SEPARATION SCIENCE AND ENGINEERING

Chinese Journal of Chemical Engineering, 17(1) 27ü35 (2009)

Simulation of 1,3-Butadiene Production Process by Dimethylfomamide

Extractive Distillation

YANG Xiaojian (ཷ໌ߒ)1,*, YIN Xuan (࿚༭)1 and OUYANG Pingkai (૘଼ཽ࢚)2
1
Controlling Engineering Center, Nanjing University of Technology, Nanjing 210009, China
2
College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009, China

Abstract Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated
the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most
important parameter to the extractive distillation process. The article has given out the proper solvent ratios, reflux
ratios, distillate ratios, and bottom product ratios of the columns. It also discusses the thermal loads of several col-
umns. The results of simulation are consequently compared with the plant data, which shows good accordance with
each other.
Keywords simulation, 1,3-butadiene, dimethylfomamide, extractive distillation

1 INTRODUCTION ances, thermodynamic parameters, phase equilibrium,

Extractive distillation is the main technique to
produce 1,3-butadiene, which is easy and cost-efficient.
The extractive distillation methods can be separated
into 3 kinds according to the extraction solvents, and
they are acetonitrile (ACN) method, dimethylfoma-
mide (DMF) method (also called GPB method), and
N-methyl-pyrrolidone (NMP) method [1]. The disad-
vantage of ACN method is the complexity to recover
the solvent [2]. Furthermore, ACN is toxic to the en-
vironment [3], so its application is limited now. Di-
methylfomamide is hypo-toxic, miscible with C4 at
any proportion, and it does not become azeotropic
with any component in C4. The shortage is that an in-
hibitor should be added to prevent polymerization.
Some materials might be hydrolyzed into formic acid
and dimethylamine when there is water. And the hy-
drolysates are corrosive to carbon steel [47]. NMP has
good selectivity and solubility, high boiling point, and
low vapor pressure. The solvent is avirulent and bio-
degradable. The solvent loss is very low [810]. About
70% of the processes in China use DMF methods [3, 11].
Other newly developed methods for the production of
butadiene are Houdry technology, oxydehydrogena-
tion of n-butylene, catalytic reaction of ethanol, and so
on [12].
The demand for 1,3-butadiene in Asia increased
by 3% in 2005, which came to 3.9 million tons. Be-
tween 20052010, the growth rate of 1,3-butadiene
and distillation modeling. Aspen Plus is used to simu-
late the processes [14, 15]. The thermodynamic method
chosen is NRTL-RK. The rigorous multistage separa-
tion (RADFRAC) model has been used to calculate
the distillation columns. All the calculations are based
on mass. According to the characteristics of the real
process, the process is separated into four sections.
2 DMF PROCESS
The process uses GPB technology (industrialized
in 1965 by Geon Company, Japan) to extract
1,3-butadiene from C4 materials. The process contains
two extractive distillation sections, one ordinary dis-
tillation section, and one solvent purification section,
as shown in Fig. 1. In the first extractive distillation
section, substances that have higher relative volatility
compared with 1,3-butadiene in DMF are removed. In
the secondary extractive distillation section, sub-
stances of lower relative volatility are removed. Only
the substances whose boiling points differ far from
1,3-butandiene can be removed in the third section.
The solvent purification section is used to purify and
recover the solvent.
3 PROCESS DATA
This set of equipment is designed to treat
1.08×108 kg·a 1 C4 material, and the production of
ˉ

consumption in Asia will reach 4.1% per year [13]. 1,3-butadiene is 6.0×107 kg·a 1. The equipment com-
ˉ

The capacity and efficiency of 1,3-butadiene produc- monly runs under 50% of the design capacity. The
tion in China is still much lower than that of other running time is 7800 h·a 1. The C4 feed to the plant is
ˉ

3 ˉ1
countries. The aim of this work is to study the DMF (14.018.0)×10 kg·h . In the simulation, it is set to
method by simulation, to improve production effi- the average value of 16.0×103 kg·h 1. There are four
ˉ

ciency, and to optimize the operation conditions. feeds to the whole process, one of C4, two of DMF,
This simulation incorporates fundamental chemi- and one of p-tert-butylcatechol (TBC). The following
cal engineering principles and advanced software tools are the conditions of the feeds under the typical opera-
for the DMF process. It includes mass and energy bal- tion condition.

