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ONE-STEP

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

UDC 542.941.7 +547.214

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:

C4HI0 -~ 2HCI "- 0~--> [C41{sCI~]~- 2H~0


i
CtH6 -~-211CI
C~tI10-{- 1/~0~-[- HC1~ [C~HgC1]+ H~O
C4Hs-t" HC1

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.

Academy of Sciences of the USSR. Translated from


R-o. 6, pp. 1288-1293, June.. 1909. Originalarticle

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

I Yieldon the basis of reacted butane, %

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

found after 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

*Has the same composition of the active portion as catalyst 3, but


a different carrier,
s o l u t i o n on a w a t e r b a t h and d r y i n g in a d r y i n g o v e n , the c a t a l y s t s w e r e h e a t e d in a c a t a l y t i c tube in a
s t r e a m of a i r at 600~
T h e c a r r i e r s w e r e a l u m i n u m oxide and b r a n d KSK s i l i c a g e l with a g r a i n s i z e of
2-3 r a m . C a t a l y s t 4 was p r e p a r e d b y i m p r e g n a t i n g s i l i c a g e l with i r o n n i t r a t e and d e c o m p o s i n g the s a l t
in a s t r e a m of a i r . E x p e r i m e n t s w e r e c o n d u c t e d in a f l o w - t y p e a p p a r a t u s with a h o r i z o n t a l f u r n a c e 600 m m
l o n g in a q u a r t z r e a c t o r ( i n n e r d i a m e t e r 8 r a m ) , into which the c a t a l y s t (8-10 ml) was loaded, and p i e c e s
of b r o k e n q u a r t z w e r e p l a c e d in f r o n t of it. E a c h e x p e r i m e n t l a s t e d 45 m i n ; the c a t a l y s t was h e a t e d and
c o o l e d in a s t r e a m of a i r .
S t a r t i n g m a t e r i a l s : n - b u t a n e had the c o m p o s i t i o n (% b y weight): n - b u t a n e 92.4, i s o b u t a n e 4.4, p r o p a n e

2.3, and e t h a n e 0.8. T h e s o u r c e of oxygen was a i r ; a t m o s p h e r i c n i t r o g e n was the d i l u e n t . T h e gas m i x t u r e


was p r e p a r e d b y m i x i n g a i r a n d b u t a n e in a g a s o m e t e r ; its c o m p o s i t i o n w a s v a r i e d in b u t a n e : a i r r a t i o s f r o m
1:2 to 1:6 (vol.); the e x a c t c o m p o s i t i o n was e s t a b l i s h e d c h r o m a t o g r a p h i c a l l y . H y d r o c h l o r i c acid was u s e d
in 10, 20, and 25% c o n c e n t r a t i o n s ; its c o n c e n t r a t i o n was d e t e r m i n e d by t i t r a t i o n . G a s e o u s h y d r o g e n c h l o r i d e was p r o d u c e d by the a d d i t i o n of c o n c e n t r a t e d HC1 to h e a t e d H2SO 4. H y d r o b r o m i c acid was u s e d in a 40%
c o n c e n t r a t i o n ; c h l o r i n e was t a k e n f r o m a c y l i n d e r ; the r a t e of its d e l i v e r y was m o n i t o r e d with a r h e o m e t e r .
B u t e n e was p r o d u c e d by d e h y d r a t i o n of b u t a n o l at 400-420~ o v e r p r o m o t e d A12Oa [7]; b u t e n e had the c o m p o s i t i o n (% b y weight): butene--1 94.6, t r a n s - b u t e n e - 2 1.7, and c i s - b u t e n e - 2 3.7.
T h e r e a c t i o n t e m p e r a t u r e was m e a s u r e d with an A l u m e l - C h r o m e l t h e r m o c o u p l e ,
was in a pocket w i t h i n the l a y e r of the c a t a l y s t . On a c c o u n t of the e x o t h e r m i c c h a r a c t e r
t e m p e r a t u r e was r a i s e d by 5-10~ d u r i n g the e x p e r i m e n t , d e p e n d i n g on the c o m p o s i t i o n
m i x t u r e and on the a c t i v i t y of the c a t a l y s t . T a b l e s 1-5 i n d i c a t e the a v e r a g e t e m p e r a t u r e
The airwas m o n i t o r e d
ringe burette.
in a g a s o m e t e r

