Thethatworld production of synthetic rubber exceeded

of all natural rubber products for the first

time in 1962 (6). At the same time, the proportion of
polybutadiene in synthetic rubber greatly increased;
therefore, butadiene has become a n important petro-
chemical base material.
I n the USA, the bulk of the butadiene-namely
about 850jo-is obtained by the dehydrogenation of
butanes and butenes. However, in Western Europe
and Japan the main base material for the production
of butadiene is the C4 hydrocarbon fraction obtained in
cracking naphtha to yield ethylene. T h e amount of
butadiene produced in this process is about one seventh
of the amount of ethylene. Table I indicates that the
butadiene content of the cracked fractions is between
40 and 5oOj0, the actual amount depending on the sew
erity of cracking, and is thus decidedly higher than that

BASF of dehydrogenation fractions ( 2 ) . The content of acetyl-

enes--i.e., up to 1.5%-is greater than that in the de-
hydrogenation fractions by a factor of about 10.

Process A modern process of recovering butadiene from C4

hydrocarbon mixtures must give a good yield of buta-
diene with the high degree of purity required for the

for production of stereospecific butadiene rubber. The

guaranteed values for the purity of butadiene of “poly-
cis quality” are also listed in Table I ; accordingly

Production the content of 1,3-butadiene should be a t least 99.5%.

T h e catalysts for the stereospecific polymerization con-
tain metalorganic compounds, and the content of reac-

of tive impurities in the monomeric butadiene should be

very low-e.g., less than 25 ppm for acetylenes and 50
ppm for allenes. This requirement must be met, even

Pure
Butadiene TABLE I. TYPICAL COMPOSITION OF C, FRACTIONS
CONTAINING BUTADIENE AND GUARANTEED VALUES
FOR BUTADIENE PRODUCT (POLY-CIS-QUALITY)
U. WAGNER Dehydro- Product
H. M. WElTZ Cracked
fraction,
genation
fraction,
butadiene
(guarantee
Compound % VOl % wt values)
Propane + propene ca. 0.2
iso-Butane 1 .o
n-Butane 4.7
BASF method uses iso-Butene 23.5 80-35 2 < 0.5y0 vol
1-Butene 12.6
N-me thylpyrrolidone as solvent trans-2-Butene 6.4
cis-2-Butene 5.4
of proved high selectivity, 1,3-Butadiene 44.6 20-45 >99,50J, vol
Propadiene 0.1
2: < 50 ppm voI
low separation costs 1,2-Butadiene
Propyne
0.2
0.3
1-Butyne 0.2
2-Bu tyne Traces
Vinylacetylene 0.8
Diacetylene Traces
C.K+ hydrocarbons Traces

VOL. 6 2 NO. 4 APRIL 1970 43

 if the feedstock is the Cq cracked fractions obtained in
modern high-severity cracking processes and thus have a
very high content of C4 acetylene-i.e., greater than 3Yc.
T h e large amount of acetylenes and other highly
unsaturated compounds in the cracked fractions incurs
the risk of polymer formation in separation plants and
thus of fouling and choking of columns, equipment,
fittings, and pumps. A number of processes have been
described for avoiding these difficulties by chemical
pretreatment of the Cg fraction or by partial hydrogena-
tion ( 4 ) . However, these demand additional capital
investment and utilities. Although in thc second
method the higher unsaturated compounds and part of
the Cd acetylenes are selectively hydrogenated, the effect
is usually accompanied by a not insignificant loss of
butadiene.
I n a process for recovering butadiene from C,cracked
fractions, the butadiene content in the butene mixture
should be so lom-e.g., less than lyo-that this iriixture
can be used for further chemical purposes or, for ex-
ample, for the recovery of pure 1-butene.