Received 2008-04-28, accepted 2008-11-12.

* To whom correspondence should be addressed. E-mail: yxj_cec@126.com
28 Chin. J. Chem. Eng., Vol. 17, No. 1, February 2009

Figure 1 DMF (GPB) process to produce 1,3-butadiene

3.1 C4 feed 3.2 Solvent (DMF) feed

Raw C4 material includes butylenes, butanes, and
some other impurities (C3, C5). The water content in
C4 material must be˘500 mg·kg 1 to prevent hy-
ˉ
drolysis of DMF. 1,3-Butadiene content of C4 material
is generally between 45.0%52.0% (by mass). Three
typical compositions of the C4 material are shown in
Table 1.
The solvent contains 4.0% (by mass) tar and
96.0% (by mass) DMF. In the first extractive distilla-
tion column T1, the flow of solvent (DMF) is ap-
proximately 78 times than that of C4. Another solvent
stream feeds the secondary extractive distillation
column (T3), and the amount of solvent is 0.81.2
times that of C4 feed in T1.

Table 1 Main components of C4 materialķ 3.3 Polymerization inhibitor (TBC) feed

Content/% (by mass)
Component
No.1 No.2 No.3 In order to prevent 1,3-butadiene polymerization,
1,3-butadiene 0.4530 0.4837 0.5000 TBC is added in column T6 as the polymerization in-
1-butene 0.3747 0.3845 0.3778
hibitor [16]. The dosage is 0.003% (by mass) of the
total feed in T6.
trans-2-butene 0.0516 0.0451 0.0471
cis-2-butene 0.04 0.0338 0.0343
n-butane 0.058 0.0259 0.0221 4 THERMODYNAMIC METHOD AND EQUA-
isobutene 0.0117 0.0093 0.0065
TIONS
vinylacetylene 0.007 0.0073 0.0062
water 0 0.0003 0 The thermodynamic method used in the simula-
others 0.004 0.0101 0.006 tion is NRTL-RK. Non-Random Two Liquids (NRTL)
total 1.0 1.0 1.0
equations are suitable to describe the hydrocarbons
and water. The NRTL activity coefficient equations for
ķ Data source: Yangzi Petro-Chemical Plant, Sinopec. binary systems are:
 Chin. J. Chem. Eng., Vol. 17, No. 1, February 2009 29

ª W 21G21 2
W12G12 º can be calculated from 'g12 and 'g 21 . 'g12 and
ln J 1 x22 «  2» (1) 'g 21 vary with temperature, and can be described as
¬«  x1  x2 G21   x2  x1G12  ¼»
2
linear equations in Ref. [17]: 'g12 A12T  B12 , 'g 21
A21T  B21 .
ª W12G12 2
W 21G21 º
ln J 2 x12 «  » (2)
¬«  x2  x1G12   x1  x2G21 2 ¼»
2
5 SIMULATION RESULTS

