, particularly China, which will account for nearly
75% of new capacity, added before 2012. Operating rates in Asia are expected to be strong at
85%-90%, while operating rates in Europe will be highest, at about 90%, analysts say. Operating
rates in North America are expected to hover in the 70% range, they say. Table 2.3 shows the
butadiene producer and production rate in Asia. Notice that in Malaysia, there is only 100,000
MT /year production totally.
Table 1.2 Production of butadiene worldwide
Country
Producers
Production Rate
(in thousands of MT./year)
Yangzi Petrochemical
185
CNOOC Shell Petrochemicals4
155
Maoming Petrochemical
150
Jilin Chemical
140
Qilu Petrochemical
130
Lanzhou Petrochemical
120
China
Page 3
India
Japan
Korea
Malaysia
Shanghai Petrochemical
120
Yanshan Petrochemical
113
Others
395
Total
1508
Reliance Industries
150
Others
172
Total
322
Japan Synthetic Rubber
268
Chiba Butadiene
177
Nippon Zeon
150
Okayama Butadiene
140
Tobu Butadiene
130
Tonen General
105
Nippon Petrochemicals
70
Total
1040
Yeochon Naphtha Cracking Centre
218
Korea Kumho Petrochemical
205
LG Chemical
145
Lotte Daesan Petrochemical
109
Samsung Petrochemicals
99
LG Daesan Petrochemical
98
SK Corp.
72
SK Energy
72
Total
1018
Titan Petchem
100
Total
100
60
Singapore
Total
60
Page 4
CHAPTER-2
LITERATURE REVIEW
2.1 Butadiene Manufacturing Process Information :

Butadiene is produced commercially by four 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).
4) Dehydrogenation Dehydration of Ethanol.
Each of first three processes produces a stream commonly referred to as crude butadiene that is
rich in 1,3-butadiene.
2.1.1 Butadiene Production Via Steam Cracking of Paraffinic Hydrocarbons
The steam cracking process is reported to be the predominant method of the three processes of
production, accounting for greater than 91% of the world's butadiene supply. Figure depicts a
flow chart for a typical olefins plant. While this does not represent any particular plant, and there
are certainly many variations among olefins plants, this representation will provide the reader
with a general understanding of the process.
The indicated feedstocks (ethane, propane, butane, naphtha and gas oil) are fed to a pyrolysis
(steam cracking) furnace where they are combined with steam and heated to temperatures
between approximately 1450-1525 F (790-830 C). Within this temperature range, the feedstock
molecules "crack" to produce hydrogen, ethylene, propylene, butadiene, benzene, toluene and
other important olefins plant co-products. After the pyrolysis reaction is quenched, the rest of the
plant separates the desired products into streams that meet the various product specifications.
Process steps include distillation, compression, process gas drying, hydrogenation (of
Page 5
acetylenes), and heat transfer. The focus of this review is 1,3-butadiene;however, since butadiene
is created in the olefins plant pyrolysis furnace, and is present in the crude butadiene product
stream at concentrations up to approximately 75 wt%, the olefins plant process and the crude
butadiene stream are addressed in this publication to a limited degree.
Fig 2.1 Butadiene Production Via Steam Cracking of Paraffinic Hydrocarbons
The flow path of the C4 components (including butadiene) is indicated by bold [red] lines.
While some olefins plant designs will accommodate any of the listed feedstocks, many olefins
plants process only Natural Gas Liquids (NGLs) such as ethane, propane and sometimes butane.
The mix of feedstocks, the conditions at which the feedstocks are cracked, and the physical plant
design, ultimately determine the amount of each product produced, and for some of the streams,
the chemical composition of the stream.
Page 6
2.1.2 Butadiene Production via Catalytic Dehydrogenationof n-Butane and n-Butene (the
Houdry process)
The catalytic dehydrogenation of n-butane is a two-step process; initially going from n-butane to
n-butenes and then to butadiene. Both steps are endothermic.A major butane-based process is the
Houdry Catadiene process outlined in Figure.
Fig 2.2 Butadiene Production via Catalytic Dehydrogenation of n-Butane and n-Butene
(the Houdry process)
In the Houdry process, n-butane is dehydrogenated over chromium/alumina catalysts. The

