2.

3 Market :
According to CMAI (2007), global butadiene demand is expected to grow at just under
3.5%/year through 2012, 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.

Country

China

India

Japan

Korea

Producers
Yangzi Petrochemical
CNOOC Shell Petrochemicals4
Maoming Petrochemical
Jilin Chemical
Qilu Petrochemical
Lanzhou Petrochemical
Shanghai Petrochemical
Yanshan Petrochemical
Others
Total
Reliance Industries
Others
Total
Japan Synthetic Rubber
Chiba Butadiene
Nippon Zeon
Okayama Butadiene
Tobu Butadiene
Tonen General
Nippon Petrochemicals
Total
Yeochon Naphtha Cracking Centre
Korea Kumho Petrochemical

Production Rate
(in thousands of MT./year)
185
155
150
140
130
120
120
113
395
1508
150
172
322
268
177
150
140
130
105
70
1040
218
205

Malaysia
Singapore
Taiwan
Thailand

LG Chemical
Lotte Daesan Petrochemical
Samsung Petrochemicals
LG Daesan Petrochemical
SK Corp.
SK Energy
Total
Titan Petchem
Total
Total
Formosa Petrochemical
Chinese Petroleum
Total
Bangkok Synthetics
IRPC5
Total
Average:

145
109
99
98
72
72
1018
100
100
60
60
373
173
546
140
65
205
149.96875

2.4 Butadiene Manufacturing Process Information :

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).
Each of these processes produces a stream commonly referred to as crude butadiene that
is rich in 1,3-butadiene.
2.4.1 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 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.

The flow path of the C4 components (including butadiene) are 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.
2.4.2 Butadiene Production via Catalytic Dehydrogenationof n-Butane and nButene (the Houdry process)
The catalytic dehydrogenation of n-butane is a two-step process; initially going from nbutane to n-butenes and then to butadiene. Both steps are endothermic.A major butanebased process is the Houdry Catadiene process outlined in Figure.

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 1100-1260 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, 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.

2.4.3 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 (on-purpose) production of butadiene. Several processes and many catalyst
systems have been developed for the oxydehydrogenation of either n-butane or of nbutene feedstocks. Butenes are much more reactive, however, and they require less
severe operating conditions than that of n-butane 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 7090%, making it unnecessary to recover and recycle feedstock.

Butadiene Production via Oxidative Dehydrogenation

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 stripped from the oil, recovered in the overhead of
the stripper, then it is sent to a purification system to recover the butadiene product.

2.4.4 Conclusion of Product Selection :

Comparisons for all four products have been tabulated in Table 2.4. Based on the
comparisons, the team has decided to select butadiene as the butane derivative product.
The team decides to design butadiene production plant because;

Increasing market demand especially in Asia region. Demand in Asia will grow at a
more rapid rate, at 5% /year, although demand in some countries, particularly China,
will be at more than 10%/year (CMAI, 2007).

High market pricing of USD 0.64/lb which will give higher profit.

Only one competitor in Malaysia, which is Titan Petchem. (M) Sdn. Bhd.

Nearby neighbor, Singapore is only producing 60mt/yr.

Aiming to be the major butadiene supplier in Asia

Table : Comparison between potential Butane Derivative Product

Polyisobutylene

Maleic Anhydride

Propylene Oxide

Butadiene

Market

$1.30 per pound

$0.63 per pound

$0.64 per pound

$0.64 per pound

pricing
Complexity

(1996-2001)
Copolymerization

(2007)
Oxidation of

(1995-2000)
2 routes

(2006)
Catalytic

of the

of isobutylene

aromatic

-chlorohydrin

dehydrogenation

compound

-indirect

of normal butane

Mature market

oxidation
Price stable and

Present market

rising demand

firmed and

reactions
Strengths

Tires,tubes the
largest end user

Weaknesses

accounting for 75-

increasing

80% total

High market

consumption.

potential

Fortunes tied

Growth slowed

Demand driven by

Heavily relied on

heavily to tires

down and No

automotive,

automotive

industry

growth

housing and

industry

agriculture

construction

chemical

market

and oil
additives
The process which is here described in the project among these three processes is the
production of the n-Butadiene by oxydehydrogenation process.