 g12  g 22  'g12  g21  g11  The simulations for different C4 feeds are in good
where W12 , W 21
RT RT RT accordance with plant data. The following paragraphs
'g 21 choose a typical simulation to discuss the results.
( g 21 g12 ), G12 exp  a12W12  , G21 exp
RT
5.1 First extractive distillation section
 a12W 21  .
The above NRTL equations have three parame-
ters: 'g12 , 'g 21 , and a12 ( a12 a21 ). The value of the
parameters can be obtained by fitting gas-liquid equi-
librium data. If a12 is fixed, the equations can be
turned into a two parameter equation set. It is consid-
ered that a12 does not vary with the temperature and
the composition of solution, which is determined by
the specification of the solution. Renon et al. [17] con-
sidered a12 value as between 0.20.47 and separated
the solutions into seven types.
The thermodynamic data are obtained from the
database of Aspen Plus except several special binary
interaction data. These data should be considered by
the user. Parameter a12 in most of the binary systems
is considered to be 0.3, and only three cases are of
exception, as shown in Table 2. Thus, the equations
are converted into two parameter systems. W12 and W 21
Table 2 Parameter a12 in some binary systems
Binary system a12
trans-2-butene-vinylacetylene 0.2985
cis-2-butene-vinylacetylene 0.3021
water-dimmer 0.2
Figure 2 Flow chart of the first extractive distillation section
The first extraction distillation section includes
two columns, T1 and T2. Because 1,3-butadiene is
easy to dimerize and it is difficult to calculate the re-
action during the whole process, F1 is added before
T1 to calculate dimerization.
Figure 2 is the first extractive distillation section.
T1 is the first extractive distillation column, including
two feeds: C4 and DMF. Components lighter than
1,3-butadiene are removed from the top, whereas
1,3-butadiene and heavier components are extracted
by DMF at the bottom. T2 is a stripping column, the
feed of which is the bottom discharge of T1. The
function of T2 is to strip out hydrocarbons from DMF
[18]. The hydrocarbons stripped out at T2 top are
cooled to (35±5)°C by two stages of condenser, and
then, sent to T3 by a compressor. The stream of hy-
drocarbons must be below 80°C and 0.6MPa to pre-
vent polymerization. Streams after the compressor are
recycled back in order to improve the efficiency of
separation [19]. Table 3 shows the plant data, the plant
demand, and the simulated results of this section.
In the extractive distillation process, the solvent
ratio is very important for the final results. Fig. 3 and
Fig. 4 show the influences of the solvent ratio and the
reflux ratio upon the performance of T1. It can be seen
30 Chin. J. Chem. Eng., Vol. 17, No. 1, February 2009

Table 3 Comparison of the simulated results and the plant demand in the first section
Column Species Simulated results Plant data Plant demand
T1 1,3-butadiene content in top products/% 0.285 0.291 ˘0.3
top temperature/ć 39.99 39.17 43±5
trans-2-butene content in bottom products/% 0.0013 0.002 ˘0.05
cis-2-butene content in bottom products/% 0.052 0.061 İ2.5
bottom temperature/ć 126.35 126.14 128±3
T2 top temperature/ć 103.53  115±15
bottom temperature/ć 161.75 168.80 161165
temperature on the 8th plate/ć 150.65 156.83 ı140

Figure 5 Influences of feed plate upon the contents of

Figure 3 Influences of solvent ratio upon the contents of several key components of T1
several key components of T1 ƹ1,3-butadiene content in top products;ƶtrans-2-butene content
ƹ 1,3-butadiene content in top products; ƶ trans-2-butene
in bottom products; Ƹcis-2-butene content in bottom products
content in bottom products; Ƹcis-2-butene content in bottom
products

Figure 6 Influence of distillate ratio upon the performances

Figure 4 Influences of reflux ratio upon the contents of
several key components of T1
ƹ 1,3-butadiene content in top products; ƶ trans-2-butene
content in bottom products; Ƹcis-2-butene content in bottom
products
that larger solvent ratio and reflux ratio produce better
separation results, while more energy will be con-
of T2
ƶbottom temperature; Ƹ8th plate temperature; ƺtop tempera-
ture; Ƶheat duty of condenser
bottom temperature, and the condenser heat duty of
T2. T2 is a stripping column, which consumes large
amount of heat. So proper operation conditions can
help save a lot of energy. When the distillate ratio of
T2 is more than 0.14 kg·kg 1, the temperatures of the
ˉ

sumed. So, there exists a minimal solvent ratio and a column can meet the plant demand, but the condenser
minimal reflux ratio to reach the plant demand [20]. heat duty increases with the increase of the distillate
From the simulation results, the minimal solvent ratio ratio. Hence, the minimal distillate ratio is 0.14 kg·kg 1.
ˉ

and the minimal reflux ratio of T1 are 7.5 kg·kg 1 and

ˉ
ˉ1
The calculated bottom temperature is 161.75°C, which
1.4 kg·kg , respectively. matched the measured temperature 161.76°C well.
Figure 5 determines the best feed plate of T1.
Dimethylfomamide is fed in the first plate. The best
feed plate of C4 is in the middle of the column, which 5.2 Secondary extractive distillation section
is on the 39th theoretical plate. Fig. 6 shows the in-
fluence of distillate ratio on the top temperature, the The secondary extractive distillation section
 Chin. J. Chem. Eng., Vol. 17, No. 1, February 2009 31