1188

the end of which


of the p r o c e s s , the
of the r e a c t i o n
of the e x p e r i m e n t .

b u t a n e r e a c t i o n m i x t u r e w a s d e l i v e r e d to the r e a c t o r f r o m a g a s o m e t e r , and its v e l o c i t y


by a r h e o m e t e r . H y d r o c h l o r i c a c i d and the o t h e r l i q u i d r e a g e n t s w e r e a d m i t t e d f r o m a s y T h e e x h a u s t g a s e s p a s s e d t h r o u g h a c o i l e d t r a p , c o o l e d with ice w a t e r , and w e r e c o l l e c t e d
above b r i n e . T h e c o m p o s i t i o n of the r e a c t i o n p r o d u c t s was d e t e r m i n e d On a gas a n a l y z e r

TABLE 3. Oxidative Dehydrogenation of n - B u t a n e on V a r i o u s Catalysts


Yield on the basis of reacted
butane, %

I
t

T of ex- Volume ; Mixtureof


Cat lyst '
velocity,
9
C4111~
M
O2
h -1
a

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

TABLE 4. Influence of the C o m p o s i t i o n of M i x t u r e s on the Oxidative


Dehydrogenation

of n- Butane

I Yield Oil the basis of reacted

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

and c h r o m a t o g r a p h ; the e s t e r of t r i e t h y l e n e g l y c o l and n - b u t y r i c a c i d was u s e d as the s t a t i o n a r y p h a s e .


The liquid r e a c t i o n p r o d u c t s , which w e r e c o l l e c t e d in the c o i l e d t r a p , r e p r e s e n t e d an aqueous solution of
h y d r o c h l o r i c acid, the content of which was d e t e r m i n e d by t i t r a t i o n .
DISCUSSION

OF

RESULTS

The influence of various additives on the oxidative dehydration


lysts 2 and 3 at 544-579~
(Table i).

of n-butane was investigated on cata-

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

TABLE 5. Oxidative Dehydrol ,~enation of Butene-1 on C a t a l y s t 4


T. ofexperi-iVolume ve- Mixture of Conversion Yieldon the basisof reacted C4Hs, %
ment ~
.locity, hC4Its:Oz of C4F[s, %
(202 + CO
C4H6
G2H4
: HC1, M
546

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

Thus, of all the a d d i t i v e s t e s t e d , h y d r o c h l o r i c a c i d has the g r e a t e s t f a v o r a b l e effect on the one--step


