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Cyclodimerization of butadiene on cationic forms of zeolite X
Cyclodimerization of butadiene on cationic forms of zeolite X
135
REFERENCES 1. S. V. LEBEDEV, G. G. KOBLYANSKII arid A. I. YAKUBCHIK, ZhRKhO 56, 265,
1925 2. N. K. YURASHEVSKII, Zh. obshch, khimii 5, 1098, 1935 3. N. B. DOBROSERDOVA, A. I. LEONOVA and I. V. GOSTUNSKAYA, l~eftekhimiya 15, 57, 1975 4. I. V. GOSTUNSKAYA, V. Yu. FISHBEIN, N. B. DOBROSERDOVA and A. I. LEONOVA, Neftekhimiya 17, 1977 5. It. DUS', Vses. konf. pc mekhanizmu heterogenao-kataliticheskikh reaktsii (AllUnion Conference on the Mechanism of Heterogeneous Catalytic ]~eactions). Moscow, 1974 6. 1% W. SELWOOD, J. Catalysis 42, 148, 1976 7. C. G. LE FEVItE and It. J. W. L]~ FEVItE, J. Chem. Soc., 483, 1936 8. G. V. SMIT and Dzh. A. ItOT, IV Mezhdunar. kongress pc katalizu (IV Iutcrnational Congress on Catalysis). Symposium, Mekhanizm i kinetika slozhnykh katalitichcskikh reaktsii (Mechanism an4 Kinetics of Complex Catalytic ]~eactioas). Moscow, 1968 9. A. A. BALANDIN, Mul'tipletnaya teoriya kataliza (Multiple Theory of Catalysis)~ III, Iz4. Moskw. un-ta, Moscow, 1970 10. A. L. MARKMAN, Uzb. khim. zh. 5, 56, 1963 11. N. B. DOBItOSERDOVA, T. A. GULYAYEVA, A. I. LEONOVA and I. V. GOSTUNSKAYA, Neftekhimiya 14, 16, 1974
Petrol. Chem. U.S.R.R. ¥ol. 17. No. 3, pp. 185-187. Pergamon Press Ltd. 1978.Printed in Poland
0031-6458/77/0701-0135507.50/0
CYCLODIMERIZATION OF BUTADIENE ON CATIONIC FORMS OF ZEOLITE X * B. K. I~EFEDOV and N. S. SERGEYEVA 1N ~. D. Zelinskii Institute of Organic Chemistry, U.S.S.R. Academy of Sciences
(Received 10 November 1976) BUTADIENE w a s s u b j e c t e d t o c y c l o d i m e r i z a t i o n , in o r d e r t o o b t a i n v i n y l c y c l o h e x e n e a n d c y c l o - o c t a d i e n e in t h e p r e s e n c e o f n a t u r a l [1, 2] or s y n t h e t i c [3] a l u m i n o s i l i c a t e s a n d m e t a l c o m p l e x e s [4-6]. More s a t i s f a c t o r y r e s u l t s w e r e obtained with composite catalysts at a temperature of 40-115 ° and at atmos p h e r i c p r e s s u r e . F o r e x a m p l e , in t h e p r e s e n c e o f p h e n y l p h o s p h i n i c nickel complexes butadiene was converted to cyclo-l,5-octadiene to the extent of 9 6 % a t a r a t e o f 800 g / g Ni h o u r [7], while in t h e p r e s e n c e o f c a r b o n y l p h o s p h i * Neftekhimiya 17, No. 4, 516-517, 1977.
B . K . NEFEDOVe..*al.