includes three columns, the extractive distillation col-

umn T3, the 1,3-butadiene recovery column T4, and
the stripping column T5, as shown in Fig. 7. T3 has
two feeds, the stripped top discharge of T2 and DMF.
The feed of T3 contained 1,3-butadienen, vinylacety-
lene, 1-butyne, 1,2-butadiene, methyl-acetylene, and
C5. The relative volatility of methyl-acetylene in DMF
is close to 1,3-butadiene, which can not be removed in
this section. The top discharge of T3 is mainly
1,3-butadiene with small amount of impurities, which
is purified in the next section. The T3 bottom dis-
charge DMF still contains much 1,3-butadiene. The Figure 8 Influences of solvent ratio on the performances
of T3
bottom discharge of T3 is sent to T4 to recover Ƹ bottom temperature; ƺ
top temperature; Ƶheat duty of reboiler
1,3-butadiene. The top discharge of T4 is
1,3-butadiene with some other hydrocarbons, which is
recycled to the first section to keep mass balance. The
bottom discharge of T4 is DMF dissolving some hy-
drocarbons, which is sent to T5 to recover DMF. Too
large amounts of vinylacetylene might cause an ex-
plosion. When the vinylacetylene content exceeds 0.5
kg·kg 1 in the top product of T5, it should be diluted
ˉ

by butane or butylene. Table 4 compares the simulated

results of this section and the plant demands.

Figure 9 Influences of reflux ratio on the performances of T3

Ƹ bottom temperature; ƺ
top temperature; Ƶheat duty of reboiler

influences of these three parameters on the top and

bottom temperatures, and the reboiler heat duty of
column T3. The importance of the parameters is the
following: distillate ratio˚solvent ratio˚reflux ratio.
The calculated vinylacetylene content is far below the
plant demand. The proper values of the parameters are
the following: the solvent ratio 2.0 kg·kg 1, the flux
ˉ

ratio 1.0 kg·kg , and the distillate ratio 0.845 kg·kg 1.

ˉ1 ˉ

Figure 7 Flow chart of the secondary extractive distilla-
tion section
Three parameters might influence the bottom
temperature of T3. They are the solvent ratio, the re-
flux ratio, and the distillate ratio. The solvent ratio
means solvent feed: hydrocarbons feed, the reflux ra-
tio means reflux flow: distillate, and the distillate ratio
means distillate: hydrocarbons feed. Figs. 810 are the
Although the distillate ratio influences the T3 per-
formances more than the other two parameters, the
most important parameter to control here is solvent
ratio. Too low a solvent ratio might cause the distillate
and the bottom flow-off specification. And when the
solvent ratio is too high, it might induce waste of large
amount of energy.
Column T4 is very simple and is used to recover
1,3-butadiene from the solvent. Its top temperature is