reactors normally operate at 12-15 centimeters Hg absolute pressure and approximately 11001260 F (600-680 C). Three or more reactors can be used to simulate continuous operation:
while the first reactor is on-line, the second is being regenerated, and the third is being purged
prior to regeneration. Residence time for feed in the reactor is approximately 5-15 minutes. As
the endothermic reaction proceeds, the temperature of the catalyst bed decreases and a small
amount of coke is deposited. In the regeneration cycle, this coke is burned with preheated air,
Page 7
which can supply essentially all of the heat required to bring the reactor up to the desired
reaction temperature.
The reactor effluent goes directly to a quench tower, where it is cooled. This stream is
compressed before feeding an absorber/stripper system, where a C4 concentrate is produced to
be fed to a butadiene extraction system for the recovery of high purity butadiene.
2.1.3 Butadiene Production via Oxidative Dehydrogenation of n-Butenes (the Oxo-D or OX-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. 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
Page 8
stripped from the oil, recovered in the overhead of the stripper, then it is sent to a purification
system to recover the butadiene product.
Fig 2.3 Butadiene Production via Oxidative Dehydrogenation
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.
Page 9
2.1.4 Butadiene production from ethanol

Our process is divided into five main sections, as shown in Figure. The first section includes the
dehydrogenation of ethanol, in which ethanol reacts to form acetaldehyde and hydrogen. This is
followed by a separation sequence, which consists of a series of pressure and temperature
changes to separate the light components, namely hydrogen, from the heavy components. The
second section also includes a system for purifying the hydrogen so that it can be sold. The third
section consists of the second reaction, which uses the heavy products of the first reaction as its
reactants and produces butadiene and water. Finally, this is followed by a distillation train to
separate out the final product, butadiene, the byproducts, and the recyclable feeds, ethanol and
acetaldehyde, which are sent back to the second reactor. The fifth section contains the Dowtherm
heating system, which recycles Dowtherm A to the two reactor sections to pre-heat and maintain
the operating temperature of both reactions. The diagram of the process is reproduced below for
convenience.
Fig 2.4Butadiene production from ethanol
Page 10
CHAPTER-3
THERMODYNAMICS AND KINETICS
3.1 THERMODYNAMICS
FEASIBILITY OF REACTION:
The thermodynamic feasibility of chemical reaction can be formulated from the value of
standard free energy change & this help in preliminary exploratory work. It would worthwhile
to have some idea of whether or not equilibrium is favorable before we search for catalyst &
other conditions to cause reaction. If reaction is not feasible, there is no point in pursuing a long
& expensive investing on improving the rate of reaction. The equilibrium constant related to
standard free energy of reaction that gives the necessary information from thermodynamic
possibility of reaction.
If G for a reaction is zero then K is equal to one, then reaction proceeds with
considerable extent before the equilibrium is reached.
If G for a reaction is negative then K is greater than one then reaction is feasible.
If G for a reaction is greater than zero then the reaction is less feasible, but in some case
reaction with high G is certainly feasible from stand point of industry operation.
Example: In the methanol synthesis reaction with G= -46200 KJ/mol at 600 K is found to
be feasible. The reaction is carried out at high pressure to overcome unfavorable free energy
change.
Thermodynamics study on chemical system can be conducted as follows:
Calculation of heat of formation of reaction:
Heat of formation of reaction (H reaction) can be calculated by enthalpy of formation of

different inducible components.
(H) reaction = (H) products - (H) reactants
Page 11
If (H) reaction < 0, then chemical reaction is exothermic & cooling is required to maintain the
desired reaction temperature. If (H) reaction > 0, then reaction is endothermic & heating is
needed to maintain the desire reaction temperature.
Calculation of Heat of Reaction:

Heat of reaction of for any chemical reaction can be calculated from enthalpy of
formation data as follows:
(H) reaction = (H f) products - (H f) reactants

Where,
(H f)= A + BT + CT2
(H f) = Enthalpy of formation (KJ/Kmol)
A, B, C = thermodynamics constants
T = temperature in Kelvin
Table 3.1 Enthalpy of formation data for first reaction
Components
(H f 548)
. CH3CH2OH
-216.916
-6.9572e-2
3.1744e-5
-244.788
H2
CH3CHO
-154.22
-4.7166e-2
2.0279e-5
-173.977
For main Reaction of first reactor :

(H) = [(H f) CH3CHO + (H f)H2] -
[(H f)CH2CH3OH]
= [ -173.977 + 0] - [ -244.788]
(H) reaction = 70.811 KJ/Kmol.
Page 12
Table 3.2 Enthalpy of formation data for second reaction
Components
(H f 623)
. CH3CH2OH
-216.916
-6.9572e-2
3.1744e-5
-247.938
H2O
-238.41
-1.2256e-2
2.7656e-6
-244.97
CH3CHO
-154.22
-4.7166e-2
2.0279e-5
-175.733
CH2CH=CHCH2
123.286
-5.1225e-2
2.3192e-5
100.2374
For main Reaction of second reactor:

(H) = [(H f) BUTADIENE + 2(H f) H2O] -
[(H f) CH2CH3OH + (H f) CH3CHO]
= [ 100.374 + (2 * - 224.9748)] [ - 247.938 175.733 ]

(H) reaction = 34.105 KJ/Kmol
Calculation of Gibbs Free Energy:

G = H - TS
Where,
S= Entropy change
Page 13
Table 3.3 Gibbs free energy of formation data for first reaction
Components
(G f 548)
. CH3CH2OH
-236.103
2.1904e-1
2.5659e-5
-108.363
H2
CH3CHO
-167.052
1.0714e-1
1.8665e-5
-102.734
For main reaction of first reactor :

GR = (G) products - (G) reactants
= [ -102.734 +0] [- 108.363]
GR = 5.629 KJ/kmol
K = 1.01
(Reaction is feasible).
Table 3.4 Gibbs free energy of formation data for second reaction
Components
(G f 623)
. CH3CH2OH
-236.103
2.1904e-1
2.5659e-5
-89.68
H2O
-241.74
4.1740e-2
7.4281e-6
-212.85
CH3CHO
-167.052
1.0714e-1
1.8665e-5
-93.05
CH2CH=CHCH2
109.172
1.3296e-1
1.9003e-5
200.381
Page 14
Gibbs free energy for main reaction:

GR = (G) products - (G) reactants
= [ 199.81 + (2*-212.852)] [ -89.65 93.05]
GR = -43.623 KJ/Kmol
K=1.01 (reaction is feasible)
3.2 KINETICS
The first step of the process involves the dehydrogenation of ethanol to acetaldehyde. Kinetics
are readily available for this reaction using an unsupported copper-chromite catalyst and were
used to determine optimal conditions for the first reactor (Peloso, 1979). The mechanism
involved is a dual-site surface reaction of the adsorbed ethanol. The mechanism for the reaction
was derived first using a homogenous Hougen-Watson method.
CH3 CH2 OH CH3 CHO + H2
A=
(A
(1)
(2)
R pS )
(3)
The reaction rate was then corrected by a Langmuir-Hinshelwood, dual-site, surface reaction
controlled mechanism.
A
(A
(1+
R pS
(4)
2
S)
where RA is the rate of the reaction in mol/L-s, pi is the partial pressure of species i in atm, k is
the reaction rate constant in mol/s-kg cat.-atm, Ki is the adsorption coefficient for species i in
atm-1, and Ke is the equilibrium constant in atm. The corrections to the original homogenous
model were necessary due to the variance of reaction step speeds. The reaction steps were as
follows:
+
(5)
Page 15
+
+
+
(6)
(7)
(8)
(9)
Where A, S, and R denote molecules of ethanol, acetaldehyde, and hydrogen, respectively. A2

