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.

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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

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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

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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

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Total

60

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Manufacturing of 1,3-Butadiene from ethanol

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
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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.

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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,

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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

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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.

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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

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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

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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.

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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

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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

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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:
+

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Manufacturing of 1,3-Butadiene from ethanol

+
+
+

(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.

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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

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= 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.

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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.

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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

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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.

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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

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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.

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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

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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

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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

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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

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Manufacturing of 1,3-Butadiene from ethanol

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.

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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.

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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

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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

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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

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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

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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

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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

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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

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