Table 4 Comparison of the simulated results and the plant demand in the secondary section
Column Species Simulated results Plant data Plant demand
ˉ6
T3 vinylacetylene content in top products×10 0.00 3.0 İ5
top temperature/°C 40.00 41.70 41±2
bottom temperature/°C 134.31 130.46 135±5
T4 bottom temperature/°C 135.55 144.78 135±10
T5 top temperature/°C 121.92  105145
bottom temperature/°C 161.47 164.6 163±2
temperature on the 12th plate/°C 147.22 157.8 ı147
vinylacetylene content in top products/% 24.61 29.4 İ50
32 Chin. J. Chem. Eng., Vol. 17, No. 1, February 2009
Figure 10 Influences of distillate ratio on the performances
of T3
Ƹ bottom temperature; ƺ
top temperature; Ƶheat duty of reboiler
very steady. The bottom temperature increases slightly
with the increase of the bottom product ratio.
Figures 11 and 12 are the influences of the bot-
tom product ratio, and the reflux ratio on the per-
formances of T5. The bottom product ratio influences
the bottom temperature of T5 more than the reflux
ratio. In order to keep the temperature of the 12th
plate above 147°C, the bottom product ratio, and the
reflux ratio should be kept above 0.03 kg·kg 1 and
ˉ
ˉ1
0.42 kg·kg , respectively. The bottom product ratio
influences the temperature of all the plates except that
of the top one, and the reflux ratio can only adjust the
temperature of the middle plates. The vinylacetylene
content in top products decreases with the increase of
Figure 11 Influences of bottom product ratio on the per-
formances of T5
Ƹ bottom temperature;ƺtop temperature;ƶ 12th plate tem-
perature; ƽvinyl acetylene content in top products
Figure 13 Flow chart of the secondary extractive distillation section
Figure 12 Influences of reflux ratio on the performances
of T5
Ƹ bottom temperature; ƺ top temperature;ƶ 12th plate tem-
perature; ƽvinyl acetylene content in top products
the bottom product ratio and the reflux ratio. Hence, if
one wants to reduce the vinylacetylene content and to
control the temperature of the plates at some fixed
value at the same time, the best way is to increase the
bottom product ratio and to decrease the reflux ratio.
5.3 Ordinary distillation section
The ordinary distillation section is to remove the
impurities, which can not be separated out in the pre-
vious sections. This is shown in Fig. 13. The
methyl-acetylene and water can be removed by T6. The
top pressure of T6 varies with the methyl-acetylene
content and the cooling water temperature. The more
the content of methyl-acetylene in the feed stream of
T6, the more the loss of 1,3-butadiene in the distillate.
The polymerization inhibitor TBC added in this sec-
tion is to prevent the aggregation of 1,3-butadiene.
The retained minor constituent of cis-2-butene,
1,2-butadiene 1-butyne, and C5 are removed by T7.
Table 5 compares the simulated results of this section
and the plant demands.
Figure 14 is the influence of bottom product ratio
on the performances of T6. Fig. 15 is the influences of
reflux ratio on the performances of T6. The bottom
product ratio influences the performances of T6 more
than other parameters. The T6 top temperature can
meet the demand when the bottom product ratio is
 Chin. J. Chem. Eng., Vol. 17, No. 1, February 2009 33

Table 5 Comparison of the simulated results and the plant demand in the secondary section
Column Key target Simulated results Plant data Plant demand
T6 methyl-acetylene content in top products/% 14.09 19.1 İ38
top temperature/°C 40.09 40.05 42±4
bottom temperature/°C 50.48 50.70 52±4
T7 top temperature/°C 43.83 45.78 48±5
1,3-butadiene content in the top products/% 99.34 98.9 ı99.3
bottom temperature/°C 63.38 55.51 63±5
ˉ6
vinylacetylene content in top products×10 0.00 3.0 İ5
1,3-butadiene content in the bottom products/% 0.03 0.08 İ5

Figure 16 Influences of bottom product ratio on the per-

Figure 14 Influences of bottom product ratio on the per-
formances of T6
Ƹ bottom temperature;ƶtop temperature;Ƶmethyl-acetylene
content of the distillate
formances of T7
Ƹ bottom temperature; ƹ 1,3-butadiene content of the distillate;
Ƶ1,3-butadiene content of the bottom product

5.4 Solvent purification section

The solvent purification section is to refine and

to reuse the solvent. There is only one column T8 in
this section, which is to separate out such materials as
water, dimer, and some hydrocarbons. The refined
DMF is obtained at the bottom of T8. Table 6 com-
pares the simulated results of this column and the
plant demand.