denotes a reactive intermediate, and L denotes the catalyst surface. The controlling steps of the
mechanism are the surface reactions (6) & (7), which occur in parallel on the catalyst. In this
model, ethanol approaches the catalyst and then adsorbs to its surface which is a fast step (5).
The surface reaction takes place where hydrogen is adsorbed away from acetaldehyde on a
second site of the catalyst surface which are the rate controlling slow steps, (6) and (7). Finally,
desorption of acetaldehyde and hydrogen occurs, freeing both molecules from the catalyst, which
are fast steps, (8) and (9). The following mass balance, based on the above mechanism, was
presented in the literature.
(10)
where pB is the catalyst bed density, S is the cross sectional area of the reactor, nAo is the ethanol
feed rate, and is the ethanol conversion. The mass balance (10) and reaction rate (4), in
conjunction with the following expressions for K values, were used and manipulated to calculate
the reaction conversion and to determine an optimal operating temperature and pressure at which
to run the reaction. Expressions for K values were determined by fitting curves to experimental
data.
lnKe = 11.82 6189.1/Tk
(11)
lnk = 17.900 5810.5/Tk
(12)
lnKA = 1.175 1166.6/Tk
(13)
lnKR,S = 1.057 690.2/Tk
(14)
where Tk is the reaction temperature, k is the reaction rate constant in mol/s-kg cat.-atm, Ki is
the adsorption coefficient for species i in atm-1, and Ke is the equilibrium constant in atm.
Page 16
CHAPTER-4
MATERIAL AND ENERGY BALANCE
4.1 MATERIAL BALANCE
Composition of Fresh Feed:
Basis: 1500 Kmol/hr ethanol solution = 66900 Kg/hr.
Pure ethanol in ethanol solution = 0.95 * 1500
= 1425 Kmol/hr
= 65,550 Kg/hr.
Water in ethanol solution = 75 Kmol/hr
= 1350 Kg/hr.
Material balance over first heat exchanger:
Input
Output
As composition remains the same, therefore

Output
Input
Therefore, output consists of

Pure ethanol in ethanol solution = 0.95 * 1500
= 1425 Kmol/hr
Page 17
= 65,550 Kg/hr.
Water in ethanol solution = 75 Kmol/hr
= 1350 Kg/hr.
Output = 66900 Kg/hr.
Material balance over first reactor:

Dehydrogenation of Ethanol:
Main Reactions:
1. CH3 CH2 OH CH3 CHO + H2
Selectivity = 92%
Side Reaction for first reactor:

1. CH3CH2OH
CO + CH4 + H2
(0.75 %)
2. CH3CH2OH + H2O
CO2 + CH4 + 2H2
(0.75 %)
3. CH3CH2OH + H2O
CH3COOH + 2H2
(2.5 %)
4. 2CH3CH2OH
CH3CH2OCH2CH3 + H2O
5. CH3CH2OH + CH3COOH
(2.5 %)
CH3COOCH2CH3 + H2O.
(1.75 %)
For main reaction :

CH3 CH2 OH CH3 CHO + H2
Conversion = 55%
Ethanol converted = 1425/2

=712.5 Kmol/hr.
= 32,775 Kg/hr.
Page 18
Ethanol reacted to form acetaldehyde = 0.92 * 32,775

= 655.5 Kmol/hr.
= 30,153 Kg/hr.
Acetaldehyde produced = 655.5 Kmol/hr
= 28,842 Kg/hr
Hydrogen produced = 655.5 Kmol/hr
= 1311 Kg/hr.
For side reactions of first reactor:

First reaction:
Ethanol reacted = 32,775 * (0.75/100)
= 5.343 Kmol/hr.
= 245.8125 Kg/hr.
Carbon monoxide produced = 5.343 Kmol/hr
= 149.625 Kg/hr.
Methane produced = 5.343 Kmol/hr
= 85.48 Kg/hr.
Hydrogen produced = 5.343 Kmol/hr
= 10.686 Kg/hr.
Page 19
Likewise for all other side reactions, a chart is prepared below to estimate the amount of
ethanol reacted and by products formed.
Table 4.1: Amount of ethanol reacted to form by products (Kmol/hr)
Components
. CH3CH2OH
5.343
5.343
17.8125
17.8125
12.46875
CO
5.343
CO2
5.343
CH4
5.343
5.343
CH3CH2OCH2CH3
8.90625
H2
5.343
10.686
35.625
H20
5.343
17.8125
8.90625
12.46875
CH3COOH
17.8125
12.46875
CH3COOCH2CH3
12.46875
Page 20
Table 4.2: Composition of output stream from first reactor
Components
Kmol/hr
Mol wt
Kg/hr
CH3CH2OH (Unreacted)
712.5
46
32,775
CH3CHO
655.5
44
28,842
CO
5.343
28
149.625
CO2
5.343
44
235.125
CH4
10.686
16
170.976
CH3CH2OCH2CH3
8.90625
74
659.0625
H2
707.154
02
1414.309
H20
71.43
18
1285.8885
CH3COOH
7.125
60
427.514
CH3COOCH2CH3
10.6875
88
940.50
TOTAL
66900
As hydrogen is produced in considerable amount in first reactor ,so it is sent to the

hydrogen recovery unit for purifying upto 99% and can be sold.
Page 21
Material balance over second reactor:

Dehydration:
CH3 CH2 OH + CH3 CHO CH2CH=CHCH2+ 2H2O
Selectivity = 55%
Acetaldehyde fed = 19.363 kmol/hr

= 852 Kg/hr.
Ethanol fed = (3 * 712.5) = 2137.5 Kmol/hr

= 98,325 Kg/hr.
Table 4.3: Input stream of second reactor

Components
Kmol/hr
. Components from first
Mol wt
Kg/hr
65485.691
reactor (excluding H2)

Ethanol (Recycle)
1425
46
65,550
Acetaldehyde (Recycle)
19.363
44
852
TOTAL
131887
For main reaction:

CH3 CH2 OH + CH3 CHO CH2CH=CHCH2+ 2H2O
Conversion = 45%
Ethanol converted = (98,325 * 0.45) = 44,246.25 Kg/hr
Page 22
Ethanol reacted = (0.55 * 44,246.25) = 24,335.43 Kg/hr
Selectivity = 55%
= 529.03 Kmol/hr
Acetaldehyde reacted = 529.03 Kmol/hr
= 23,277.375 Kg/hr
Butadiene produced = 529.03 Kmol/hr
= 28,567.62 Kg/hr.
Water produced = 2 * 529.03
= 1058.06 Kmol/hr
= 19045.08 Kg/hr.
Side Reaction for second reactor:
1. 2CH3CH2OH
C4H9OH + H2O
2. 2CH3CH2OH
CH3CH2OCH2CH3 + H2O
(5%)
(20 %)
3. CH3CH2OH
C2H4 + H2O
(10%)
4. 2CH3CH2OH
C4H8 + 2H2O
(5%)
5. CH3CH2OH + CH3CHO + C2H4

6. 2CH3CHO
C2H4 + H2O
C6H10+ H2O
(5%)
(9% based on CH3CHO)
For side reactions of second reactor:

First reaction:
Ethanol reacted = 44,246 * (5/100)
= 48.09375 Kmol/hr.
= 2212.3125 Kg/hr.
Page 23
Butanol produced = 24.0468 Kmol/hr

= 1779.4687 Kg/hr.
Water produced = 24.0468 Kmol/hr
= 432.8437 Kg/hr.
Likewise for all other side reactions, a chart is prepared below to estimate the amount of
ethanol reacted and by products formed.
Table 4.4: Amount of ethanol reacted to form by products (Kmol/hr)
Components
. C4H9OH
24.0468
CO
CO2
CH4
CH3CH2OCH2CH3
192.375
H20
24.0468
96.1875
96.1875
48.0937
96.1875
C4 H 8
24.0468
C2 H 4
96.1875
48.0937
CH3COOH
CH3COOCH2CH3
29.4975
C6H10
48.0937
Page 24
Table 4.5: Composition of output stream from second reactor