Principle of the Process

The most important processes for recovering butadiene
from ( 2 4 hydrocarbon mixtures are those employing
selective solvents--i.e., extractive distillation or counter-
Figure 7. Absorption process: straight-through scrubbing current scrubbing. I n the BASF process for recovery
of butadiene, :V-methylpyrrolidone (NMP) containing
water is used as the selective solvent (7). The solvent
has also proved successful in the recovery of acetylene,
the extraction of aromatics, and various other separation
processes. In this paper it will be demonstrated that
NMP more than meets all the requirements imposed on a
selective solvent for the recovery of pure butadiene from
crude Cq cracked fractions.
T h e separation of gas mixtures with the aid of physical
selective solvents exploits the different solubilities of the
ingredients in the solvent. For example, carbon dioxide
can be removed from synthesis gas by scrubbing with
water under pressure. Only small amounts of the
other ingredients are contained in the water, because
their solubility in water is much less than that of carbonic
acid.
However, if there is little difference in the solubilities,
it is still possible to obtain the less soluble component
in the pure form a t the head of the absorber, but the
solvent runs off at the bottom of the absorber and will
always contain a mixture of the two components (Figure
1).
Natta (5) was the first to recognize in 1938 that, in
analogy to distillation, the more readily soluble compo-
nent can be obtained in gas scrubbing if a zone of de-
sorption fractionating is inserted between the absorption
fractionating and the degassing zones (Figure 2).
This is the principle of countercurrent scrubbing or
extractive distillation, which is the basis of all butadiene
processes employing physical solvents. T h e only differ-
ences between the individual processes are the arrange-
Figure 2. Absorption process: counter-current scrubbing or extractive ment Of the stages and the method Of
distillation recovery.

44 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
 ___

TABLE I I . PHYSICAL DATA OF HYDROCARBONS T O BE SEPARATED

Bunsen
solubility
coeficient a!
at I atm and
40 O C , m3
Compound BP, OC NTP/m3 atm
Propane -42.07 3.08 13.5
iso-Butane -11.73 4.87 8.52
Propene -47.70 5.37 7.73
n-Butane - 0.50 9.5 4.37
iso-Butene - 6.90 15.42 2.69 * Main scrubber (tops)
1-Butene - 6.26 15.6 2.66
Propadiene -34.5 18.4 2.29
trans-2-Butene + 0.88 20.4 2.03
cis-2-Butene + 3.72 25.1 1.65 ,
1,3-Butadiene - 4.41 41.5
Propyne -23.22 43 .O
1,2-Butadiene + l o . 85 78.0
1-Butyne + 8.1 102
2-Butyne +26.9 206
Vinylacetylene + 5.1 226
Diacetylene +10.3 2,200

T o give a n idea of the separation task to be accom-
plished, the components of the C4 fraction are arranged
in Table I1 in sequence of increasing solubility in N-
methylpyrrolidone.
A distinction can be made between three groups of
compounds.
(1) Hydrocarbons whose solubility is less than that of
1,3-butadiene. These, together with the butanes and
butenes, represent the bulk of the other components of
the feedstock and are withdrawn from the head of the
main scrubber.
(2) Compounds whose solubility is greater than that
of butadiene-1,3. These consist of small amounts of
C 4 acetylenes and 1,2-butadiene impurities. They are
separated in a second absorber from the 1,3-butadiene,
which in this case is withdrawn a t the head of the
column. This group of compounds also includes some
that are not listed in the table but are usually present in
small amounts in Cd cracked fractions-namely Cg
hydrocarbons (mainly pentanes and pentenes), carbonyl
compounds such as acetaldehyde, and sulfur compounds
such as methylmercaptan.
(3) Compounds whose solubility does not differ
very much from that of butadiene. Here this only
concerns propyne, but because its boiling point differs
by ca. 20 "C from that of 1,3-butadiene, it can be sepa-
rated by distillation quite easily.
T h e ingredients of the mixture whose solubilities
differ least from that of 1,3-butadiene are referred to as
key components. They govern the amount of solvent
required in the stripper for separation. They are cis-
2-butene and 1,2-butadiene. However, other compo-
nents could also be present in high concentrations in the
feedstock, but present in only small amounts in the end
product.
A schematic diagram showing the separation of the
three groups of materials from 1,3-butadiene is presented
in Figure 3.
Comparison between Various Solvents
T h e greater the solubility of the gas, the less is the
amount of solvent primarily required for physical
scrubbing.
However, the closer the selectivity S, which is defined
by
solubility of 1,3-butadiene
= aB'aK {CQ:
CYK: solubility of key component