2.5 CONCEPTUAL DESIGN ANALYSIS

The Hierarchical Decomposition Approach suggested by Douglas (1988) is consisted of
3 hierarchy of decisions, which are:
Level 1: Batch vs. Continuous
Level 2: Input-output Structure
Level 3: Recycle / Reactor Synthesis
Level 4: Separation
2.5.1 BATCH vs. CONTINUOUS
Continuous processes are designed so that every unit will operate continuously for close
to a year at almost constant conditions before the plant shut down for maintenance. On
the other hand, batch processes normally contain several units that are designed to be
started and stopped frequently. During a normal batch operating cycle, the units are
filled with material and perform their desired function for a specified period. After that,
the units will be shut down, drained and cleaned before the cycle is repeated (Douglas
J.M, 1988).
According to Douglas (1988), there are a few criteria that needed to be considered when
selecting the type of process, which are:

1. Production rates:
Plant that has a capacity that is greater than 10 x 10 6 Ib/yr is usually continuous. In
contrast, if the plants capacity is less than 1 x 10 6 Ib/yr, then batch process will be
chosen. Batch process is usually simpler and more flexible. Therefore, a satisfactory
product can be produced with a large uncertainty in the design. Besides that,
because of greater flexibility, batch plants are most common when a large number of
products are produced in essentially the same processing equipment.
2. Market forces:
Batch plants are often preferred for products with a seasonal demand. Batch process
is also preferred for products with a short life time.
3. Operational problems:
It is very difficult to build continuous processes when a low capacity of slurries
must be handled. This is because it is very hard to pump slurries at low flow rate
without having the solid settling out of the suspension and plugging the equipment
problem. Some materials tend to foul the equipment frequently that the equipment
must be shut down and cleaned very often. Hence, batch process is suitable for this
kind of process instead of continuous.
Butadiene demand is not seasonal and it is forecasted to have 3.5 percent growth per
year through 2012 (CMAI, 2007). Besides, the production rate of butadiene plant
that is decided is more than 10 x 106 Ib/yr and no slurry material is involved in the
process. Therefore, continuous process is selected for butadiene production.
2.5.2 Purification of Feed
A decision to purify the feeds before they enter the process is equivalent to a decision to
design a preprocess purification system. Some design guidelines to be considered are as
follows (Douglas, 1988):
i. If a feed impurity is not inert and is present in significant quantities, remove it.
Otherwise it will lead to raw-material losses, and usually a much complicated
separation system is required to recover the additional by-products.
ii. If a feed impurity is present in a gas feed, as a first guess process the impurity.
iii. If a feed impurity in a liquid feed stream is also a by-product or a product
component, usually it is better to feed the process through the separation system.

iv. If a feed impurity is present in large amounts, remove it.

v. If a feed impurity is present as an azeotrope with a reactant, often it is better to
process the impurity.
vi. If a feed impurity is inert but is easier to separate from the product than the feed, it
is better to process the impurity.
vii. If a feed impurity is a catalyst poison, remove it.

Table shows the composition of the component in feed. The main component that is to
be used in butadiene production is n-butane. However, the amount of isobutane in the
stream is large (39.3 mole %). If isobutane is not separated from the feed and is
processed, additional by product might be produced and thus complicated the separation
process downstream. This will imposed additional cost (capital and operating) to the
plant. Hence, with reference to guideline i and iv, the team decided to purify the stream
first before entering to the reactor.

Table : Composition of the Components in the Feed

Component

Formula

Mole %

Propane

C3H8

9.0

i-Butane (isobutene)

C4H10

25.9

n-Butane

C4H10

72.2

Other Hydrocarbon

C5+

1.0

Figure : Purification of the feed

Figure shows the schematic diagram of the feed purification section. Distillation column
is used to separate the impurities from the feed. As shown in the diagram, n-butane will
be withdrew as side draw product, while isobutane and propane will be withdrew from
the distillation column as the top product and C5+ as bottom product.
To convert n-butane to butadiene, two stages of dehydrogenation reaction are involved
(non-oxidative and oxidative dehydrogenation). The by product of the processes are
hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), short chain hydrocarbon
(C1-C3) and steam (H2O). Figure 4.3 shows the schematic diagram of two stages of
dehydrogenation process. Only approximately 33% of n-butane will be converted to
butadiene. Hence the unreacted n-butane will be recycled.

Figure : Two Stages Dehydrogenation of n-butane

Since only approximately 33% of n-butane will be converted to butadiene, the unreacted
n-butane will be recycled after separated of the product stream. It is impossible to
achieve sharp separation in the separation process. Hence, the recycle stream will
consist of low fraction of impurities. Hence, part of the recycle stream will be purged to
avoid accumulation of the impurities in the process stream.

