TRANSFORMATIONS OF n-PENTANE, n-HEXANE, AND BENZENE ON HIGH-SILICA ZEOLITES CONTAINING GROUP VIII METALS V. I. Garanin, I. L. Mironova, A. S.

Fomin, and Kh. M. Minachev UDC 542.97:547.21:547.532.:549.67

The high-silica zeolites TsVK and TsVM, the Soviet analogs of type ZSM zeolite, are active in such industrially important reactions as conversion of synthesis gas [i], alkylation of aromatic hydrocarbons by olefins [2], and mutual transformations of aromatic hydrocarbons [3]. The catalytic properties of Pd-containing TsVM (Si02/AI=03 ratio = 33) and TsVK zeofires (SiOo/Al20s = 47 and 83), and zeolites with no transition metals were studied [4, 5] in transformations of C~-C6 n-paraffins and hydrogenation of benzene. Their elevated activity in isomerization, hydrocracking~ hydrogenolysis, and disproportionation of hydrocarbons was demonstrated. The transformation of n-pentane, n-hexane, and benzene on high-silica zeolites containing Rh, Ru, Ir, and Ni was investigated in the present study. EXPERIMENTAL The metal-containing catalysts were prepared from high-silica zeolites with Si02/A1203 = 33 (TsVM) and 83 (TsVK). The H forms of the zeolites were fabricated by ion exchange with a solution of NH4CI and subsequent calcination at 600~ The Pd, Rh, Ru, Ir, and Ni catalysts were prepared by impregnation and ion exchange using solutions of Pd(NH3)~CI=, H2PdCI~, RuCI3, H2IrCI6, and Ni(N03)2. The following hydrocarbons were used: pure n-pentane, n-hexane, and benzene. The experiments were conducted in a flow-type setup with a 7.5 g (i0 ml) load of catalyst. The catalysts were calcined for 5 h at 380~ in a current of air and then reduced for 5 h with hydrogen at the same temperature before the experiments. The catalytic properties of the zeolites were studied at I00-400~ a volume feed rate of the hydrocarbons of 1 h -I. and 0.1-3 MPa with

The products were analyzed by GLC on an LKhM-SM chromatograph with a column pa=ked with Celite-545 with 18% triethylene glycol dibutyrateo DISCUSSION OF RESULTS As Table i shows, the Na form of TsVM containing Pd is inactive in isomerization of n-pentane in the 300-3807C range and thus does not catalyze carbonium ion type reactions, like the Na forms of other zeolites. Decationization of the zeolite resulted in an effective catalyst of isomerization. At 310~ and 3 MPa, the yield of isopentane was close to equilihrium andwas 60% with a selectivity of 93%, and the catalyst prepared by exchange was slightly more active and selective than the impregnation catalyst. These indexes are higher than for the existing metal--faujasite catalysts in the H and cationic forms containing Pt and Pd, but are comparable in activity to Pd--H-mordenite [6~. A comparison of the data obtained on the catalytic activity of H-mordenite and HTsVM (HZSM) with the data in [7, 8] showed that the concentration and features of the crystal structure of the zeolites, not the difference in the nature of the active sites, are determining here. Substitution of Na + ions by Ca 2+ and La 3+ in Pd/TsVM results in almost the same yields of isopentane (57%) as on Pd/HTsVM, but these yields of isopentane are obtained at higher N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow~ Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1732-1736, August, 1986. Original article submitted March 12, 1985.

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9 1987 Plenum Publishing Corporation

TABLE i. Transformations of n-Pentane on 0.5% Me/TsVM Catalysts (3 MPa; pH2/PCsH12 = 3.2; v = I h -I) Yield of prod~.~,:7:~,%
Catalyst

0,5% Pd/Na TsVM impregnation 0,5% Pd/H;TsVM impregnation 0',5% Pd/K TsVM exchange

300-380 330 310 300 320 350 380 250 350 4O0 220 240 280 120 200 250 280 3t0 270 310 330 66,3 60,0

No reaction 9,2 3,9 Trace~ 0,2 1,0 0,4 3,8 4,8 i0,4 13,0 2,0 9,8 0,5 IA 13,0 0,6 617 16,3

1,0 0,9 Traces 0,3 0,4 0,6

0,50/0Pd/CaNs TsVM impregnation

6,7 18,2 42,7 57,t 1,2 37,1 56,8 i8,3 32,0 40,2 t,6 5,8 J4,6 25,6 39,5 5,3 27,4 30,5

0,5% Pd/LaNaTsVM impregnation

0,5% Rh/HTsVM impregnation 0,5% Ru/HTsVM exchange 0,5% Ir/H TsVM impregnation

Traces 0,1 Traces

0,5% Ni/HTsVK impregnation

0,2 1,1 Traces Traces 0,4

TABLE 2. Transformations of n-Hexane on 0.5% Me/TsVM Catalysts (3 MPa; pH2/PC6HI, = 3.2; v = ! h -I)
Yield of products Catalyst
T,, ~ i-C~ C~--C~ ]~C5

