United States Patent (19) 11) 4,401,515

Arakawa et al. 45) Aug. 30, 1983

54). PROCESS FOR PRODUCING 4,128,457 12/1978 Barba et al. ........................... 2O3/53
1,3-BUTADIENE OR 4,246,073 1/1981 Umeda et al. ......................... 2O3/25
2-METHYL-1,3-BUTADIENE HAVING HIGH OTHER PUBLICATIONS
PURITY
Hydrocarbon Processing, vol. 47, No. 11, pp. 131-134.
75) Inventors: Masatoshi Arakawa; Kazuyoshi
Nakazawa, both of Yokkaichi, Japan Primary Examiner-Wilbur L. Bascomb, Jr.
73 Assignee: Japan Synthetic Rubber Co., Ltd., Attorney, Agent, or Firm-Oblon, Fisher, Spivak,
McClelland & Maier
Tokyo, Japan
(57) ABSTRACT
(21) Appl. No.: 242,676
22 Filed: Mar. 11, 1981
In a process for producing butadiene or isoprene having
a high purity comprising a step of treating a C4 or C5
30 Foreign Application Priority Data hydrocarbon mixture containing butadiene or isoprene
Mar. 15, 1980 JP Japan .................................. 55-32161 by an extractive distillation method in the presence of a
selective solvent to obtain crude butadiene or crude
51 Int. Cl. ...... ... B01D 3/40; C07C 7/08 isoprene and a step of separating a heavy fraction con
52 U.S. C. ........................................ 203/25; 203/53; tained in a small quantity in the thus obtained crude
203/82; 203/84; 203/DIG. 19, 202/154; butadiene or crude isoprene by a conventional distilla
585/810; 585/864 tion method in a heavy fraction separating tower, the
(58) Field of Search ....................... 203/53, 60, 58, 62, heat energy can be saved to a great extent by thermally
203/78, 84, 82, 85,79, 93, 97,99, 21, 25, 26, 27, coupling the tower for distilling crude butadiene or
DIG. 19, 202/154; 585/810, 864
crude isoprene used in the above-mentioned extractive
56) References Cited distillation step with the above-mentioned heavy frac
U.S. PATENT DOCUMENTS tion separating tower, namely by feeding a part or the
2,600,106 6/1952 Garrett .................................. 2O3/60 whole of the vapor stream from the top of said tower
2,901,404 8/1959 Kirshenbaum et al. ............ 202/154 for distilling crude butadiene or isoprene to said heavy
2,971,036 2/1961 James .................................... 203/29 fraction separating tower and feeding a liquid at a rate
3,058,893 10/1962 Cahn et al. .. ... 203/84 corresponding to the whole or a part of the reflux rate
3,230,157 1/1966 Hill et al. ........ ... 203/53 necessary for the operation of the tower for distilling
3,254,024 5/1966 Huckins et al. . ... 203A25 crude butadiene or crude isoprene, from the heavy
3,378,465 4/1968 Brandt et al. ... ... 203/25 fraction separating tower to the tower for distilling
3,554,873 1/1971 Luther et al. ... ... 203A60
3,769,217 10/1973 Bannister et al. ..................... 2O3/60 crude butadiene or crude isoprene.
3,844,898. 10/1974 DeGraf .............................. 2O2/54
4,025,398 5/1977 Haselden ............................. 2O2/154 19 Claims, 5 Drawing Figures

HEAVY FRACTION
SEPARATING
TOWER

4 HEAVY FRACTION
SOLVENT STRIPPING
COLUMN
 U.S. Patent Aug. 30, 1983 Sheet 1 of 2 4,401,515

F. G. F. G.2
PRIOR ART

SOLVENT
8
HEAVY FRACTION HEAVY FRACTION
SEPARATING SEPARATING
TOWER TOWER

3 3
EXTRACTIV 4 HEAVY FRACTION
E.TION SOLVENT HEAVY FRACTION SOLVENT STRIPPING
STRIPPING COLUMN
COLUMN

F. G. 3

HEAVY
FEED 2 FRACTION
SEPARATING
TOWER

FIRST
58FE FIRST SOLVENT HEAVY FRACTION
COLUMN STRIPPING COLUMN
SECOND SECOND SOLVENT
EXTRACTIVE STRIPPING COLUMN
DISTILLATION
COLUMN
 U.S. Patent Aug. 30, 1983 Sheet 2 of 2 4,401,515

F. G. 4
SOLVENT
SOLVENT

HEAVY FRACTION
SEPARATING
TOWER

FIRST
EXTRACTIVE HEAVY FRACTION
DISTILLATION FIRSTSOLVENT SECOND Y
COLUMN STRIPPING COLUMN EXTRACTIVE SER
DISTILLATION STRIPPING