2.6 Input Output Structure :

2.7 RECYCLE / REACTOR SYNTHESIS

Good reactor performance is of paramount importance in determining the economic

viability of the overall design and fundamentally important to the environmental impact

of the process (Smith, 2005). Therefore, issues to be addressed for a good reactor design
should include;
1. Reactor type
2. Catalyst
3. Size
4. Operating Conditions (Temperature and Pressure)
5. Phase
6. Feed Conditions (Concentration and temperature)
At early stages in design, a kinetic model normally is not available. Thus, material
balance calculations should be based on a correlation of the product distribution
(Douglas, 1998). This type of kinetic analysis is very crude but in most cases the reactor
cost is not nearly as important as the product distribution costs.

2.7.1 Reactor Selection

The selection of reactor is crucially important in order to make sure that the feed
operates at its maximum. For single reaction, the highest rate of reaction is maintained
by the highest concentration of feed (Smith, 2005). Based on the design guidelines for
reactors by Douglas, 1998 stated that in order to maximize the conversion, reactor that
always maintains the highest concentration should be selected. The ideal plug flow
reactor (PFR) is chosen for all three reactors because it always maintains higher
concentration of the reactant. Beside, all three reactions is in gas phase and PFR is also
suitable for gas phase reaction.
Since the reaction is carried out in gas phase over a selective catalyst, the options for
type of reactor selection for this type of reaction are fixed-bed catalytic reactor and
fluidized bed reactor. The structure of fixed bed catalytic reactor is similar to a shell and
tube heat exchanger. It is a tubular reactor that is packed with solid catalyst particles. It
gives the highest conversion per weight of catalyst of any catalytic reactor. It is suitable
to be used for high pressure reaction where smaller diameter cylinder vessels are used to
allow usage of thinner vessel walls. Fixed bed catalytic reactor is also suitable for
process that uses catalyst with a long life time. However, it has difficulty with

temperature control because heat loads vary through the bed. Temperature in the catalyst
might become locally excessive, which may lead to undesired product and catalyst
deactivation. The catalyst is usually troublesome to replace too. Besides, channeling of
the gas flow might occur in the reactor which will result ineffective use of parts of the
reactor bed.
On the other hand, fluidized bed reactor is designed to be operated in a well mixed
condition between the gas phase reactant and catalyst, which result in an even
temperature distribution throughout the bed. Since the temperature is relatively uniform
throughout the reactor, the possibility of having hot spots n the reactor can be
eliminated. The heat transfer rate is high due to the rapid motion of the catalyst. It can
also handle large amounts of feed and solids and has good temperature control. One of
the disadvantages of fluidized bed reactor is high operating cost. Furthermore, the
attrition of catalyst can cause generation of catalyst fines which could be carried over
and lost in the system. This may cause fouling in the pipelines or equipment
downstream. Hence, fluidized bed reactor is Preferable for gas-solid non-catalytic
reactions. The advantages and disadvantages of both types of reactors are summarized
in Table .

Table : Advantages and Disadvantages of Packed Bed and Fluidized Bed Reactor
Reactor

Fixed Bed Catalytic Reactor

It gives the highest

Fluidized Bed Reactor

conversion per weight of catalyst of

any catalytic reactor.

Advantages

to rapid motion of catalyst.

Used for high pressure

of thinner vessel walls.

The temperature is
relatively uniform throughout the

reaction where smaller diameter

cylinder vessels is used to allow usage

High heat transfer due

catalyst, thus avoiding hot spots.

Can handle large

amounts of feed and solids and has
good temperature control.

Difficult to control the

High cost of the reactor

temperature because heat loads vary

and catalyst regeneration

through the bed.

equipment.

Disadvantages

Temperature in the catalyst

Attrition of catalyst

becomes locally excessive, which may

can cause generation of catalyst

lead to undesired product and catalyst

fines which could be carried over

deactivation.

and lost in the system, and may

cause fouling in pipelines and

The catalyst is usually

equipment downstream.

troublesome to replace.

Channeling of the gas flow

occurs, resulting in ineffective use of

Preferable for gas-solid

non-catalytic reactions.

parts of the reactor bed.

After comparing both types of reactor, tubular fixed-bed catalytic reactor is chosen for
all three reactors involve in the process. This is due to the:
a.

lower capital and operating cost

The reactions involved in the butadiene production are required to be operated in

high pressure condition.

The required volume for tubular fixed bed catalytic reactor is smaller compared
to fluidized bed reactor for high pressure operation, and thus lower capital cost.

The operating cost for fluidized bed reactor is very high because it is more
difficult to maintain the gas phase reactant and catalyst to be in the well mixed
condition if it is operated in high pressure.

b.

less losses in catalyst

There will be losses in catalyst if fluidized bed reactor is selected.

