BASF Process Butadiene Separation
BASF Process Butadiene Separation
BASF Process Butadiene Separation
Thethatworld
of all natural rubber products for the first
BASF
Process
for
Production
of
Pure
Butadiene
U. WAGNER
H. M. WElTZ
Compound
Propane
propene
iso-Butane
n-Butane
iso-Butene
1-Butene
trans-2-Butene
cis-2-Butene
1,3-Butadiene
Propadiene
1,2-Butadiene
Propyne
1-Butyne
2-Bu tyne
Vinylacetylene
Diacetylene
C.K+ hydrocarbons
Cracked
fraction,
% VOl
ca. 0.2
1 .o
4.7
23.5
12.6
6.4
5.4
44.6
0.1
0.2
0.3
0.2
Traces
0.8
Traces
Traces
VOL. 6 2
Dehydrogenation
fraction,
% wt
80-35
20-45
Product
butadiene
(guarantee
values)
>99,50J, vol
2:
NO. 4
APRIL 1970
43
Figure 7.
Absorption process:
straight-through scrubbing
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 .
Compound
Propane
iso-Butane
Propene
n-Butane
iso-Butene
1-Butene
Propadiene
trans-2-Butene
cis-2-Butene
1,3-Butadiene
Propyne
1,2-Butadiene
1-Butyne
2-Butyne
Vinylacetylene
Diacetylene
BP, OC
-42.07
-11.73
-47.70
- 0.50
- 6.90
6.26
-34.5
0.88
3.72
- 4.41
-23.22
+ l o . 85
8.1
+26.9
5.1
+10.3
+
+
+
+
Bunsen
solubility
coeficient a!
at I atm and
40 O C , m3
NTP/m3 atm
3.08
4.87
5.37
9.5
15.42
15.6
18.4
20.4
25.1
41.5
43 .O
78.0
102
206
226
2,200
T o give a n idea of the separation task to be accomplished, the components of the C4 fraction are arranged
in Table I1 in sequence of increasing solubility in Nmethylpyrrolidone.
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the feedstock and are withdrawn from the head of the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which in this case is withdrawn a t the head of the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
13.5
8.52
7.73
4.37
2.69
2.66
2.29
2.03
1.65
NO. 4 A P R I L 1 9 7 0
45
cyB(OLB/oLK
- 1)
= aB(S
- 1)
I n this equation the selectivity, S, for the key components 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 butadiene to use the selectivity for a component that can be
readily separated--e.g., 1-butene-or
to use the selectivity for all butenes in general.
A few efficiency factors for the separation of 1,3butadiene 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), becomes 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 important for the assessment of a selective solvent besides
TABLE I I I.
Acetonitrile
82
AT-methylpyrrolidone 206
Dimethylformamide
153
Dimethylacetamide
168
46
80
86
83
85
1.47
1.66
1.40
1.40
38
57
33
35
VOL. 6 2
NO. 4
APRIL 1 9 7 0
47
r
Figure 6.
[m3 N TP/rn3cP]
Cm/y
Tray eflcicncj-system
NMP/H20-C( hjdrocarbons
TABLE IV.
Company
p,
dynamic vis-
Site
Erdolchemie
Cologne (Germany)
IC1
Wilton (England)
Industrialimport Pitesti (Rumania)
TABLE V.
Metric
tons of
butadiene
per year
75,000
80,000
15,000
Taken onstream
March 1968
June 1968
July 1969
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