8
82
83 84 PRODUCT

SECOND
DISTILLATION
COLUMN
FIRST
DISTILLATION
COLUMN

HEAVY FRACTION
 4,401,515
1.
PROCESS FOR PRODUCING 1,3-BUTADIENE OR
2-METHYL-1,3-BUTADIENE HAVING HIG
PURTY
This invention relates to a process for purifying a C4
or C5 hydrocarbon mixture obtained by naphtha crack
ing process, dehydrogenation process or the like by an
extractive-distillation method with an economized heat
energy, thereby producing 1,3-butadiene (hereinafter,
simply referred to as butadiene) or 2-methyl-1,3-butadi
ene (hereinafter, simply referred to as isoprene) having
a high purity.
As a process for separating and recovering butadiene
or isoprene having a high purity from a C4 or C5 hydro
carbon mixture containing butadiene or isoprene in a
high yield, an extractive distillation method is widely
known and industrially practised. As the selective sol
vent for the extractive distillation, polar substances such
as acetonitrile, dimethylformamide, N-methylpyrroli
done, furfural, acetone, dimethylacetamide and the like
are used.
In Hydrocarbon Processing, Vol. 47, No. 11, pp.
131-134, a one-step extractive distillation process for
butadiene using furfural as a selective solvent is dis 25 thermally coupling the tower for distilling crude butadi
ene or crude isoprene in the above-mentioned extrac
closed. In this process, the fractions lighter than butadi
ene are removed in the first extractive distillation step,
the crude butadiene containing a small quantity of
heavy fraction is distilled out of a solvent stripper and
the heavy fraction is removed in the subsequent heavy
fraction separating tower to give a high purity butadi
e.
In Chem. Techn., 28 Jg., Heft Aug. 8, 1976, pp.
463-466, a two-step process for the extractive distilla
tion of butadiene using dimethylformamide as a selec
tive solvent is disclosed. In this process, the components
weaker than butadiene in affinity to the solvent are
removed as the light fraction in the first extractive dis
tillation step, the components stronger than butadiene in
affinity to the solvent are removed as the heavy fraction
in the second extractive distillation step and crude buta
diene containing a small quantity of impurity is purified
in the subsequent heavy fraction separating tower to
give high purity butadiene.
In U.S. Pat. No. 2,971,036, a one-step process for the
extractive distillation of isoprene using acetone or ace
tonitrile as a selective solvent is disclosed. Further, in
U.S. Pat. No. 3,230,157, a two-step process for the ex
tractive distillation of isoprene using acetone or acetoni
trile as a selective solvent is disclosed. 50
In all these processes, a light fraction separating
tower and/or a heavy fraction separating tower are (is)
usually provided for the purpose of further purifying
the crude butadiene or the crude isoprene obtained in
the extractive distillation step. In the hitherto known 55
techniques, these towers are operated independently of
the extractive distillation step.
With the rapid rise of energy cost in the recent years,
it is intensely requested to convert the processes to
those of energy saving type. 60
In the hitherto known techniques, and extractive
distillation tower or the solvent stripper for distilling
out crude butadiene or crude isoprene in the extractive
distillation step has a condenser at the top, where the
vapor stream is cooled and condensed in order to secure 65
a quantity of reflux necessary for the operation of
tower. Since sea water, river water or the like is used as
the cooling water for the condensers in economical
2
consideration and from the necessity that the tower
must be operated at a pressure as low as possible in
order to suppress the polymerization of crudebutadiene
or crude isoprene, the heat transferred from the top
vapor stream to the cooling water in the condenser is
disposed without being used effectively at all at the
present time. On the other hand, the heavy components
contained in a small amount in the crude butadiene or
crude isoprene obtained in the extractive distillation
10 step are considerably difficult to remove because their
boiling points are very close to that of crude butadiene
or crude isoprene, so that a distillation tower having a
high plate number and a considerable quantity of reflux
are necessitated. :
5 The present inventors have analyzed this tower in
detail to find a surprising fact that the minimum quan
tity of reflux necessary for the separation in this tower
is determined by the rectifying section above the feed
stage, and the stripping section requires a much smaller
20
quantity of minimum reflux. Thus, the inventors have
conducted extensive research on a measure for making
the best of this fact to rationalize the process and to save
energy. As a result, this object has been achieved by
tive distillation process with the heavy fraction separat
ing tower.
According to this invention, there is provided a pro
cess for producing butadiene or isoprene having a high
30
purity comprising a step of treating a C4 or Cs hydrocar
bon mixture containing butadiene or isoprene by an
extractive distillation method using a selective solvent
to obtain crude butadiene or crude isoprene, and a step
35 of separating the small quantity of heavy fraction con
tained in said crude butadiene or crude isoprene by a
conventional distillation method in a heavy fraction
separating tower, characterized by thermally coupling
the tower for distilling crude butadiene or crude iso
40 prene used in the extractive distillation step with said
heavy fraction separating tower.
In the process of this invention, the term "thermally
coupling" means feeding the whole or a part of the top
vapor stream of the tower for distilling crude butadiene
45 or crude isoprene into the heavy fraction separating
tower without condensing the stream in the condenser
and returning a liquid from the latter tower to the for
mer tower in an amount sufficient to secure the quantity
of reflux necessary for the operation of the tower for
distilling crude butadiene or crude isoprene, by said
liquid in combination with the reflux from the con
denser of said distillation tower. By this measure, the
heat quantity removed from the condenser by cooling
water can be saved to a great extent. That is, according
to this invention, the heat quantity added from the out
side of the system can be saved because the heat quan
tity discarded from the condenser is heat added in any
form from the outside of the system. In addition, there
are obtained further advantages according to this inven
tion such as saving of cooling water supplied to con
denser, reduction of apparatus cost, and so on.
This invention will be explained in detail below refer
ring to the accompanying drawings, in which FIGS.
1-5 illustrate the process for separating butadiene or
isoprene of high purity from a C4 or C5 fraction by a
extractive distillation process, wherein
FIG. 1 is a flow sheet illustrating the hitherto known
process and
 4,401,515
3 4.
FIGS. 2-5 are flow sheets illustrating embodiments processes in that the whole or a part of the vapor stream