lies to 1-i.e., the less the selectivity-the more recycle

AUTHORS U . Wagner and H . M . Weitz are with Badische
Anilin- €3 Soda-Fabrik AG, Ludwigshafen/Rhine, West
Germany. This paper is from the Symposium on Novel
Processes and Technology of the European and Japanese Chemi-
cal Industry presented at the 158th Meeting of the American
Chemzcal Society, New York, N . Y., September 7-12, 1969.
gas to be returned from the desorption fractionating to
the absorber zone (corresponding to the reflux in normal
distillation) has to be used, and this increases the amount
of solvent required. A measure of the amount of solvent
required is given by the efficiency factor F, which allows
for both solubility a n d selectivity.

VOL. 6 2 NO. 4 A P R I L 1 9 7 0 45
 Figure 3. Schematic diagram of a Cq separating with N-methylpyrrolidone

F = cyB(OLB/oLK - 1) = aB(S - 1) these thermodynamic criteria. A particular advantage

I n this equation the selectivity, S, for the key compo-
nents should be used, because these require the greatest
amount of solvent. It is a common source of error in
comparing various solvents for the separation of buta-
diene to use the selectivity for a component that can be
readily separated--e.g., 1-butene-or to use the selec-
tivity for all butenes in general.
A few efficiency factors for the separation of 1,3-
butadiene and cis-2-butene are listed in Table 111.
From these it is clear that N-methylpyrrolidone shows
the highest value.
Similar conditions pertain to the separation of the
components that are more readily soluble than butadiene.
Thus vinyIacetylene, which is a component that can be
readily separated with N-methylpyrrolidone (NMP), be-
comes a key component in acetonitrile. Separation with
selectivities below 1.6-corresponding to a boiling point
difference of about 10 OC-in normal distillation can be
considered as difficult. It demands either large amounts
of solvents or a large number of trays or even both.
There are a number of other aspects that are im-
portant for the assessment of a selective solvent besides
TABLE I I I. COMPARISON OF VARIOUS SOLVENTS
Acetonitrile 82 80 1.47
AT-methylpyrrolidone 206 86 1.66
Dimethylformamide 153 83 1.40
Dimethylacetamide 168 85 1.40
of AV-methylpyrrolidone is its very high hydrolytic and
thermal stability. Thus it does not give rise to corrosion
in any part of the plant, and all equipment can be made
of normal carbon steel. The low vapor pressure a t
normal temperature (Pzs DC= 0.4 mm Hg) facilitates
the recovery of the solvent vapors from the product
stream; owing to the ready solubility of NMP in water,
this operation is most easily accomplished by scrubbing
with water or alternatively with hydrocarbons. Inas-
much as the boiling point of N-methylpyrrolidone is
greater than that of water, it is quite simple to maintain
the water balance in the solvent circuit. All of these
properties entail very low solvent losses. Another
factor worth stressing is the fact that *V-methylpyrroli-
done is physiologically harmless and can be readily
biologically degraded.
Practical Realization of Process
T h e following steps were required to develop the
separating process to technical maturity :
(1) T h e whole separation process had to be minutely
investigated in a pilot plant, and all important operating
data had to be measured exactly.
(2) T h e separation process had to be described
mathematically, and the calculated results had to be
compared with the empirical results obtained in the
pilot plant. T h e mathematical expressions had then
to be adjusted until agreement was obtained.
T h e principle of butadiene separation in the main
scrubbing stage is shown schematically in Figure 4.
T h e gaseous C4 mixture is introduced in the center of
the column, which is subdivided into scrubber and
38 butene stripper. The descending stream of solvent
57 preferentially absorbs the more readily soluble buta-
33 diene, whereas the butenes leave the head of the scrub-
35 ber. 1,3-Butadiene, together with 1,2-butadiene and Cq
acetylenes, which behave very similarly to butadiene in
this section of the plant, is boiled off from the solvent.