p r o d u c t i o n of b u t a d i e n e fron n - b u t a n e .
The amount of h y d r o c h l o r i c a c i d p a s s e d into the r e a c t o r above c a t a l y s t s 3 and 6 (Table 2) and the
amount of the acid c o l l e c t e d a f t e r the e x p e r i m e n t d i f f e r by an amount not e x c e e d i n g the e x p e r i m e n t a l e r r o r .
A p p a r e n t l y h y d r o c h l o r i c acid, while r e q u i r e d for the o x i d a t i v e d e h y d r o g e n a t i o n of n - b u t a n e , is not consumed.
The data obtained on the influence of the c o m p o s i t i o n of the c a t a l y s t s a r e given in T a b l e s 3 and 4.
In the p r e s e n c e of s i l i c a gel, which s e r v e d as a c a r r i e r of the c a t a l y s t s , only r e a c t i o n s of c r a c k i n g and
oxidation to CO 2 and CO take p l a c e . On c a t a l y s t 1, containing c o p p e r and p o t a s s i u m c h l o r i d e s , the r e a c tions of f o r m a t i o n of u n s a t u r a t e d C 4 h y d r o c a r b o n s , c r a c k i n g and oxidation take p l a c e to equal d e g r e e s .
Without h y d r o c h l o r i c acid on this c a t a l y s t , a l l the c o n v e r t e d butane is o x i d i z e d to CO 2 and CO.
In the p r e s e n c e of a i r and p o t a s s i u m s a l t s ( c a t a l y s t 2), the f o r m a t i o n of C 4 h y d r o c a r b o n s b e c o m e s
the p r i n c i p a l r e a c t i o n , while the y i e l d of b u t a d i e n e r e a c h e s 30%; the f r a c t i o n of c r a c k i n g and oxidation r e a c tions is s u b s t a n t i a l l y r e d u c e d . In the p r e s e n c e of c o p p e r , iron, and p o t a s s i u m c h l o r i d e s ( c a t a l y s t 3, s e e
T a b l e 4), t h e r e is a s u b s t a n t i a l f o r m a t i o n of butenes and b u t a d i e n e (a total of up to 80%), and a c o m p a r a t i v e l y s m a l l y i e l d of oxidation and c r a c k i n g p r o d u c t s is obtained. J u s t as high y i e l d s of butenes and butadiene (a t o t a l of up to 83%) a r e obtained in the p r e s e n c e of c a t a l y s t 4, c o n s i s t i n g of f e r r i c oxide and p o t a s sium c h l o r i d e on s i l i c a gel; the y i e l d of oxidation p r o d u c t s is even lower than on c a t a l y s t 3.
C a t a l y s t 5, p o s s e s s i n g the s a m e c o m p o s i t i o n of the a c t i v e p o r t i o n as c a t a l y s t 3, but a d i f f e r e n t o a r r i e r (A1203), is l i t t l e s u i t e d for the r e a c t i o n of o x i d a t i v e d e h y d r o g e n a t i o n of butane at 453-602~
J u s t as
on c a t a l y s t 1, without h y d r o c h l o r i c a c i d butane is c o n v e r t e d only to CO 2 and CO; the addition of h y d r o c h l o r i c
acid at low t e m p e r a t u r e (460~ p r o d u c e s the f o r m a t i o n of b u t e n e s , while at h i g h e r t e m p e r a t u r e s (553 and
602~
b u t a d i e n e is f o r m e d , but the y i e l d of C 4 h y d r o c a r b o n s does not e x c e e d 38%. Consequently, b r a n d
KSK s i l i c a gel is m o r e s u i t a b l e as a c a r r i e r than A1203. In the a b s e n c e of a c a t a l y s t in a r e a c t o r f i l l e d with
q u a r t z , the r e a c t i o n does not t a k e p l a c e .
F r o m the data of T a b l e 4 it is evident that the t e m p e r a t u r e has l i t t l e influence on the o x i d a t i v e deh y d r o g e n a t i o n of butane. In e x p e r i m e n t s 17 and 21, the r e a c t i o n t e m p e r a t u r e changes by 32~
in this c a s e
the c o n v e r s i o n of butane i n c r e a s e s by 10%, and the y i e l d of C 4 h y d r o c a r b o n s d e c r e a s e s by only 6%.
I n c r e a s i n g the r e l a t i v e amount of oxygen in the initial m i x t u r e f r o m 0.4 to 1.3 m o l e s / m o l e of butane,
with the s a m e amount of h y d r o c h l o r i c acid ( e x p e r i m e n t s 10, 11, and 12, T a b l e 4) has no effect on the y i e l d
of b u t a d i e n e , but the y i e l d of butenes d r o p s by a l m o s t twofold, and the y i e l d of p r o d u c t s of c o m p l e t e o x i d a Lion i n c r e a s e s by t h r e e - to fourfold. The i n c r e a s e in the r e l a t i v e amount of h y d r o c h l o r i c acid ( e x p e r i m e n t s
13 and 14) with a s i m u l t a n e o u s i n c r e a s e in the t e m p e r a t u r e (up to 592~ gives a m a x i m u m y i e l d of butadiene
of 34-38% and 32-14% b u t e n e s , r e s p e c t i v e l y , on the b a s i s of the r e a c t e d butane; the y i e l d s on the b a s i s of the
butane p a s s e d through c o m e to 23-24 and 22-12%, r e s p e c t i v e l y . However, a l m o s t half of the r e a c t e d butane
is c o n v e r t e d to c r a c k i n g and o x i d a t i o n p r o d u c t s in this c a s e .
In e x p e r i m e n t s with c a t a l y s t 4 the s a m e influence of h y d r o c h l o r i c acid was o b s e r v e d ( e x p e r i m e n t s
16, 18, 20, and 21). The y i e l d of b u t a d i e n e r e a c h e d 36% on the b a s i s of the r e a c t e d butane or 29% on the
b a s i s of the butane p a s s e d through, but the y i e l d of butenes changed l i t t l e , while the y i e l d s of all the o t h e r
p r o d u c t s w e r e r e d u c e d . F u r t h e r i n c r e a s i n g the amount of h y d r o c h l o r i c acid 3.5 m o l e s / m o l e of C4H10 did
not influence the y i e l d s of the r e a c t i o n p r o d u c t s ( e x p e r i m e n t 22). In the o x i d a t i v e d e h y d r o g e n a t i o n of butane
with h y d r o c h l o r i c acid, u s u a l l y equal amounts of butene-1 and b u t e n e - 2 a r e obtained in the r e a c t i o n p r o d u c t s
(with the exception of e x p e r i m e n t 14); the l a t t e r i s o m e r contains equal amounts of the c i s - and t r a n s - f o r m s .