of the process of this invention. In the Figures, the is fed to the middle stage of the heavy fraction separat
numerals refer to the followings: ing tower 12 via the conduit 19 directly without being
Conduit-1, 3, 4, 5, 8, 10, 11, 14, 15, 17, 18, 19, 20, 21, condensed in the condenser (accordingly, the con
23, 24, 25, 27, 29, 31, 32, 34, 35, 38, 39, 41, 42, 43, 45, 5 denser 9 is unnecessary when the whole of the vapor
46, 51,53, 54, 55, 57, 59, 60, 61, 64, 66, 67, 70, 71, 73, stream is fed to the heavy fraction separating tower). A
74, 75, 76, 78, 80, 81, 83, 84, 85, 88, 89 part of the liquid flow descending in the heavy fraction
Extractive distillation tower-2, 22, 28, 52, separating tower is withdrawn from the middle stage of
Solvent stripper-6, 26, 44, 56, 62 the tower (preferably from the same stage as the stage
Heavy fraction separating tower-12, 36, 68 O to which the conduit 19 is connected or its neighboring
Tower-77, 86 stage) via the conduit 20 and fed to the solvent stripper
Reboiler-7, 13, 30, 37, 63, 69,79, 87 6 via the conduit 10 either directly or after being joined
Condenser-9, 16, 33, 40, 65, 72, 82 with a stream from the condenser 9 if it exists. In this
For simplicity and clarity, most of the pumps, heat case, the operation is controlled so as to secure the same
exchangers and the like not particularly necessary to 15 flow rate of liquid as that of the reflux in FIG. I. While
explain are omitted in the Figures, and only the main the reflux rate via the conduit 17 should be slightly
parts are shown. Where some kinds of raw materials are increased to secure the same separation in the heavy
used, a pretreatment step and/or an after-treatment step fraction separating tower 2 in the FIG. 2 scheme com
may be necessary before or after the steps mentioned pared to the FIG. 1 scheme, the degree of this increase,
below, but they are omitted because they are irrelevant 20 however, is very small as compared with the decrease
to the essence of this invention. in amount of condensate in the condenser 9 of the sol
FIG. 1 illustrates the flow scheme of the hitherto vent stripper 6. This means that the required energy for
known one-step extractive distillation process. A C4 or the separation can be saved to a great extent according
C5 fraction containing butadiene or isoprene is fed to the to this invention.
middle stage of the extractive distillation tower 2 via the 25 FIG. 3 illustrates the flow scheme where this inven
conduit 1. A selective solvent composed of at least one tion is applied to a two-step extractive distillation pro
polar solvent is fed to the neighborhood of the top of cess. A C4 or C5 fraction containing butadiene or iso
the tower 2 via the conduit 3. From the top, the compo prene is fed to the middle stage of the first extractive
nents weaker than butadiene or isoprene in affinity to distillation tower 22 via the conduit 21. A selective
the solvent are discharged via the conduit 4, while the 30 solvent is fed to the neighborhood of the top of the
components having a strong affinity to the solvent are tower 22 via the conduit 23. Components weaker than
discharged together with butadiene or isoprene from butadiene or isoprene in affinity to the solvent are dis
the bottom via the conduit 5 and fed to the middle stage charged from the top via the conduit 24, while compo
of the subsequent solvent stripper 6. The reboiler 7 is ments having strong affinity to the solvent are dis
provided at the bottom of the solvent stripper 6, while 35 charged from the bottom via the conduit 25 together
the condenser 9 is provided at the top of the stripper. with butadiene or isoprene and fed to the middle stage
From the bottom of the solvent stripper 6, the selective of the subsequent first solvent stripper 26. The solvent
solvent separated from hydrocarbons is discharged, and free from hydrocarbons is discharged from the bottom
recycled to the extractive distillation tower 2 via the of the tower 26 and recycled to the first extractive
conduit 3. From the top of the tower 6, a vapor com- 40 distillation tower 22 via the conduit 23. Thus, a fraction
posed mainly of crude butadiene or crude isoprene is composed mainly of butadiene or isoprene is discharged
discharged via the conduit 8, and this stream is con from the top of the first solvent stripper 26 via the con
densed by the condenser 9, and a part of the condensate duit 27 and fed to the middle stage of the second extrac
is returned to the solvent stripper 6 as a reflux via the tive distillation tower 28. To the neighborhood of the
conduit 10 while the remainder is fed to the heavy frac- 45 top of the tower 28, the solvent discharged from the
tion separating tower 12 via the conduit 11 as a tower bottom of the second solvent stripper 44 is recycled and
top distillate. The heavy fraction separating tower 12 is fed through the conduit 29. The second extractive distil
equipped with the reboiler 13 at the bottom and with lation tower 28 is equipped with the reboiler 30 at the
the condenser 16 at the top. The small quantity of heavy bottom and with the condenser 33 at the top if neces
fraction contained in the crude butadiene or crude iso- 50 sary. From the bottom of the tower 28, a stream com
prene fed via the conduit 11 is discharged from the prising a hydrocarbon composed mainly of the compo
bottom via the conduit 14. On the other hand, a vapor nents stronger than butadiene or isoprene in affinity to
stream composed mainly of butadiene or isoprene free the solvent and the solvent is discharged via the conduit
from the heavy fraction is discharged from the top via 31, and sent to the middle stage of the second solvent
the conduit 15 and condensed by the condenser 16, and 55 stripper 44. A stream of hydrocarbon is discharged
a part of the condensate is returned to the heavy frac from the system at the top of the tower 44 via the con
tion separating tower 12 via the conduit 17 as a reflux duit 45, while the solvent free from hydrocarbon is
while the remainder is discharged from the system via discharged from the bottom and recycled to the second
the conduit 18 as a tower top distillate. This distillate extractive distillation tower 28 via the conduit 29. On
consists essentially of butadiene or isoprene, and is sent 60 the other hand, the whole or a part of the vapor stream
to the next step not shown in the figure if the purifica composed mainly of crude butadiene or crude isoprene,
tion thereof is necessary. discharged from the top of the tower 28 via the conduit
FIG. 2 illustrates the flow scheme of an improved 32, is fed to the middle stage of the heavy fraction sepa
process wherein the solvent stripper 6 and the heavy rating tower 36 via the conduit 35 directly without
fraction separating tower 12 are thermally coupled 65 being condensed in the condenser 33 (accordingly, the
according to this invention. The stream of the vapor condenser 33 is unnecessary when the whole of the