46 INDUSTRIAL AND ENGINEERING C H E M I S T R Y

 An amount equivalent to that in the feed mixture is
withdrawn as crude butadiene, and the rest is returned
as recycle gas to the stripper. The crude butadiene
thus obtained is still contaminated with 1,2-butadiene
and the acetylenes, from which it is freed in a completely
analogous second stage. These two steps can be com-
bined to save equipment. T h e flow diagram of a
technical plant (Figure 5) shows that the second scrubber
stage is operated as a side stream column of the main
scrubbing stage. This diagram also shows the removal
of propyne by distillation in the pure butadiene column.
One compressor is required for a standard plant oper-
ating a t optimum economic efficiency ( 3 ) . Nevertheless,
the number of compressors, the arrangement of the
columns, and other design considerations in the separa-
tion process can be modified for given local conditions.
A special computer program was designed for the
separating process. With the aid of this program, the
concentrations of all hydrocarbons a t the top and bot-
tom of the columns and on each theoretical tray can be
calculated. A feature of this calculation is equating the
solubility of each individual component in terms of the
pressure, temperature, and concentration of the other
hydrocarbons in the solvent.
The pilot plant had a monthly capacity of 15 tons of
hydrocarbon feedstock, and the diameter of the column
was 200 mm. A knowledge of the tray efficiency is
required for the technical realization of a separation
process employing mass transfer trays. At present, it
cannot be calculated with a sufficiently high degree of
reliability from the properties of the system, particularly
under the conditions of extractive distillation or counter-
current gas scrubbing. Even extrapolation of results of
Figure 4. Separation of a butene-butadiene mixture by countercurrent mass exchange efficiency obtained with similar systems
scrubbing is unreliable. This applies particularly if high demands

Figure 5. B A S F process for recovery of butadiene. Flow diagram of a commercialplant

Symbols: a, 0 vaporizer; 6 , scrubber; c, butene stripper; d , second scrubber; e, recycle gas compressor; fpdegaser with off-gas scrubber; g , pure butadiene distilla-
tton; h, solvent heat exchanger

VOL. 6 2 NO. 4 APRIL 1 9 7 0 47

a r e imposed on the purity, in which case a large number
of theoretical trays are required. For this reason, ex-
tensive experinients were carried out on a bubble-cap
column with 10 practical trays. T h e relationship of
tray efficiency to all important engineering and design
parameters was investigated. T h e results were evalu-
ated by the computer program mentioned above.
Collating the tray efficiency and solubility model allowed
correct design of the technical plant. T h e tray effi-
ciency determined was 20 to 40%, which are reasonable
[m3 N TP/rn3cP]
r Cm/y
figures for extractive distillation. According to our
measurements, the tray efficiency increases with rise in
temperature and thus with decrease in the viscosity of
the liquid. I t also increases with the hidrocarbon
content of the solvent. I n Figurc 6 the tray efficiencies,
7, calculated from the measurements, are presented
as suggested by O’Connell (7)-z.e., they are plotted
against the magnitude B C?,J,LL, where C, is the concen-
tration of hydrocarbons in the solvent (m3KTP/m3) and p
is the dynamic viscosity of the solvent-hydrocarbon
mixture (cP). Within the limits of error--- z.e., f 15%--
most of the measured points fall on the curve representing
the serniempirical correlation formulated by O’Connell.
T o discover methods of preventing fouling, the forma-
tion of polymers, obtained essentially frorn butadiene,
was investigated during operation of the pilot plant.
T h e deposits can choke columns and equipment and are
particularly disturbing when they are formed in the
heat exchangers. I n a special apparatus the rate of
contamination of heat exchangers was measured under
the operating conditions a t various parts of the plant.
T h e successful avoidance of breakdowns in the plant
was finally achieved and fouling of the heat exchangers
was suppressed (eveii by crude untreated Cd fractions)
by suitable design of the equipment in which poly-
merization occurred and in particular by discovering a
very effective antifouling agent.