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In the oxidative dehydrogenation of butene-1 on catalyst 4 at 545-585~ without hydrochloric acid,


48% butene reacted; it was only 25% converted to butadiene, and 70% to CO 2 and CO (Table 5). When byd r o c h l o r i c acid was added, the yield of butadiene r o s e to 65-73% on the basis of the reacted butene; m o r e over, at a lower t e m p e r a t u r e m o r e of it was formed than at a higher t e m p e r a t u r e . The yield of oxidation
products was lowered to 25%. No isomerization with displacement of the double bonds was observed.
CONCLUSIONS
1. The oxidative dehydrogenation of n-butane on metal chlorides in the t e m p e r a t u r e interval 550-590~
is a heterogeneous catalytic reaction and proceeds when h y d r o c h l o r i c acid is added.
2. Copper, iron, and potassium chlorides, as weI1 as f e r r i c oxide on silica gel, were studied as
catalysts for this reaction; the content of the acid ingredient was 10-12%.
3. The yields of butenes and butadiene r e a c h e d 34-40 and 35-38% on the basis of r e a c t e d butane, r e spectively, with an optimum reagent ratio C4H10:O2:HCIclose to 1:1.2.
4. Oxidative dehydrogenation of butene-1 proceeded under the s a m e conditions; in this ease 63-73%
butadiene was formed on the basis of the r e a c t e d butene; without h y d r o c h l o r i c acid the yield of butadiene
r e a c h e d only 25%.
LITERATURE
1.

2.

3.

4.

5.
6.
7.

CITED

V. K. Skarchenko, Uspekhi Khimii, 37, 3 (1968).


G. A. Stepanov, V. A. Kolobikhin, R. Ya. Chugunnikov, and M. I. Myasoedov, Khim. P r o m - s t ' , No. 4,
260 (1967); A. P. Tsailingol'd, G. A. Stepanov, E. E. Chekhov, and T. P. Vernov, ibid., No. 3, 186
(1962); S. V. Adel'son and V. I. Nikonov, ibid., No. 8, 572 (1966).
Great Britain Patent No. 1032276; RZhKhim., No. 10N8 (1967); F r e n c h Patent No. 1385650; Chem.
A b s t r s . , 62, 13043 (1965); US Patent No. 3268611; RZhKhim. No. 23N17 (1967); US Patent No. 33081853308198, OfitsiaUnaya Gazeta, 836, Section II; Khimiya, 1 (10), M a r c h 7, 1967, p. 72.
B. A. Kren~sel', Chlorination of Paraffin Hydrocarbons [in Russian], Nauka (1964), p. 60.
Ya. T. l~idus and N. I. Ershov, Kinetika i Kataliz, 8, 1387 (1967).
D. V. Tishchenko, Zh. Obshch. Khim., 17, 460 (1947).
N. I. P i s ' m a n , V. V. Kas'yanov, and M. A. Dalin, Kinetika i Kataliz, 6, 741 (1965).

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