discharged from the top of the solvent stripper 6 via the vapor stream is fed to the tower 36). From the middle
conduit 8 is different from that in the hitherto known stage of the heavy fraction separating tower 36, a part
 5
4,401,515. 6
of the liquid flow descending in the tower is withdrawn heavy fraction separating tower, because the excessive
via the conduit 43 and then fed via the conduit 34 as a selective solvent if any acts so as to disturb the separa
reflux to, the top of the second extractive distillation tion of the crude butadiene or crude isoprene from the
tower 28 either directly or after being joined with the heavy olefins in the heavy fraction separating tower. In
reflux from the condenser 33 if it exists, Explanation of 5 the case of light solvents such as acetonitrile or acetone,
the heavy fraction separating tower 36 is omitted here it is sometimes difficult to satisfy the above-mentioned
because it is the same as the explanations of the heavy conditions. In such a case, the problem can be coped
fraction separating towers in FIGS. 1 and 2. with by, for example, providing, on the way of the flow
FIG. 4 illustrates the flow scheme where this inven to the heavy fraction separating tower, a step of wash
tion is applied to another two-step extractive distillation ing with water by such a method as not to cause phase
process. In this flow scheme, the first extractive distilla change of the vapor stream. As another method, it can
tion step comprising... the first extractive distillation also be coped with by withdrawing the whole liquid
tower 52 and the first solvent stripper 56 is for removing from the middle stage of the tower, feeding a part
the components stronger than butadiene or isoprene in thereof to the extractive distillation step, washing the
affinity to the solvent (the components are discharged 15: remaining liquid flow with water to remove the selec
from the system via the conduit 57), while the second tive solvent, and then returning it to the heavy fraction
extractive distillation step comprising the second ex separating tower because it is mainly at the stripping
tractive distillation tower 58 and the second solvent section that the existence of the selective solvent would
stripper 62 is for removing the components weaker than affect adversely the separation of heavy olefins from
butadiene or isoprene in affinity to the solvent (the 20
butadiene or isoprene in the heavy fraction separating
components are discharged from the system via the tower.
conduit 60), and the crude butadiene or crude isoprene This invention will be explained below in more detail
is obtained as a tower top component of the tower 62. In referring to Examples, which are not by way of limita
this flow scheme, accordingly, it will be easily under tion but by way of illustration. 2
stood that the anode of thermal coupling between the 25
second solvent stripper 62 and the heavy fraction sepa EXAMPLE 1
rator tower 68 is just the same as in FIG. 2. Isoprene was purified along the flow scheme of FIG.
In FIGS. 24, the difference between the quantity of 3 by using a solvent mixture consisting of acetonitrile
vapor streams 19, 35 or 67 fed to the heavy fraction and water. Though it is not shown in the Figure, the
separating tower 12, 36 or 68 and the quantity of liquid 30
raw C5 fraction was previously heat-treated to dimerize
stream 20, 43 or 75 from said tower 12, 36 or 68 corre the major part of cyclopentadiene, and then it was
sponds to the feed rate to the heavy fraction separating treated in a preliminary concentration tower to separate
tower in the hitherto known processes. Therefore, the the heavy fraction and concentrate isoprene to some
feeding points, and withdrawing points for these flows extent. The fraction thus obtained was fed to the first
are usually positioned on the same stage, though there is 35
extractive distillation step via the conduit 21 and the
no problem practically so far as they are provided on concentrated isoprene stream which was obtained as
the stages near one another. the overhead product of the first solvent stripper 26 via
FIG. 5 illustrates another embodiment of this inven conduit 27 was fed to the second extractive distillation
tion. In this scheme, solvent stripper or extractive distil tower 28. The operating conditions of the tower 28 and
lation tower and heavy fraction separating tower are 40
the tower 36 were as follows::
thermally coupled to each other in a different way from
FIGS. 2-4. The tower 77 is a unification of the towers
to be thermally coupled in the extractive distillation Tower 28 Tower 36
step in FIGS. 2-4 and the rectifying section of a heavy Total number of plates 110 110
fraction separating tower, and the tower 86 is composed 45. Raw material feed point
only of the stripping section of the heavy fraction sepa (counted from the bottom) 40th plate 50th plate
rating tower. To the tower 77 is supplied the feed via Solvent feed point
(counted from the bottom) 104th plate w
the conduit 76 (corresponding to the conduits 5, 27 and Top pressure (kg/cm2 G) . O.2
61 in FIGS. 2 to 4) and the circulating solvent is fed via top temperature (C.) 54 41
the conduit 78 (only in the case corresponding to FIG. 50 Bottom temperature (C.) 102 50
3). From the top of the tower 77, a stream of purified Reflux ratio (3.0) 6.2,
butadiene or isoprene is discharged out of the system
via the conduit 84 (corresponding to the conduits 18, 42 The flow rates in the main conduits were as follows:
and 74 in-FIGS. 2 to 4). Apart of the liquid descending
in the tower 77 is withdrawn from the middle stage 55
above the conduits 76 and 78 of the tower 77 via the
conduit 85 and fed to the top stage of the tower 86. A (Unit: kg/hr)
part of this liquid is discharged out of the system from conduit 27 conduit 42
the bottom via the conduit 88 as a heavy fraction, while 14 Pentadiene
2-Butyne:187
256
87
256
the remainder is heated in the reboiler 87 and returned 60
-Pentene
from the top of the tower. 86 via the conduit 89 to the } 21 21
tower 77 as a vapor stream. Though the position at 2-Methyl-1-butene
which, the conduit 89 is connected to the tower 77 is 2-Methyl-1-buten-3-yne 26 60 ppm
preferably at the safne-stage as the position at which the Isoprene 4,292 4,240
conduit 85 is connected, there is no problem practically 65 2-Pentene
} 24 24
so far as they are at neighboring stages. 2-Methyl-2-butene
It is preferred that substantially no selective solvent 1,3-Pentadiene 38 50 ppm
be, contained in the stream 19, 35, 67 or 85 fed to the 1-Pentyne 2
 4,401,515
7 8
-continued EXAMPLE 3
- Onitke?h) - Butadiene was purified along the flow scheme of
conduit 27 conduit 42 FIG. 3 by using a solvent mixture consisting of acetoni
Cyclopentadiene 84 0.5 ppm 5 trile and water according to the process of this inven
agnitrile : tion in which the second extractive distillation tower 28
Total 5087 4640.5 and the heavy fraction separating tower 36 were ther
mally coupled.
.. The operating conditions of the tower 28 and the
Conduit 39: 24,700 kg/hr. 10 tower 36 were as follows:
Conduit 31: 24,877 kg/hr .
Conduit 35: 19,640 kg/hr
Conduit 38: 593 kg/hr Tower 28 Tower 36
ConduitP 43: 14,730 kg/hr (= Conduit 34) Total NG f Flat
Raw material feed point
130 100
Conduit 45: 179 kg/hr 15 (counted from the bottom) 5th plate 50th plate
Conduit 46: 400 kg/hr Solvent feed point
Condenser 33 was not used. Water was fed to the top (counted from the bottom) i 10th plate
stage of the tower 36 by means of the conduit 46 in Top pressure (kg/en G) 3.8 2.9
order
a
to wash the acetonitrile, coming into the system Top-temperature (C)
Bottom temperature (C.)
41
13
36
50
via the conduit 35. The acetonitrile removed by the 20 Reflux ratio (2.8) 5.
water washing was separated as an aqueous phase from
the hydrocarbon and withdrawn from the bottom (in The f in th dui follows:
FIG. 3, it is summarized in the conduit 38). In this case, e flow rates 1 the main conduits Were as Olows:
the quantities of heat added to the reboilers 30, and 37
were as follows: 25
Reboiler 30: 1,970X 103 Kcal/hr (Unit; kg/hr)
Reboiler 37: 1,130X 103 Kcal/hr conduit 27 conduit 42
COMPARATIVE EXAMPLE 1 i-Butene } 8 8
In Example 1, the operation was carried out by the 30 1-Butene
hitherto known process.
a
That is, without thermally Trans-2-butene
Cis-2-butene
34
332
25
32
coupling the extractive distillation tower 28 and the ,3-Butadiene 12,397 12,263
heavy fraction separating tower 36, the top vapor 1,2-Butadiene 41 10 ppm.
stream of the tower 28 was wholly condensed in the 35 Methylacetylene 146 146
condenser 33, and it was partially returned to the tower Ethylacetylene
Vinylacetylene 4.
162 16 ppm.
24 ppm.
28 as a reflux (reflux ratio = 3.0) and the remainder was Acetonitrile 4. e
fed to the tower 36 in the liquid state. A reflux ratio of Water 26 2.
6.0 was necessary for realizing the same separation in Total 3.19 12,486
the tower 36 as in Example 1. In this case, the quantities 40
of heat added to the reboilers 30 and 37 were as follows. Conduit 29:21,224 kg/hr
Reboiler 30: 1,970X 103 Kcal/hr Conduit 31:. 21,673 kg/hr
Reboiler 37: 2,820x103 Kcal/hr Conduit 35: 48,420 kg/hr
By comparing these values with those in Example 1, Conduit 38: 256 kg/hr
it is apparent that the quantity of heat necessary for the 45 Condit 43. 35,678 kg/hr
operation of the tower 36 could be reduced to 40% by Conduit 45: 445 kg/hr
this invention, as compared with hitherto known pro- In this Example, the condenser 33 was not used, and
CSS. the quantities of heat added to the reboilers 30 and 37
EXAMPLE 2 were as follows:
50 Reboiler 30: 5,030x 103 Kcal/hr
Butadiene was purified by using a solvent mixture Reboiler 37: 2,530X 103 Kcal/hr
consisting of acetonitrile and water according to the
process of this invention wherein the solvent stripper 6 COMPARATIVE EXAMPLE 3
and the heavy fraction separating tower 12 were ther- In Example 3, the operation was carried out by the
mally coupled along the flow scheme in FIG. 2. In this 55 hitherto known process. That is, without thermally
case, the condenser 9 was not used. For obtaining, from coupling the extractive distillation tower 28 and the
the conduit 18, butadiene having the same purity as in heavy fraction separating tower 36, the top vapor
the hitherto known process wherein the solvent stripper stream of the tower 28 was wholly condensed in the
6 and the heavy fraction separating tower 12 are not condenser 33, and it was partially returned to the tower
thermally coupled (the flow is the same as in FIG. 1 and 60 28 as a reflux (reflux ratio=2.8), and the remainder was
the condenser 9 is used), the flow rates in the conduits fed to the tower 36 in the liquid state. A reflux ratio of
3, 5, 8, 10, 14 and 18 were the same in both cases, but the 4.6 was necessary for realizing the same separation in
flow rate (reflux rate) in the conduit 17 had to be in the tower 36 as in Example 3. In this case, the quantities
creased by 10%. Although the heat duty in the reboiler of heat added to the reboilers 30 and 37 were as follows:
7 was the same in both cases at this time, the heat duty 65 Reboiler 30: 5,030x 103 Kcal/hr
in the reboiler 13 was reduced to 49% according to the Reboiler 37; 6,400X 103 Kcal/hr
process of this invention, as compared with that in the By comparing these values with those in Example 3,
hitherto known process. it is apparent that the quantity of heat necessary for the
 4,401,515
10
operation of the tower 36 could be reduced to 40% by from the top of said extractive distillation column,
this invention, as compared with the hitherto known withdrawing a stream of components weaker than
process. buadiene or isoprene in affinity to said selective
What is claimed is: solvent;
1. A process for producing high purity butadiene or from the bottom of said extractive distillation, col
isoprene comprising treating a C4 or Cs hydrocarbon umn, withdrawing a liquid stream comprising se
mixture containing butadiene or isoprene by an extrac lective solvent, components stronger than butadi
tive distillation method, comprising at least one extrac ene or isoprene in affinity to said selective solvent
tive distillation step and at least one solvent-stripping and butadiene or isoprene, and feeding said liquid
step, in the presence of a selective solvent to obtain 10 stream to the middle section of a solvent stripping
crude butadiene or crude isoprene containing a small column;
quantity of heavy fraction; and separating said heavy from the bottom of said solvent stripper column,
fraction from said crude butadiene or crude isoprene in withdrawing a liquid stream of said selective sol
a heavy fraction separating tower, wherein said crude vent and recycling a portion of the same to the
butadiene or crude isoprene is taken out of the top of a 5 upper section of said extractive distillation column,
column as a top vapor in the extractive distillation step the remaining portion passing through a reboiler
or the solvent-stripping step, at least a part thereof is fed and being returned to the bottom of the column as
to the middle stage of said heavy fraction separating vapor;
tower, the remainder is condensed and refluxed to said from the top of said solvent stripping column, with
column, and a liquid is withdrawn from said middle 20 drawing a vapor stream comprising crude butadi
stage or its neighboring stage of said heavy fraction ene or crude isoprene containing a small quantity
separating tower and then fed to said column together of heavy fraction and feeding at least a portion of
with said remainder, the total flow rate of said liquid the vapor stream to the middle section of a heavy
and said remainder corresponding to the reflux rate fraction separating tower, the remaining portion of
necessary to operate said column. 25
the vapor stream being condensed and returned to
2. A process according to claim 1, wherein said heavy the upper section of said solvent stripping column;
fraction separating tower comprises a rectifying section from the middle section of said heavy fraction sepa
and a stripping section, and said rectifying section is rating tower, withdrawing a portion of the liquid