Components
Kmol/hr
Mol wt
Kg/hr
BUTADIENE
529.03
54
28,567.62
. C4H9OH
24.0468
74
1779.4687
CO
5.343
28
149.625
CO2
5.343
44
235.125
CH4
10.686
16
170.976
CH3CH2OCH2CH3
105.093
74
7776.9375
H20
1490.20
18
26,823.624
C2H4
48.0937
28
1346.625
CH3COOH
7.1252
60
427.514
CH3COOCH2CH3
40.185
88
3536.28
C6H10
48.0937
82
3943.6875
C4H8
15.205
56
851.50
Ethanol recycled
1175.625
46
54,078.75
Acetaldehyde recycled
19.38
44
852.72
TOTAL
131887
Page 25
Material balance over distillation column:

Distillate
Material in
Residue
Table 4.6 : Input stream composition for distillation column

Components
Kmol/hr
Mole frac.
Kg/hr
Wt. frac.
Ethylene
48.0937
0.073
1346.625
0.043
Butadiene
529.03
0.807
28,567.62
0.912
Water
78
0.120
1404
0.045
Total
655.1237
1.0
31,318.245
1.0
Page 26
Table 4.7 : Output stream composition of distillation column

Components
Distillate
Kmol/hr
Mole
Kg/hr
frac.
Residue
Wt.
Kmol/hr
Frac.
Mole
Kg/hr
Wt.
frac.
Frac.
Ethylene
43.28
0.882
1211.96
0.825
4.80
0.007
134.665
0.004
Butadiene
4.23
0.086
228.54
0.155
524.79
0.865
28,339.08
0.949
Water
1.56
0.032
28.08
0.020
76.44
0.128
1375.92
0.047
Total
49.07
1.0
1468.58
1.0
606.03
29849.665
1.0
1.0
Page 27
4.2ENERGY BALANCE CALCULATIONS

General energy balance equation:
Whenever any matter undergoes a physical or chemical change, change in energy can be found
out by applying laws of thermodynamics.
For steady state process the accumulation of energy is zero.
Energy out = [Energy in] + [Energy Generated]
[Energy consumed] [Energy accumulated]
Energy balance over first heat exchanger:

Heat required to increase the temperature of the feed stream from 298 K to 548 K
Q = m * mix
mix = xi i
= 38,701.3 KJ/Kmol
Q = 1500 * 38,701.3
= 58051950 KJ/hr.
Heat lossed by steam = heat gained by the process stream
m v = m CP T
m = 58051950/40626
m= 1428.93 Kmol/hr of steam required.
Page 28
Energy balance over reactor :

Heat lost in the reactor due to endothermic reaction = heat required for the dowtherm to supply
H = 70.811 * 1500
= 106216.5 KJ/hr.
QDOWTHERM = m Cp T
106216.5 = m * 2.403 * (592 548 )
m = 1004.57 kg/hr
= 1004.57/166
= 6.051 Kmol/hr
Energy balance over second heat exchanger :

Heat required to remove to decrease the temperature of the feed stream from 548 K to 322 K
Q = m * mix + m Cp T
CP mix = xi Cpi
= 85.71
mix = 31691.69
Q = (1487.52 * 31691) + (1487.52 * 85.71 *226)
= 75955965.37 KJ/hr.
Cooling water required
75955965.37 = m * Cp * T
m = 75955969.37/ (31.10 * 70) = 34890.19 Kmol/hr of cooling water required.
Page 29
Energy balance over third heat exchanger:

Heat required to increase the temperature of the feed stream from 338 K to 623 K
Q = m * mix
mix = xi i
= 35356.7052 KJ/Kmol
Q = 2931.883 * 35356.7052
= 103661722 KJ/hr.
Heat lossed by steam = heat gained by the process stream
m v = m CP T
m = 103661722/40626
m= 2551.61 Kmol/hr of steam required.
Energy balance over second distillation column :

Enthalpy of feed = QC + Enthalpy of distillate + Enthalpy of residue + Heat loss
Enthalpy of feed = m * CP * T
= 655.1237 * 103.91 * (623-315)
= 209667.62 KJ/hr.
Gases leave at 315 K. The refrigerant is used to cool the gases at 264 K, therefore
Page 30
m * mix = m * CP * T
mix = 13872.41 KJ/Kmol.
Heat removed by refrigerant
Q = m * mix
= 49.07 * 13872.41
= 680719.1587 KJ/hr.
Therefore, m * CP * T = 680719.1587
CPmix = 48.29
m = 680719.1587 / 48.29 * (315- 264)
= 276.40 Kmol/hr of refrigerant required .
HIN to condenser = m * mix + m * CP * T

= (49.07 * 48.29 * 51) + (680719.1587)
= 801568.264 KJ/hr.
HOUT distillate = 801568.264 680719.158

= 120849.114 KJ/hr
Page 31
Enthalpy of residue
Liquid leaves at 330 K.
HRESIDUE = m * CP * T
CPmix = 79.762
HRESIDUE = 606.03 * 79.762 * ( 330 -315)
= 725072.47 KJ/hr.
Refering overall energy balance,

Qr = Qc + Enthalpy of distillate + Enthalpy of residue Enthalpy of feed
= 680719.1587 + 120849.114 + 725072.47 209667.62
= 1316973.12 KJ/hr.
Hence mass flow rate of steam = 1316973.12/40626
= 32.41 Kmol/hr
Page 32
CHAPTER-5
DESIGN
5.1 Fixed Bed Reactor Design

Rate equation for acetaldehyde synthesis:
A
(PA
(1+
pS)
2
S)
Where,
RA = Rate of reaction (Kmol/kg.hr.)
k = Reaction rate constant (Kmol/hr.kg catalyst)
Ki = adsorption coefficient for species (atm-1)
Ke = Equilibrium constant
lnKe = 11.82 6189.1/Tk
lnk = 17.900 5810.5/Tk
lnKA = 1.175 1166.6/Tk
lnKR,S = 1.057 690.2/Tk
Operating conditions:
Temperature = 548 K
Pressure = 2.388 Kgf/cm2
k = 4.08 * 10-4 Kmol/hr.kg catalyst.
Ke = 1.692
Page 33
For main reaction:

CH3CH2OH CH3 CHO + H2
BASIS: 1 mole of CO fed to reactor
Let,
X A = fractional conversion of CO
Moles of any
Component = Initial no. of moles - (Stoichiometric coefficient/Basis)*conversion
Unreacted
1. Moles of CH3 CH2 OH unreacted = 1- (1/1)* X A = (1- X A)
2. Moles of H2 formed = X A)
3. Moles of acetaldehyde formed = X A
Total no. of moles in product stream = (1- X A) + X A + X A
= (1 + X A)
1. Partial pressure of CH3 CH2 OH = (Moles of CH3 CH2 OH / Total No. of moles)* Pressure
= [(1- X A) / (1 + X A)]* 2.388
2. Partial Pressure of H2 = [X A / (1 + X A)]* 2.388

3. Partial Pressure of methanol = [X A/ (1 + X A)]* 2.388
Page 34
Table 5.1 : partial pressure of species & rates at various values of XA
XA
PC2H5OH
P H2
P CH3CHO
-r C2H5OH
-1/r C2H5OH
0.1
1.95
0.217
0.217
7.84 * 10-4
1275
0.2
1.592
0.398
0.398
6.11 * 10-4
1635
0.3
1.28
0.55
0.55
4.49 * 10-4
2225
0.4
1.023
0.68
0.68
3.05 * 10-4
3269
0.5
0.796
0.798
0.798
1.712 * 10-4
5840
0.6
0.597
0.895
0.895
5.042 * 10-4
19832
Performance equation for fixed bed reactor is given as-
Where,
W= Weight of catalyst required for desired conversion (Kg)
FA0 = Molar flow rate of CH3CH2OH entering to reactor = 1425 (kmol/hr)
Integral term is evaluated by plotting graph of [-1/r] Vs XA