136
nic nickel complexes vinylcyclohexene was mainly obtained (40% with a butadiene conversion of < 8 5 % ) [8]. In the presence of natural and synthetic aluminosilicates the vinylcyclohexene formed is hydrogenated to ethylbenzene. C Y C L O D I M E R I Z A T I O N OF B U T A D I E I ~ E I N T H E I~RESENCE OF N A X
Z E O L I T E A N D ITS C A T I O N I C
:FORMS AT AT1KOSPHERIC P R E S S U R E
Butadiene conT,
°C
version, %
_ %Olig°mer°f yield
Butadiene cong/g eata- T, °C version, lyst • hr %
C,H6 passed through
Without catalyst 300 320 360 360
3'9 7"4 9.5
27.o
300 320 340 360
0"08 0.2 0.8 NaX I 26.7
I
0.1
360
Oligomer yield % of C4He passed through
0.5 % RhNaX 16.0 14.7 21.9 18.7 23.6 24.8 43.9 38.7 0.25% RhNaX 42.1 I 39.3 t
g/g catalyst. hr
0"05 0"09 0'15 0"32 0.40
A study is made of the catalytic activity of N a X zeolite and cationic forms of X type zeolite in dimerization of butadiene at atmospheric pressure, since ~he activity of the Cu(I) form of zeolite X or Y was noted previously in a p a t e n t [9]. It follows from tabulated results that N a X zeolite at 360 ° has low polymerization activity. Thermal polymerization of C4H6 in the range of 300360 ° takes place to a slight extent. The addition to N a X zeolite of Cu(II), Ni(II), Cr(III) and Co(II) cations in a proportion of 0.5-1.0% has no marked effect on activity. In the presence of R h N a X zeolite with a Rh content of 0.250.5% the rate of oligomerization of butadiene increased 2-2.5-fold. On reducing rhodium content from 0.5 to 0.25%, reaction rate related to 1 g-arm R h increased from 658 to 16,464 g oligomer/g-atm Rh.hour. The catalyst of 0.5% R h N a X did not change activity for 105 hours. The main product of oligomerization of butadiene was vinylcyclohexene (b.p. 126 °, n~° 1.4633, yield 98-99% of liquid reaction products). In the N M R spectrum of 18C (15.08 rag) in the experiment off resonance revealed the following: doublets at 143.76; 126.97; 126.26; 38.07 p.p.m, and triplets: at 112-56; 31.45; 28.84; 25.19 p.p.m. The I R spectrum contained frequencies (v, cm -1) at: 3087, 3070, 1643, 998, 915 ( C H = C H ~ group); 3010, 1655 ( C = C in the ring). I t was thus shown that the R h form of zeolite X is an active catalyst in cyclodimerization of butadiene at 320-360 ° and at atmospheric pressure. Under the conditions indicated at a space velocity of 300-500 hr -1 butadiene reacts to the extent of 22-44%, being converted te vinylcyclohexene to 98-99%.
Cyelodimerization of butadieno on cationic forms of zeolite X
137
EXPERIMENTAL
E x p e r i m e n t s were carried o u t in a continuous a p p a r a t u s in a q u a r t z t u b e w i t h a n i n t e r n a l d i a m e t e r of 20 m m , into which 5 g c a t a l y s t was placed. L i q u i d p r o d u c t s were collected in a c o n t a i n e r a t 25 ° a n d analysed using a n LKhM-8M_D c h r o m a t o g r a p h (phase of 1 0 ~ polyethyleneglycol a d i p a t e on chromosorb W, f r a c t i o n of 30-60 mesh, carrier gas (helium) v e l o c i t y 40 ml/min, c o l u m n length 5 m). Vinylcyclohexene was isolated b y rectification. The NI~IR s p e c t r u m o f la(3 was r e c o r d e d using a B r u k e r Spectrospin device in CCI~ solution w i t h TMS as i n t e r n a l s t a n d a r d . Ii~ spectra were recorded in a Ul~-20 device in a t h i n l a y e r of p u r e material. Catalysts were p r e p a r e d b y cationic e x c h a n g e of N a X zeolite (containing 2 0 % b i n d e r -- G l u k h o v clay) f r o m dilute solutions o f m e t a l chlorides neutralized to a p H o f 7 w i t h a 20% dilute solution o f I~HaOH. T h e catalysts were h e a t e d in air to 500 ° for 5 hr before t h e experiments. SUMMARY