Figure 6. Tray eflcicncj-system NMP/H20-C( hjdrocarbons

Results Obtained with Commercial Plant
Symbols: 7, tray eficiency; C ,, concentralion of hydrocarbons in solvent; p, dynamic vis-
cosity of solvent-hydrogen mixture (cP) T o date, three plants for the recovery of butadiene
by the BASF process have been erected. T h e sites and
capacities of these plants are listed in Table IV. T h e
thrce plants were taken on-stream rapidly and ivithout
any trouble. Within a short time, butadiene of rnarket-
able quality was being produced, and since then the
TABLE IV. PLANTS PRODUCING BUTADIENE BY
BASF PROCESS plants have been operating without breakdown. All
Metric the results, in particular the high degree of purity of the
tons of butadiene product, fulfilled expectations. Fouling was
butadiene Taken on- so slight that all heat exchangers kept operating without
Company Site per year stream
Erdolchemie Cologne (Germany) 75,000 March 1968 change for more than one year. Other production units
IC1 Wilton (England) 80,000 June 1968 will be erected in the near future.
Industrialimport Pitesti (Rumania) 15,000 July 1969 By virtue of the beneficial properties of the selective
solvent AY-methylpyrrolidone, the capital and utilities
costs for the separation process are low. Typical values
for utilities are given in Table V. Hence, the BASF
process is a very economic means of producing butadiene
TABLE V. BASF PROCESS FOR RECOVERY
O F BUTADIENE of high quality from crude C4cracked fractions.
Feedstock C1 crack fraction with ca. 45% wt butadiene
Product Butadiene of poly-czs quality
RE FER ENCES
Butadiene losses 3y0
(1) O’Connell, Trans. rimer. Inrt. Chern. En:., 42, 741-6 (1946).
Utilities per ton butadiene product (2) Kirk, R., and Othrnrr, D., “Encyclopedia of Chemical Technology,” Vol. 3,
2nd ed, New York, 1964, p 784 A .
Steam 2.1 tons (3) Klein, I<., and Weitz, H. > f . , Hjdiocarboii Process. Petrol. Rejizer, 47 ( l l ) , 135-8
Electricity 250 kWh (1965).
(4) Kronig, W., EtdoelKohle, 21, 140-8 (1965).
Cooling water 150 m3 ( 5 ) Natta, G., Italian Patent 364,723 (1938).
Condensate 0 . 2 m3 (6) T h e Secrctariat of the International Rubber Study Group, Rubber Statistical
Buiietzn, 2 2 ( l l ) , 2, 20-1 (1968).
,V-Rlethylpyrrolidone < 0 . 2 kg ( 7 ) Weitz, H. hi., tt‘agner, K., and Schmidt, 0. I%.,Chern.-lng.-Ttck.,32, 796-801
Chemicals ca. 0 . 2 Dhl (1960).
(8) KrBper, H., Weitz, H. hf., and Lt‘agner, I?., Pelrol. Rejner, 4 1 ( l l ) , 191-6 (1962).
( 9 ) Weitz, H. M., and Wagner, U., 6th World Petrol. Congr., €‘roc., June 19-26, 1963,
Section IV, Paper 41.
(10) KrBper, H., and LVeitz, H. M., Oil Gni J., 65 (Z), 98-104 (1967).

48 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY