Documente Academic
Documente Profesional
Documente Cultură
PRODUCTION
n-BUTANE
BY O X I D A T I V E
IN T t I E
PRESENCE
G. A . T a r a s o v a
OF
BUTADIENE
DEItYDROGENATION
OF HYDROCHLORIC
and
FROM
Z. A.
ACID
Solomatina
At the present time, the oxidative dehydrogenation of olefins is used for the production of diene hydrocarbons [1]. However, attempts to apply this reaction to saturated h y d r o c a r b o n s have encountered a number of difficulties. Under these conditions the oxidative c r a c k i n g of the paraffin hydrocarbon proceeds
v e r y readily, but when the t e m p e r a t u r e of the reaction is lowered, oxygen products are formed. To obtain
dienes on paraffins, dehydrogenation is conducted in the p r e s e n c e of oxygen, iodine, and an acceptor of hydroiodic acid. This method has been well developed and has been described in detail [2]. The use of other
halogens and hydrogen halides in the oxidative dehydrogenation reaction is mentioned in certain patents [3];
however, the c o r r e s p o n d i n g alkene is most often indicated as the initial hydrocarbon for the production of
the diene.
In this work we investigated the formation of divinyl fron n-butane under conditions of oxidative dehydrogenation at 550-590~
The catalysts were chlorides of metals of variable valence, usually used as
catalysts of the chlorination and oxidative chlorination of h y d r o c a r b o n s [4]. In addition to a catalyst, the
p r e s e n c e of a s u p p l e m e n t a r y component is needed to s u c c e s s f u l l y conduct a reaction of oxidative dehydrogenation [5]. We tested water, chlorine, hydrogen chloride, hydrochloric and h y d r o b r o m i c acids as this
component. With h y d r o c h l o r i c acid the reaction proceeded with a high yield of unsaturated C 4 hydrocarbons,
while without it only products of complete oxidation and cracking w e r e formed f r o m n-butane. Hydrochloric
acid was not consumed as a r e s u l t of the reaction and was isolated in almost the same amount together with
the reaction products. In the absence of a solid catalyst, the reaction did not proceed. The best results
were obtained with a catalyst containing f e r r i c oxide: butadiene was f o r m e d f r o m butane in the p r e s e n c e of
air and hydrochloric acid in one step with a yield of up to 36%; m o r e o v e r , the yield of butenes reached 34%.
Such high yields of unsaturated C 4 hydrocarbons were observed at a m o l a r ratio C4Ht0.~O2:HC1close to 1:1:2.
The results obtained p e r m i t us to propose the following scheme of the formation of butenes and butadiene
f r o m butane, in which the intermediate steps are chlorination and dehydrochlorination:
The absence of c h l o r o - d e r i v a t i v e s in the reaction products does not contradict this scheme. As was
shown in [6], on sulfides and chlorides of magnesium and calcium, butadiene is f o r m e d from 1,4-dichlorobutane at 300-350~ with a yield of 78%. T h e r e f o r e , at the t e m p e r a t u r e of the reaction that we investigated,
the dichloride should be entirely decomposed.
In this work it was also shown that butene-1 in a mixture with air and hydrochloric acid on catalyst
4 at 560~ can also form butadiene with a yield of 73%; without hydrochloric acid the yield of butadiene is
only a third as great (25%), and the principal reaction becomes oxidation to CO2 and CO (70%).
EXPERIMENTAL
METHOD
The catalysts had the following composition (% by weight): i) 8CUC12, 2KCI, 90SIO2; 2) 6FeCI3, 2KCI,
92SIO2; 3)7CuCl 2, 3FeCI3, 88SiO2; 4)10Fe203, 2KCI, 88SIO2; 5)7CuCI 2, 3FeCI3, 2KCI, 88A1203. The catalysts were prepared by impregnating a carrier with aqueous solutions of the salts. After evaporation of the
N. D. Zelinskii Institute of Organic Chemistry,
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,
submitted June 5, 1968.
1187
T A B L E 1. I n f l u e n c e of V a r i o u s A d d i t i v e s to an A i r - B u t a n e
n-Butane
Numher
M i x t u r e on the Oxidative D e h y d r o g e n a t i o n of
Additive
p
(g
~d
name
~ ~o
'
-I
1
2
3
4
5
6
3
3
3
3
2
2
555
550
550
555
573
579
579
8
9
2
2
544
558
800
480
720
820
715
770
770
700
720
1:0.4
1:0.4
:ff
].:0.4
1:0.4
1:1.7
1:1.6
1:1,6
t:1.0
1:0.9
HC1 (acid)
The same
HC1 gas
The same
HBr (acid)
The same
0.5
2.7
~3.7
~2.0
1.3
I.I
61
46
88
74
73
62
16
27
9
8
70
.... [3
0
0
31
30
8
12
0
0
27
23
7.8
0.8
Nol!e
Water
C12
I0
16
20
12
30
20
15
28
22
II
18
34
14
40
C
41 -: 27
45-27
15-12
6+4
21~17
27-5
29+23
15-22
14+44
T A B L E 2. B a l a n c e of H y d r o c h l o r i c Acid
ItC1 (acid), g
Catalyst No.
3
3
6*
6
passed through
in experiment
difference
2.00
3.81
2.68
2.48
2.29
3.67
2.68
2.37
+0,29
-0.!4
0
-0.11
1188
I
t
Conver-
sion of
butane, %
8+
o
:3+
Quartz
SiO z
l
554
579
548
551
1000
680
740
680
1:0,8:0,7
1:0,8:1,3
1:0,8:1,0
1:1,3:0
t~
52
62
29
550
584
573
710
710
715
1:0,8:1,0
1:1,0:1,7
1:1,7:2,7
56
67
t~8
453
460
553
602
650
630
655
350
1:0,8:0
1:0,8:0,5
1:0,8:1,2
l:0,8:1,4
26
27
42
43
i,
19
1~
1~
i,
23
1~
27
29
30
2?
57+7
18+11
, 76-M7
18
15
58
1!
I~
14 i-9
12.X-ll
214-1z
90+2
444-14
43~12
43+20
of n- Butane
Number
experi- c a t a ment lyst
19
ii
12
13
14
16
17
18
19
20
21
22
81 >0 _ a9 =
555
557
556
592
587
558
558
559
560
593
590
b79
450
1250
1080
685
715
739
733
730
760
829
733
740
Mixture of
C4H10 : Oz
: HC1, M
but__a_ne,%
CO:+
.!-CO
L) o
1:0,4:0,9
I :0,8:0,8
46
53
68
70
90
62
71
77
72
62
81
73
1:1,3:0,8
1:1,0:1,8
1:1,3:2,1
1:0,8:1,3
1:1,0:1,7
1:1,1:2,8
I:1,5:2,0
1:1,0:0,9
t:1,0:1,7
1:1,0:3,5
28
18
16
17
31
15
16
15
II
25
22
20
20
17
17
16
25
22
20
18
15
17
17
22
20
24
34
38
26
32
35
32
20
36
31
lO
13
16
13
21
12
9
1
13
23
16 I
16 !
5 i-3
19 ~14
15-12
10 1-12
12+14
4 @6
6 .':-8
7+9
9+7
114-13
6+7
OF
RESULTS
With catalyst 3 in the presence of water, the reaction proceeds just as with the air-butane mixture
alone: butane reacts to an extent of only 22%, being 68-72% converted to products of complete oxidation
(CO 2 and CO) and 23-27% to products of cracking (C2II 4 and C3H6). When chlorine is added, the yield of
C 4 hydrocarbons reaches 57%; however, butadiene comprises only 10% of them; the yields of the products
of cracking and complete oxidation are reduced. Hydrochloric acid even more increases the yield of C 4
hydrocarbons
(to 77%) and lowers the yield of products of cracking and oxidation.
A comparison of the effects of hydrochloric acid and gaseous HCI on the conversion of butane was
conducted on catalyst 2. In the presence of hydrogen chloride, the conversion of butane is lowered from
88 to 74%, and the yield of C 4 hydrocarbons is lowered from 47 to 40%: but the reaction of cracking is appreciably intensified - from 15 to 28%. In the presence of hydrogen chloride, the catalyst is rapidly poisoned: in the second experiment, conducted after the first without regeneration of the catalyst, the yields
of butenes and butadienes were reduced by 1.5-fold, while that of oxidation products was almost doubled
(Tables 6 and 7). The addition of hydrobromic
acid even at a comparatively low temperature (544~
leads
to strong cracking and complete oxidation of n-butane. The yield of unsaturated hydrocarbons with C~ composition is substantially lower than in the presence of hydrochloric acid, although the yield of butadiene is
50% higher than that of butenes (experiments 5, 8, and 9).
1189
583
586
580
720
720
720
710
1
1
1
1
1,0 : 1,6
1,0 : 1,5
1,0:0,9
1,3 : 0
33
54
44
48
73
63
45
25
25
32
52
70
1190
2.
3.
4.
5.
6.
7.
CITED
1191