unified with said column and said liquid from the mid flow descending the tower and feeding the liquid to
dle stage of said unified tower is withdrawn and fed to the upper section of said solvent stripping column,
said stripping section, and top vapor stream of said the total flow rate of this liquid and the condensed
stripping section is returned to said unified tower. vapor returned to the upper section of said solvent
3. A process according to claim 1 or 2, wherein ex stripping column corresponding to the reflux rate
tractive distillation is effected by a one-step extractive necessary to operate said solvent stripping column;
distillation process and said column functions as a sol 35 from the top of the heavy fraction separating tower,
vent stripper. withdrawing a vapor stream comprising butadiene
4. A process according to claim 1 or 2, wherein ex or isoprene free from heavy fraction, condensing
tractive distillation is effected by a two-step extractive the vapor stream, returning a portion of the con
distillation process by which fractions lighter than buta densate to the tower as reflux and withdrawing a
diene or isoprene are separated in a first step and frac 40 portion as product;
tions heavier than butadiene or isoprene are separated in from the bottom of the heavy fraction separating
a second step, and said column acts as a second extrac tower, withdrawing a liquid stream comprising
tive distillation tower in the second step of said two-step said heavy fraction from said tower and returning
extractive distillation process. -
5. A process according to claim 1 or 2, wherein said 45 only a portion of said liquid stream to said tower as
extractive distillation is effected by a two-step extrac a vapor after passage through a reboiler.
tive distillation process by which fractions heavier than 8. The process according to claim 7, wherein all of
butadiene or isoprene butadiene are separated by means the vapor stream withdrawn from the top of said sol
of a first extractive distillation tower and a first solvent vent stripping column is fed to the middle section of the
stripper as a first step and fractions lighter than butadi 50 heavy fraction separating tower and the liquid with
ene or isoprene butadiene are separated by means of a drawn from the middle section of the heavy fraction
second extractive distillation tower and a second sol separating tower supplies the reflux necessary to oper
vent stripper as a second step, and said column acts as a ate said solvent stripping column.
second solvent stripper. 9. The process according to claim 7, wherein the
6. A process according to claim 1, wherein thermal 55 vapor stream withdrawn from the top of said solvent
energy is transferred by feeding the whole of the top stripping column is fed to the heavy fraction separating
vapor stream from said column to said heavy fraction tower at the same stage at which liquid is withdrawn
separating tower, and feeding a liquid from said heavy from the heavy fraction separating tower for feed to the
fraction separating tower to said column at a rate corre upper section of said solvent stripping column.
sponding to reflux rate necessary to the operation of 60 10. A process for producing high purity butadiene or
said column. isoprene comprising:
7. A process for producing high purity butadiene or feeding a C4 or Cs hydrocarbon mixture containing
isoprene comprising: butadiene or isoprene to the middle section of a
feeding a C4 or Cs hydrocarbon mixture containing first extractive distillation column;
butadiene or isoprene to the middle section of an 65 feeding a selective solvent to the upper section of said
first extractive distillation column;
extractive distillation column;
feeding a selective solvent to the upper section of said from the top of said first extractive distillation col
extractive distillation column; . . .. . umn, withdrawing a stream of components weaker
 4,401,515
1. 12
than butadiene or isoprene in affinity to said selec 11. The process according to claim 10, wherein all of
tive solvent; the vapor stream withdrawn from the top of said second
from the bottom of said first extractive distillation extractive distillation column is fed to the middle sec
column, withdrawing a liquid stream comprising tion of the heavy fraction separating tower and the
selective solvent, components stronger than buta- 5 liquid withdrawn from the middle section of the heavy
diene or isoprene in affinity to said selective solvent fraction separating tower supplies the reflux necessary
and butadiene or isoprene, and feeding said liquid to operate said second extractive distillation column.
stream to the middle section of a first solvent strip 12. The process according to claim 10, wherein the
ping column; vapor stream withdrawn from the top of said second
from the bottom of said first solvent stripping col O extractive distillation column is fed to the heavy frac
umn, withdrawing a liquid stream of said selective tion separating tower at the same stage at which liquid
solvent and recycling the same to the upper section is withdrawn from the heavy fraction separating tower
of said first extractive distillation column; for feed to the upper section of said second extractive
from the top of said first solvent stripping column, distillation column.
withdrawing a vapor stream composed mainly of 15 13. The process according to claim 10, further com
butadiene or isoprene and feeding said vapor prising: feeding water to the upper section of said heavy
stream to the middle section of a second extractive fraction separating tower, whereby any selective sol
distillation column; vent remaining in the vapor stream coming from the top
feeding a selective solvent to the upper section of said of the second extractive distillation column is removed
second extractive distillation column; 20 as an aqueous phase in the liquid stream withdrawn
from the bottom of said second extractive distillation from the bottom of said heavy fraction separating
column, withdrawing a liquid stream comprising tOWer.
selective solvent and component stronger than 14. A process for producing high purity butadiene or
butadiene or isoprene in affinity to said selective isoprene comprising:
solvent, recycling a portion of this liquid stream to 25 feeding a C4 or C5 hydrocarbon mixture containing
the bottom of said second extractive distillation butadiene or isoprene to the middle section of a
column as vapor after passage through a reboiler first extractive distillation column;
and feeding the remaining portion of said liquid to feeding a selective solvent to the upper section of said
the middle section of a second solvent stripping first extractive distillation column;
column; 30 from the bottom of said first extractive distillation
from the top of said second solvent stripper column, column, withdrawing a liquid stream comprising
withdrawing a vapor stream comprising compo selective solvent and components stronger than