Figure 15 Influences of reflux ratio on the performances

of T6
Ƹ bottom temperature; ƶtop temperature;Ƶmethyl-acetylene
content of the distillate

more than 0.91 kg·kg 1, but the best bottom product

ˉ

ratio is 0.98 kg·kgˉ1. The proper reflux ratio is 10

kg·kg 1. When the reflux ratio is more than 10 kg·kg 1,
ˉ ˉ

the 1,3-butadiene content is over the specification and

the top temperature decreases only slightly. So the
proper reflux ratio here is 10 kg·kgˉ1.
Figure 17 Flow chart of the solvent purification section
Figure 16 is the influence of bottom product ratio
upon the performance of T7. T7 is the secondary dis-
tillation column used to remove high boiling point Figure 18 and Fig. 19 show the influence of re-
materials, such as cis-2-butene, 1,2-butadiene, vi- flux ratio and bottom flow ratio on the performance of
nylacetylene, and so on. From Fig. 14, the suitable T8. Fig. 18 shows that all the performances changed
bottom product ratio is 0.026 kg·kg 1. When it is
ˉ
little by changing the reflux ratio. When the products
lower, the bottom temperature is too high, and the can not meet the demand, the reflux ratio should be
1,3-butadiene content of the bottom product will ex- increased. The minimum reflux ratio here is 0.06
kg·kg 1. It can be seen from Fig. 19 that, if the DMF
ˉ
ceed the specification.
34 Chin. J. Chem. Eng., Vol. 17, No. 1, February 2009
Table 6 Comparison of the simulated results and the plant demand in the secondary section
Column Species
T8 DMF content of top product/%
ˉ6
water content of bottom product×10
top temperature/°C
bottom temperature/°C
Figure 18 Influences of reflux ratio on the performances
of T8
Ƹ bottom temperature;ƶ top temperature; × DMF content of
top product;ƽwater content of the bottom product
Figure 19 Influences of bottom product ratio on the per-
formances of T8
Ƹ bottom temperature;ƶtop temperature; × DMF content of
top product;ƽwater content of the bottom product
content of top product can be controlled above 1% (by
mass), the suitable bottom product ratio should be in
the range of 0.940.962 kg·kg 1. When the bottom
ˉ
product ratio is above 0.97 kg·kg 1, the top tempera-
ˉ
ture and the bottom temperature decline greatly. And
the separation result will be deteriorated.
6 CONCLUSIONS
This study simulated the 1,3-butadiene produc-
tion process with DMF extractive distillation method
by Aspen Plus. The thermodynamic equations used
here are NRTL equations, and the method chosen in
the software is NRTL-RK. The whole process contains
8 columns, which are separated into 4 sections for
simulation. The calculated results show good accor-
dance with the plant data.
The discussion includes the influences of the op-
Simulated results Plant data Plant demand
1.0 1.1 İ1
447 550 İ500
104.85 105.60 98±6
159.95 166.30 163±4
erations upon the performances of the columns. The
solvent ratio is the most important parameter to the
extractive distillation process. The simulation studied
the best solvent ratios. T1 and T3 are extractive distil-
lation columns, and the best solvent ratios of T1 and
T3 are 7.5 kg·kg 1 and 2.0 kg·kg 1. T2 and T5 are
ˉ ˉ
stripping columns. When fixing the reflux ratio, en-
ergy consumption must be considered. The least reflux
ratios of T2 and T5 are 0.14 kg·kg 1 and 0.42 kg·kg 1,
ˉ ˉ
respectively. When something goes wrong with these
two columns, increasing the reflux ratio properly will
stabilize the column. T6 and T7 are distillation col-
umns. They are used to purify the product
1,3-butadiene. The bottom product ratio of T6 should
be kept above 0.91 kg·kg 1, and the best result is 0.98
ˉ
ˉ1
kg·kg . The bottom product ratio of T7 should be
more than 0.026 kg·kg 1. T8 is to recycle DMF. Its
ˉ
least reflux ratio is 0.06 kg·kg 1, and the proper bot-
ˉ
tom product ratio should be controlled within the
range of 0.940.962 kg·kg 1.
ˉ
The simulated results show that proper parame-
ters will make productions meet the demands and save
large amount of energy. The study gives us a clear
understanding of the whole process and provides
methods to adjust the process when it is unstable.
ACKNOWLEDGEMENTS
We gratefully acknowledge China Petroleum &
Chemical Corporation for supporting the software,
and Yangzi Petro-Chemical Plant, Sinopec for provid-
ing the plant data. And we are also thankful to
Petro-CyberWorks Information Technology Co., Ltd.
for their assistance in this work.
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