0,5% Pd/HTsVM exchange 0,5% Rh/HTsVM impregnation 0',5% Ru/HTsVM exchange

320 220 a00

53,~ 13.l 25,3 32,8 6,2 i6,0 ig,i Ii.2 2418 i7,8

3,7 2,9 8.1 2f2 4,9 ]~, 1 32,3 3,0 14,9 33,7

18,2 7.8 15,1 10,7 3,4 14,8 15,7 1.8 9,4 i8,7

~5o
23O 25O 28O 25O

0,5% Ir/HTsVM impregnation

temperatures (380-400~ on the cationic forms. As demonstrated in [4], the yield of products of all ionic reactions (isomerization, hydrocracking, etc.) on the HTsVM catalyst with no metal attains 43% in the transformation of n-pentane at 2500C, while CaTsVM is inactive at this temperature. This difference is apparently due to the weak acidity of CaTsVM, since the decrease in the channels on introduction of Ca 2+ is insufficient for the appearance of a molecular-sieve effect which would result in the reaction taking place on the external surface of the catalyst. The catalytic properties of Pd/HTsVM significantly differ from the H forms of TsVM containing other group VIII metals (see Table i)~ They exhibit low isomerizing and high hydrocracking activity like faujasites [6]. If a value of 0.93 (for Pd/HTsVM) is used as the optimum characteristic of the selectivity of the catalysts with respect to the isomerization reaction, Ru/HTsVM is totally nonselective: the selectivity for isopentane is less than 0.5 even at 120-200~ The yield of isopentane on Ir and Rh zeolite catalysts is 26 and 18% with a selectivity of 0.96 and 0.79, respectively. The lowest isomerizing activity is exhibited by the 0.5% Ni catalysts prepared from the H form of TsVK (Si02/A1203 = 83). At 270~ the yield of isopentane did not exceed 5.3%. The Pd-containing zeolites with a modulus of 83 are less active then the samples with a SiO=/AI203 ratio of 33 [4].

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TABLF 3. Transformations of Benzene on 0.5% Me/TsVM Catalysts (pH2/PC6H6 = 5; v = I h -I) ~oducts

Cataly~ ~ 0,5% Pd/HTsVM i m pregnation T., ~ p, MP a cyclo- . methyl- [ hexane cyclopen~ c,--c~ tane /
Traces )) >>

34,8. 0,5% Rh/HTsVM i m pregnation

Traces
>> >>

2,8 49,9 0,5% Ru/HTsVM exchange 0,5% Ir/HTsVM i m pregnation Traces 0,2 Traces
>>

The data in Table 2 indicate the analogous character of the transformations of n-hexane and n-pentane. On the Pd catalyst, hexane is isomerized into isohexanes by 54%, while the Rh, Ir, and Ru catalysts have the same orders of activity with respect to the isomerization and hydrocracking reactions as for n-pentane. All of these catalysts, especially Ru/HTsVM, are very active in hydrocracking and like Pd-zeolite catalyze hydrogenolysis of n-hexane with the formation of pentane, which distinguished them from HU and HM containing the same metals [6]. The data in Table 3 show that all of the catalysts prepared from the H form of TsVM are highly active in the hydrogenation of benzene. The Rh catalyst exhibits very high hydrogenating activity. Even at 100~ and 0.i MPa, benzene is almost totally and selectively hydrogenated into cyclohexane, which has not been observed on other metal-containing zeolites [9]. It is impossible to conduct the reaction at a lower temperature, since the gas-phase conditions of the process in this case can turn into liquid-phase conditions, and the comparison of the activities of the catalysts (conversion of benzene) will not be rigorous. With an increase in the temperature, hydroisomerization of benzene into methylcyclopentane begins to take place on metal-containing catalysts, but not selectively. At 280~ only 22% methylcyclopentane and 50% products of hydrocracking and hydrogenolysis of CI-C~ composition are formed on the Rh catalyst, while the figures are ii and 35% on Pd/HTsVM at 300~ The catalytic properties of HTsVM zeolites containing Rh and Pd thus differ from the properties of metal--faujasite and mordenite catalysts, on which hydroisomerization takes place much more selectively [9]. CONCLUSIONS i. It was found that reactions of hydrocracking and hydrogenolysis of n-pentane and n-hexane take place intensively on high-silica zeolites containing rhodium, iridium, ruthenium, and nickel, in contrast to pallasium-containing zeolites, which are active and selective catalysts of isomerization of n-pentane. 2. Rhodium and iridium zeolite catalysts also exhibit very high activity in the hydrogenation of benzene. At I00-120~ and atmospheric pressure, benzene is selectively hydrogenated into cyclohexane, which is not obtained on the other metal-containing zeolite catalysts investigated. LITERATURE CITED i. 2. 3. I. V. Kalechits, Vestn. Akad. Nauk Kh. M. Minachev and Ya. I. Isakov, Kh. M. Minachev, D. A. Kondrat'ev, Nefedov, and T. V. Alekseeva, Izv. SSSR, Khim. A. A. Akad. No. 5, 55 (1981). Tverd. Topliva, No. 6, 7 (1982). Dergachev, I. V. Mishin, I. N. Oleshko, B. K. Nauk SSSR, Sar. Khim., 1706 (1982).