The losses in catalyst are resulted from:

catalyst will settle at the bottom of the reactor if it is not well mixed with the gas
phase reactant.

catalyst fine might be generated during the operation of the reactor when the
catalyst hit on the wall of the reactor or through attrition. The catalyst fine will

be brought to the downstream of the process when together with the product
stream.
c.

lower maintenance cost

If fluidized bed reactor is selected, the catalyst that settle at the bottom of the
reactor will foul and plug the reactor while the generated catalyst fine will cause
fouling in the pipeline and equipment downstream

Plant might need to be shut down often for maintenance.

2.8 SEPARATION STRUCTURE

The core reaction in butadiene production is the dehydrogenation using n-butane as the
reactant. However, the feed stream contains significant amount of i-butane which is up
to 39.3%. Thus, in order to increase yield, we need to convert i-butane into n-butane.
The conversion is done in the Isomerization Reactor.
The deisobutanizer column in pretreatment section employs side draws to yield purified
n-butane. The n-butane stream is drawn as a vapor side product a few trays above the
bottom, leaving a small heavy end stream which is only about 1% of the feed stream to
be the bottom product. Thus, the system consists of two prominent products and we can
assume that the small stream does not exist.
The initial assumption for distillation columns is to have 0.02 mole percent of light key
component in bottom and 0.01 mole percent of heavy key component in the overhead
product. Also, we assume that all the component lighter than the light key leave with
overhead and that all components heavier than the heavy key are taken at the bottoms.
2.8.1 Design of Extractive Distillation Column :
According to Seader (1998), extractive distillation is a partial vaporization process in
the presence of a miscible, high-boiling, non-volatile mass separation agent, normally
called the solvent, which is added to an azeotropic or non-azeotropic feed mixture to
alter the volatilities of the key components without the formation of any additional
azeotropes.

2.8.2 Solvent selection:

Since the solvent is the heart of extractive distillation, more attention should be paid on
the selection of potential solvents. The affinity of hydrocarbon to polar solvent depends
directly on their degree of un-saturation. A highly unsaturated hydrocarbon is more
soluble in a polar solvent, and the solvent decreases the volatility of the hydrocarbon.
Based on Perrys Handbook, several features are essential:
1. The solvent must be chosen to affect the liquid-phase behavior of the key
components differently; otherwise no enhancement in separability will occur.
2. The solvent must be higher boiling than the key components of the separation and
must be relatively nonvolatile in the extractive column, in order to remain largely in
the liquid phase.
3. The solvent should not form additional azeotropes with the components in the
mixture to be separated.
4. The extractive column must be a double-feed column, with the solvent feed above
the primary feed; the column must have an extractive section.
From Ullmans handbook (1985), there are five solvents that are commonly used in
industry:
a. n-methyl-2-pyrrolidone (NMP),
b. dimethylformamide (DMF)
c. Dimethylacetamide (DMAC)
d. Acetonitrile (ACN)
e. Furfural
Of all possible solvents that can be used for the separation of butadiene-butane mixture
we have chosen dimethylformamide (DMF). DMF is recommended as a potential
entrainer because it gives great alteration in relative volatility. This in turn will make the
separation easier and cheaper, as the utilities and trays required are lesser. Even though
NMP gives greater value, it costs almost twice the DMF.

CHAPTER 3: PROCESS DESCRIPTION

Process Description
In this project, butadiene is produced in continuous process. Here the 1,3-butadiene is
produced by oxidative dehydrogenation reaction.

3.1 Preprocess Purification Deisobutanizer :

E-102

C-101

E-101

Figure : Preprocess Purification Section

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.

The feed omposition is as follows :

Table : Feed Composition
Component

Formula

Mole %

Propane

C3H8

9.0

i-Butane

C4H10

25.90

n-Butane

C4H10

72.2

Other Hydrocarbon

C5+

1.0

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 C101 while the vapor product which is mainly i-butane will be sent to the Alkylation
Section. N-butane is extracted as the side product. This n-butane 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.
3.2 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.

Figure : Dehydrogenation Section

The process gas from Section 1, the preprocess unit enters the furnace (F301) at
42.92oC. The furnace will heat up the process gas up to 600 oC. 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 500oC 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 Sn0.6Cs0.5K0.5 La3.0 which gives the conversion of 32.9 %
and selectivity of 96%.
The butenes from R301 will be cooled down from 600oC to 420oC by Dehydrogenation
Inter-cooler (E301) before further supplied to Oxidative Dehydrogenation Reactor
(R302). The R302 is also a fixed bed tubular reactor and is operating at temperature of
330oC and pressure of 3 bar.