B u t a d i e n e is c o n v e r t e d to 1-vinyleyclohex-3-ene to t h e e x t e n t o f 2 2 - 4 4 % in t h e presence o f R h N a X zeolite a t a t e m p e r a t u r e of 320-360 ° a n d a t a t m o spheric pressure w i t h a selectivity of 9 8 - 9 9 % . REFERENCES
1. F. Yu. RACHINSI~H and N. I. RZHEKHINA, Zh. obsheh, khimii 25, 244, 1955 2. Ya. M. SLOBODIN, F. Yu. RACHINOVSKII and I. N. SHOKHOR, Zh. obsheh, khimii 17, 9, 374, 1659, 1947 3. S. R. SERGIYENKO and N. V. ZHDANOVA, Dokl. AI~ SSSR 104, 737, 1955 4. Pat. of GFR 2417985; 1975 Chem. Abstrs. 83, 9308, 1975 5. S. E. JACOBSON and C. U. PITTMAN, Chem. Com., 187, 1975 6. G. WILKE, E. W. MULLER and M. KRONER, Angew. Chem. 73, 33, 1961; 75, 10, 1963 7. P. HEIMBACH au4 W. BRENNER, Angew. Chem. 79, 819, 1967 8. W. BRENNER, P. HEIM~ACH, H. HEY, E. W. MULLER and G. WILKE, Lieb. Aim. 727, 161, 1969 9. U.S.A. Pat. 3444253, 1969; Chem. Abstrs. 71, 38433, 1969
135
REFERENCES 1. S. V. LEBEDEV, G. G. KOBLYANSKII arid A. I. YAKUBCHIK, ZhRKhO 56, 265,
1925 2. N. K. YURASHEVSKII, Zh. obshch, khimii 5, 1098, 1935 3. N. B. DOBROSERDOVA, A. I. LEONOVA and I. V. GOSTUNSKAYA, l~eftekhimiya 15, 57, 1975 4. I. V. GOSTUNSKAYA, V. Yu. FISHBEIN, N. B. DOBROSERDOVA and A. I. LEONOVA, Neftekhimiya 17, 1977 5. It. DUS', Vses. konf. pc mekhanizmu heterogenao-kataliticheskikh reaktsii (AllUnion Conference on the Mechanism of Heterogeneous Catalytic ]~eactions). Moscow, 1974 6. 1% W. SELWOOD, J. Catalysis 42, 148, 1976 7. C. G. LE FEVItE and It. J. W. L]~ FEVItE, J. Chem. Soc., 483, 1936 8. G. V. SMIT and Dzh. A. ItOT, IV Mezhdunar. kongress pc katalizu (IV Iutcrnational Congress on Catalysis). Symposium, Mekhanizm i kinetika slozhnykh katalitichcskikh reaktsii (Mechanism an4 Kinetics of Complex Catalytic ]~eactioas). Moscow, 1968 9. A. A. BALANDIN, Mul'tipletnaya teoriya kataliza (Multiple Theory of Catalysis)~ III, Iz4. Moskw. un-ta, Moscow, 1970 10. A. L. MARKMAN, Uzb. khim. zh. 5, 56, 1963 11. N. B. DOBItOSERDOVA, T. A. GULYAYEVA, A. I. LEONOVA and I. V. GOSTUNSKAYA, Neftekhimiya 14, 16, 1974
Petrol. Chem. U.S.R.R. ¥ol. 17. No. 3, pp. 185-187. Pergamon Press Ltd. 1978.Printed in Poland
0031-6458/77/0701-0135507.50/0
CYCLODIMERIZATION OF BUTADIENE ON CATIONIC FORMS OF ZEOLITE X * B. K. I~EFEDOV and N. S. SERGEYEVA 1N ~. D. Zelinskii Institute of Organic Chemistry, U.S.S.R. Academy of Sciences
(Received 10 November 1976) BUTADIENE w a s s u b j e c t e d t o c y c l o d i m e r i z a t i o n , in o r d e r t o o b t a i n v i n y l c y c l o h e x e n e a n d c y c l o - o c t a d i e n e in t h e p r e s e n c e o f n a t u r a l [1, 2] or s y n t h e t i c [3] a l u m i n o s i l i c a t e s a n d m e t a l c o m p l e x e s [4-6]. More s a t i s f a c t o r y r e s u l t s w e r e obtained with composite catalysts at a temperature of 40-115 ° and at atmos p h e r i c p r e s s u r e . F o r e x a m p l e , in t h e p r e s e n c e o f p h e n y l p h o s p h i n i c nickel complexes butadiene was converted to cyclo-l,5-octadiene to the extent of 9 6 % a t a r a t e o f 800 g / g Ni h o u r [7], while in t h e p r e s e n c e o f c a r b o n y l p h o s p h i * Neftekhimiya 17, No. 4, 516-517, 1977.
B . K . NEFEDOVe..*al.