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4.

5. 6. 7.

8. 9.

Kh. M. Minachev, V. I. Garanin, T. A. Isakova, I. L. Mironova, A. S. Fomin, and B. A. Lipkind, in: Use of Zeolites in Catalysis, III All-Union Conference [in Russian], Moscow (1981), p. i00. Kh. M. Minachev, V. I. Garanin, T. A. Isakova, I. L. Mironova, A. S. Fomin, and B. A. Lipkind, Izv. Akad. Nauk SSSR, Set. Khim., 1227 (1982). Kh. M. Minachev, V. I. Garanin, V. V. Kharlamov, T. A. Isakova, and E. ~. Senderov, Izv. Akad. Nauk SSSR, Set. Khim., 1737 (1969). A. A. Klyachko, G. I. Kapustin, G. O. Glonti, T. R. Brueva, and A. M. Rubinshtein, Proceedings of the 6th Soviet--French Seminar on Catalysis [in Russian], Moscow (1983), p. 83. L. M. Kustov, V. Yu. Borokov, and V. B. Kazanskii, Proceedings of the 6th Soviet--French Seminar on Catalysis [in Russian], Moscow (1983), p. 63. Kh. M. Minachev, and Ya. I. Isakov, in: Metal-Containing Zeolites in Catalysis [in Russian], Nauka, Moscow (1976), p. 56.

OXIDATION OF AMINES BY MOLECULAR OXYGEN. COMMUNICATION 13, ROLE OF ROO' AND HOO" RADICALS IN THE CHAIN

OXIDATION OF AMINES AND THE QUANTITATIVE DETERMINATION OF PEROXIDES A. L. Aleksandrov UDC 541.515:542.943:547.551

The question of the nature of peroxy radicals in alkylarylamines undergoing oxidation is unresolved -- there are contradictory conclusions with regard to the contribution of ~aminoperoxide [i] and hydroperoxide [2, 3] radicals. The causes of these disagreements are discussed in the present work. EXPERIMENTAL The amines were purified with A1203, activated charcoal, and iso- or diisocyanate [i, 4]. The criterion of purity was a direct proportionality between the rate of oxidation of the amine (v) and the concentration of the initiator [azoisobutyrodinitrile (AIBN)] to the exponent 1/2. The value of v was measured volumetrically according to the absorption of 02. The degree of oxidation was in the range of 0.5"10-2-5"10 -2 M, when the overall peroxide concentration corresponded to the absorbed 02 ([ROOH E] > 0.95A[02]). The same results were obtained in the analysis of the oxidates for the content of ROOH E by iodometric titration and using Ti(S04)2. In the latter case the sample of oxidate or mixture of amine with H202, with a volume of 0.05-0.5 ml, was diluted to 2 ml with purified n-C~HTOH or (CH3)2NCOCH3 to create a homogeneous system. After purging of the solution with argon, 14 ml of an aqueous solution containing 0.4 M H2SO~ and 1.4"10 -2 M Ti(SO~)2 was added. After 5 min the optical density D was measured on a Specord UV VIS instrument in a cuvette with I 4 cm. For H202 and ROOH of the oxidate the spectrum was the same, and at ~ 410 nm the coefficient of extinction e 719 i0 liters/mole.cm. In an analysis by the stopped-flow method [5], the oxidate was diluted with dry CHsOH in such a way that after mixing with an equal volume of the Ti(IV) solution, a final optical density D~ = 0.3 was obtained. The fraction of H202 was determined by extraction [6]. For this purpose 2 ml of pC6H~4 and 2 ml of H=O, containing 20% NaCI, were added to 2 ml of the oxidate~ The test tube was closed with a ground stopper and shaken vigorously for 1.5 min. The poorly stratified mixtures with drops on the walls were centrifuged as rapidly as possible. The aqueous and organic phases were analyzed for their content of H202 and ROOH with Ti(IV), considering that ROOH is not extracted by water. The time of contact of the oxidate with H20 before the analysis did not exceed 8 min. The degree of extraction of H202, added to the initial nonoxidized amine, was determined analogously. The results obtained are cited in Table i, where the arithmetic mean values were obtained from five determinations with different initial peroxide concentrations. Division of the Institute of Chemical Physics, Academy of Sciences of the USSR, Chernogolovka. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1736-1741, July, 1986. Original article submitted July 24, 1984. 0568-5230/86/3508-1575512.50 9 1987 Plenum Publishing Corporation 1575