nents stronger than butadiene or isoprene in affinity butadiene or isoprene in affinity to said selective
to said selective solvent; solvent, and feeding said liquid stream to the mid
from the bottom of said second solvent stripping 35 dle section of a first solvent stripping column;
column, withdrawing a liquid stream of said selec from the top of said first solvent stripping column,
tive solvent and recycling the same to the upper withdrawing a vapor stream comprising compo
section of said second extractive distillation col nents stronger than butadiene or isoprene in affinity
unn; to said selective solvent;
from the top of said second extractive distillation 40 from the bottom of said first solvent stripping col
column, withdrawing a vapor stream comprising umn, withdrawing a liquid stream of said selective
crude butadiene or crude isoprene containing a solvent and recycling the same to the upper section
small quantity of heavy fraction and feeding at least of said first extractive distillation column;
a portion of the vapor stream to the middle section from the top of said first extractive distillation col
of a heavy fraction separating tower, the remaining 45 umn, withdrawing a vapor stream comprising com
portion of the vapor stream being condensed and ponents weaker than butadiene or isoprene in affin
returned to the upper section of said second extrac ity to the selective solvent and butadiene or iso
tive distillation column; prene and feeding said vapor stream to the middle
from the middle section of said heavy fraction sepa section of a second extractive distillation column;
rating tower, withdrawing a portion of the liquid 50 feeding selective solvent to the upper section of said
flow descending the tower and feeding the liquid to second extractive distillation column;
the upper section of said second extractive distilla from the top of said second extractive distillation
tion column, the total flow rate of this liquid and column, withdrawing a vapor stream comprising
the condensed vapor stream returned to the upper components weaker than butadiene or isoprene in
section of said second extractive distillation col 55 affinity to said selective solvent;
umn corresponding to the reflux rate necessary to from the bottom of said second extractive distillation
operate said second extractive distillation column; column, withdrawing a liquid stream comprising
from the top of the heavy fraction separating tower, selective solvent and butadiene or isoprene, and
withdrawing a vapor stream comprising butadiene feeding said liquid stream to the middle section of a
or isoprene free from heavy fraction, condensing 60 second solvent stripping column;
the vapor stream, returning a portion of the con from the bottom of said second solvent stripping
densate to the tower as reflux and withdrawing a column, withdrawing a liquid stream of said selec
portion as product; tive solvent, recycling a portion of this liquid
from the bottom of the heavy fraction separating stream to the bottom of said second solvent strip
tower, withdrawing a liquid stream comprising 65 ping column as vapor after passage through a re
said heavy fraction from said tower and returning boiler and recycling the remaining portion of said
only a portion of said liquid stream of said tower as liquid to the upper section of said second extractive
vapor after passage through a reboiler. distillation column;
 4,401,515 14
13
from the top of said second solvent stripping column, from the middle section of said first distillation col
withdrawing “a vapor stream comprising crude umn, at a point above the inlet for the liquid stream
butadiene or crude isoprene containing a small from the bottom for the extractive distillation col
quantity of heavy fraction and feeding at least a umn, withdrawing a portion of the liquid descend
sportion of the vapor stream to the middle section of 5 ing the first distillation column, and feeding said
a heavy fraction separating tower, the remaining liquid stream to the upper section of a second distil
portion of the vapor stream being condensed and lation column;
returned to the upper section of said second solvent from the bottom of said second distillation column,
stripping column; withdrawing a liquid stream of heavy fraction from
from the middle section of said heavy fraction sepa- 10 said second distillation column and returning only
rating tower, withdrawing a portion of the liquid a portion of said liquid stream to the bottom section
flow descending the tower and feeding the liquid to of said second distillation column, as vapor, after
the upper section of said solvent stripping column, passage through a reboiler;
the total flow of this liquid and the condensed from the top of said second distillation column, with
vapor stream returned to the upper section of said 15 drawing a vapor stream and feeding said vapor
second solvent stripping column corresponding to stream to the middle section of said first distillation
the reflux rate necessary to operate said second column at about the stage where the liquid stream
solvent stripping column; for feed to the second distillation column is with
from the top of said heavy fraction separating tower, drawn;
withdrawing vapor stream comprising butadiene 20 from the top of the first distillation column, with
or isoprene free from heavy fraction, condensing drawing a vapor stream of purified butadiene or
the vapor stream, returning a portion of the con isoprene, condensing the vapor stream, returning a
densate to the tower as reflux and withdrawing a portion of the condensate to the top of said first
portion as product; distillation column as reflux and withdrawing a
from the bottom of the heavy fraction separating 25 portion of the condensate as product.
tower, withdrawing a liquid stream comprising 18. A process for producing high purity butadiene or
said heavy fraction from said tower and returning isoprene comprising:
only a portion of said liquid stream to said tower as feeding a C4 or C5 hydrocarbon mixture containing
vapor after passage through a reboiler. butadiene or isoprene to the middle section of an
15. The process according to claim 14, wherein all of 30 extractive distillation column;
the vapor stream withdrawn from the top of said second feeding a selective solvent to the upper section of said
solvent stripping column is fed to the middle section of extractive distillation column;
the heavy fraction separating tower and the liquid with from the top of said extractive distillation column,
drawn from the middle section of the heavy fraction withdrawing a vapor stream of components
separating tower supplies the reflux necessary to oper-35 weaker than butadiene or isoprene in affinity to
ate said second solvent stripping column. said selective solvent;
16: The process according to claim 14, wherein the from the bottom of said extractive distillation col
vapor stream withdrawn from the top of said second umn, withdrawing a liquid stream comprising se
solvent stripping column is fed to the heavy fraction lective solvent, components stronger than butadi