136
nic nickel complexes vinylcyclohexene was mainly obtained (40% with a butadiene conversion of < 8 5 % ) [8]. In the presence of natural and synthetic aluminosilicates the vinylcyclohexene formed is hydrogenated to ethylbenzene. C Y C L O D I M E R I Z A T I O N OF B U T A D I E I ~ E I N T H E I~RESENCE OF N A X
Z E O L I T E A N D ITS C A T I O N I C
:FORMS AT AT1KOSPHERIC P R E S S U R E
Butadiene conT,
°C
version, %
_ %Olig°mer°f yield
Butadiene cong/g eata- T, °C version, lyst • hr %
C,H6 passed through
Without catalyst 300 320 360 360
3'9 7"4 9.5
27.o
300 320 340 360
0"08 0.2 0.8 NaX I 26.7
I
0.1
360
Oligomer yield % of C4He passed through
0.5 % RhNaX 16.0 14.7 21.9 18.7 23.6 24.8 43.9 38.7 0.25% RhNaX 42.1 I 39.3 t
g/g catalyst. hr
0"05 0"09 0'15 0"32 0.40
A study is made of the catalytic activity of N a X zeolite and cationic forms of X type zeolite in dimerization of butadiene at atmospheric pressure, since ~he activity of the Cu(I) form of zeolite X or Y was noted previously in a p a t e n t [9]. It follows from tabulated results that N a X zeolite at 360 ° has low polymerization activity. Thermal polymerization of C4H6 in the range of 300360 ° takes place to a slight extent. The addition to N a X zeolite of Cu(II), Ni(II), Cr(III) and Co(II) cations in a proportion of 0.5-1.0% has no marked effect on activity. In the presence of R h N a X zeolite with a Rh content of 0.250.5% the rate of oligomerization of butadiene increased 2-2.5-fold. On reducing rhodium content from 0.5 to 0.25%, reaction rate related to 1 g-arm R h increased from 658 to 16,464 g oligomer/g-atm Rh.hour. The catalyst of 0.5% R h N a X did not change activity for 105 hours. The main product of oligomerization of butadiene was vinylcyclohexene (b.p. 126 °, n~° 1.4633, yield 98-99% of liquid reaction products). In the N M R spectrum of 18C (15.08 rag) in the experiment off resonance revealed the following: doublets at 143.76; 126.97; 126.26; 38.07 p.p.m, and triplets: at 112-56; 31.45; 28.84; 25.19 p.p.m. The I R spectrum contained frequencies (v, cm -1) at: 3087, 3070, 1643, 998, 915 ( C H = C H ~ group); 3010, 1655 ( C = C in the ring). I t was thus shown that the R h form of zeolite X is an active catalyst in cyclodimerization of butadiene at 320-360 ° and at atmospheric pressure. Under the conditions indicated at a space velocity of 300-500 hr -1 butadiene reacts to the extent of 22-44%, being converted te vinylcyclohexene to 98-99%.
Cyelodimerization of butadieno on cationic forms of zeolite X
137
EXPERIMENTAL
E x p e r i m e n t s were carried o u t in a continuous a p p a r a t u s in a q u a r t z t u b e w i t h a n i n t e r n a l d i a m e t e r of 20 m m , into which 5 g c a t a l y s t was placed. L i q u i d p r o d u c t s were collected in a c o n t a i n e r a t 25 ° a n d analysed using a n LKhM-8M_D c h r o m a t o g r a p h (phase of 1 0 ~ polyethyleneglycol a d i p a t e on chromosorb W, f r a c t i o n of 30-60 mesh, carrier gas (helium) v e l o c i t y 40 ml/min, c o l u m n length 5 m). Vinylcyclohexene was isolated b y rectification. The NI~IR s p e c t r u m o f la(3 was r e c o r d e d using a B r u k e r Spectrospin device in CCI~ solution w i t h TMS as i n t e r n a l s t a n d a r d . Ii~ spectra were recorded in a Ul~-20 device in a t h i n l a y e r of p u r e material. Catalysts were p r e p a r e d b y cationic e x c h a n g e of N a X zeolite (containing 2 0 % b i n d e r -- G l u k h o v clay) f r o m dilute solutions o f m e t a l chlorides neutralized to a p H o f 7 w i t h a 20% dilute solution o f I~HaOH. T h e catalysts were h e a t e d in air to 500 ° for 5 hr before t h e experiments. SUMMARY
B u t a d i e n e is c o n v e r t e d to 1-vinyleyclohex-3-ene to t h e e x t e n t o f 2 2 - 4 4 % in t h e presence o f R h N a X zeolite a t a t e m p e r a t u r e of 320-360 ° a n d a t a t m o spheric pressure w i t h a selectivity of 9 8 - 9 9 % . REFERENCES
1. F. Yu. RACHINSI~H and N. I. RZHEKHINA, Zh. obsheh, khimii 25, 244, 1955 2. Ya. M. SLOBODIN, F. Yu. RACHINOVSKII and I. N. SHOKHOR, Zh. obsheh, khimii 17, 9, 374, 1659, 1947 3. S. R. SERGIYENKO and N. V. ZHDANOVA, Dokl. AI~ SSSR 104, 737, 1955 4. Pat. of GFR 2417985; 1975 Chem. Abstrs. 83, 9308, 1975 5. S. E. JACOBSON and C. U. PITTMAN, Chem. Com., 187, 1975 6. G. WILKE, E. W. MULLER and M. KRONER, Angew. Chem. 73, 33, 1961; 75, 10, 1963 7. P. HEIMBACH au4 W. BRENNER, Angew. Chem. 79, 819, 1967 8. W. BRENNER, P. HEIM~ACH, H. HEY, E. W. MULLER and G. WILKE, Lieb. Aim. 727, 161, 1969 9. U.S.A. Pat. 3444253, 1969; Chem. Abstrs. 71, 38433, 1969