From Graph,
Area under curve from XA = 0 to 0.9 is found as: 2200 [Kg/(kmol/hr)]
Hence,
W/F Ao =2200[Kg / (kmol/hr)];
W = 2200 [Kg/ (kmol/hr)] * F Ao (kmol/hr)
W = 2200 * 1425
W = 3135000 Kg = 3135 ton
Page 35
W = 3135 ton
From literature;
Density of CuO/ ZnO/ Al2O3 catalyst = = 8240 (Kg/m3)
Porosity of catalyst bed is assumed as = = 0.38
Therefore,
Volume of catalyst bed = (Weight of catalyst)/ (Density of catalyst)
= 3135000 (Kg) / 8240 (Kg/m3)
= 380.46 m3
Actual volume occupied by catalyst bed = 380.46 m3 / (1- )

= 380.46/ (1- 0.38)
= 613.64 m3
Actual volume occupied by catalyst bed = 613.64 m3
Tube Internal Volume Calculation:
The internal volume of the cylindrical tubes can be calculated using the equation:
V = (Tuber Inner Radius)2 Ltube
= (0.7 in)2 (16 ft) = 296 in3
Number of Tubes Calculation:
Volumetric Flowrate through one tube = Tube Internal Volume
Contact Time
= 296/ 5
= 59.2 in3/s
Number of tubes =
Total volumetric flowrate
Volumetric flowrate through one tube

= 114,278.24
= 1930 Tubes.
59.2
Page 36
Page 37

Project Report

Uploaded by

Copyright:

Available Formats

Project Report

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Project Report

Uploaded by

Copyright:

Available Formats

What are the main industrial uses of butadiene?

What are the main industrial uses of butadiene?

What are the two main sources of butadiene production?

What are the two main sources of butadiene production?

Manufacturing of 1,3-Butadiene

Butadiene from ethanol

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

Table 1.1 Properties of 1, 3 Butadiene

Poor warning properties at low

Melting point [C]

Boiling point [C]

Critical temperature [C]

Vapour pressure, 20C

Relative density, gas (air=1)

Relative density, liquid (water=1)

Solubility in water [mg/l]

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

CNOOC Shell Petrochemicals4

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

Japan Synthetic Rubber

Yeochon Naphtha Cracking Centre

Korea Kumho Petrochemical

Lotte Daesan Petrochemical

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

2.1 Butadiene Manufacturing Process Information :

2.1.1 Butadiene Production Via Steam Cracking of Paraffinic Hydrocarbons

Manufacturing of 1,3-Butadiene from ethanol

Fig 2.1 Butadiene Production Via Steam Cracking of Paraffinic Hydrocarbons

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

In the Houdry process, n-butane is dehydrogenated over chromium/alumina catalysts. The

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

Fig 2.3 Butadiene Production via Oxidative Dehydrogenation

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

2.1.4 Butadiene production from ethanol

Fig 2.4Butadiene production from ethanol

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

Calculation of heat of formation of reaction:

Heat of formation of reaction (H reaction) can be calculated by enthalpy of formation of

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

Calculation of Heat of Reaction:

(H) reaction = (H f) products - (H f) reactants

For main Reaction of first reactor :

SCOE, Chemical Engineering

Manufacturing of 1,3-Butadiene from ethanol

Table 3.2 Enthalpy of formation data for second reaction

For main Reaction of second reactor:

[(H f) CH2CH3OH + (H f) CH3CHO]

= [ 100.374 + (2 * - 224.9748)] [ - 247.938 175.733 ]