separating tower at the same stage at which liquid is 40 ene or isoprene in affinity to said selective solvent
withdrawn from the heavy fraction separating tower and butadiene or isoprene, and feeding said liquid
for feed to the upper section of said second solvent stream to the middle section of a solvent stripping
stripping column. ' ' ' ' column;
17. A process for producing high purity, butadiene or from the bottom of said solvent stripping column,
isoprene comprising: . . . . . . . . 45
withdrawing a liquid stream of selective solvent
feeding a C4 or Cs hydrocarbon mixture containing and recycling said stream to the upper section of
butadiene or isoprene to the middle section of an said extractive distillation column;
extractive distillation column; from the top of said solvent stripping column, with
feeding a selective solvent to the upper section of said drawing a vapor stream composed mainly of buta
extractive distillation column 50 diene or isoprene and feeding said vapor stream to
from the top of said extractive distillation column, the middle section of a first distillation column;
withdrawing a vapor stream of components feeding a selective solvent to the middle section of
weaker than butadiene or isoprene in affinity to said first distillation column, at a point above the
said selective solvent; *:
from the bottom of said extractive distillation col- 55 inlet for said vapor stream from the solvent strip
umn, withdrawing a liquid stream comprising se ping column;
lective solvent, components stronger than butadi from the bottom of said first distillation column, with
ene or isoprene in affinity to said selective solvent drawing a liquid stream of selective solvent, return
and butadiene or isoprene, and feeding said liquid ing a portion of said selective solvent to the bottom
stream to the middle section of a first distillation 60 section of said first distillation column as a vapor
column; after passage through a reboiler and recycling the
from the bottom of said first distillation column, with remaining liquid portion of selective solvent to the
drawing a liquid stream of selective solvent, recy middle section of said first distillation column, after
cling a portion of said selective solvent to the upper removing the components stronger than butadiene
section of said extractive distillation column and 65 or isoprene in affinity to the selective solvent;
returning a portion of said selective solvent to the from the middle section of said first distillation col
bottom section of said first distillation column, as umn, at a point above the selective solvent inlet,
vapor, after passage through a reboiler; withdrawing a portion of the liquid descending
 4,401,515.
15
said column and feeding said liquid stream to the
upper section of a second distillation column;
from the bottom of said second distillation column,
withdrawing a liquid stream of heavy fraction from
said second distillation column and returning only
a portion of said liquid stream to the bottom section
of said second distillation column as a vapor after
passage through a reboiler;
from the top of said second distillation column, with
drawing a vapor stream and feeding said vapor
stream to the middle section of said first distillation
column at about the stage where the liquid stream
for feed to the second distillation column is with
drawn;
from the top of the first distillation column, with
drawing a vapor stream of purified butadiene or
isoprene, condensing the vapor stream, returning a
portion of the condensate to the top of said first
distillation column as reflux and withdrawing a
portion of the condensate as product.
19. A process for producing high purity butadiene or
isoprene comprising:
feeding a C4 or C5 hydrocarbon mixture containing
butadiene or isoprene to the middle section of a
first extractive distillation column; v ing said liquid stream to the upper section of a
feeding a selective solvent to the upper section of said
first extractive distillation column;
from the bottom of said first extractive distillation
column, withdrawing a liquid stream comprising
selective solvent and components stronger than
butadiene or isoprene in affinity to said selective
solvent, and feeding said liquid stream to the mid
dle section of a solvent stripping column;
from the top of said solvent stripping column, with
drawing a vapor stream comprising components
stronger than butadiene or isoprene in affinity to
said selective solvent;
from the bottom of said solvent stripping column,
withdrawing a liquid stream of selective solvent
and recycling the same to the upper section of said
first extractive distillation column;
from the top of said first extractive distillation col
umn, withdrawing a vapor stream comprising com
ponents weaker than butadiene or isoprene in affin
ity to the selective solvent and butadiene or iso
16
prene and feeding said vapor stream to the middle
section of a second extractive distillation column;
feeding selective solvent to the upper section of said
second extractive distillation column;
from the top of said second extractive distillation
column, withdrawing a vapor stream comprising
components weaker than butadiene or isoprene in
affinity to said selective solvent;
from the bottom of said second extractive distillation
O column, withdrawing a liquid stream comprising
selective solvent and butadiene or isoprene, and
feeding said liquid stream to the middle section of a
first distillation column;
from the bottom of said first distillation column, with
15 drawing a liquid stream of selective solvent, recy
cling a portion of said selective solvent to the upper
section of said second extractive distillation col
umn and returning a portion of said selective sol
vent to the bottom section of said first distillation
column, as vapor, after passage through a reboiler;
from the middle section of said first distillation col
umn, at a point above the inlet for the liquid stream
from the bottom of the second extractive distilla
tion column, withdrawing a portion of the liquid
25 descending the first distillation column, and feed
second distillation column;
from the bottom of said second distillation column,
withdrawing a liquid stream of heavy fraction from
30 said second distillation column and returning only
a portion of said liquid stream to the bottom section
of said second distillation column, as vapor, after
passage through a reboiler;
from the top of said second distillation column, with
35 drawing a vapor stream and feeding said vapor
stream to the middle section of said first distillation
column at about the stage where the liquid stream
for feed to the second distillation column is with
drawn;
40 from the top of the first distillation column, with
drawing a vapor stream of purified butadiene or
isoprene, condensing the vapor stream, returning a
portion of the condensate to the top of said first
distillation column as reflux and withdrawing a
45 portion of the condensate as product. . .
: k is
50
55
60
65