시클로펜텐과 1-펜텐의 불균일 촉매 산화반응

양현수; 김영호

Journal of the Korean Industrial and Engineering Chemistry, Vol.7, No.5, 888-901, October, 1996

Export Citation

시클로펜텐과 1-펜텐의 불균일 촉매 산화반응

Heterogeneously Catalyzed Oxidations of Cyclopentene and of 1-Pentene

양현수, 김영호

초록

V/Mo/P/Al/Ti-혼합 산화물 촉매상에서 고정층 적분식 반응기를 사용하여 공기로 1-펜텐과 시클로펜텐의 산화반응을 연구하였다. 고전환율에서 두 반응물들로부터 얻은 단일의 중요한 유기생성물은 무수말레인산이었고 동시에 소량의 무수프탈산을 얻었다. 한편, 1-펜텐 반응물로부터는 소량의 무수시트라콘산을 추가로 얻었다. 저전환율에서는 전체적으로 30개의 유기 산화 생성물들을 확인했으며, 그들중 일부는 위에 언급된 3개의 무수물을 형성하기 위한 반응 중간체들 이었다. 전환율에 따른 유기 생성물들의 선택성을 근거로하여 무수말레인산, 무수프탈산 및 무수시트라콘산의 형성을 위한 반응경로를 제안했다. 한편, 310℃에서 공간속도의 감소에 따라 전환율과 무수말레인산의 선택성은 증가하였고, 무수말레 인산의 최고선택성은 약 100%의 전환율에서 얻었다. 2·10⁴h^-의 일정한 공간속도에서 온도(300℃∼420℃)증가에 따라 전환율은 증가한 반면, 무수말레인산으로의 선택성은 시클로펜텐 산화반응의 경우 370℃에서 약 39%의 최고값과 1-펜텐 산화반응의 경우 400℃에서 약 30%의 최고값을 얻었다.

Oxidations of cyclopentene and of 1-pentene with air have been studied on a V/Mo/P/Al/Ti-mixed oxide catalyst in a fixed bed integral reactor. At high levels of conversion maleic anhydride was in each case produced as the major organic product, along with minor amounts of phthalic anhydride and, only starting from 1-pentene, also of citraconic anhydride. At lower levels of conversion a total of 30 organic products have been identified, some of which may be intermediates on the way from the substrates to the three anhydrides mentioned above. Based on the dependence of selectivities of the organic products on conversion, reaction schemes for the formation of maleic anhydride, phthalic anhydride and citraconic anhydride have been proposed. Oxidation at 310 ℃ led to increasing conversions and selectivities for maleic anhydride with decreasing space velocities. The highest selectivities for maleic anhydride were obtained at conversion of ca. 100%. Oxidation at a constant space velocity of 2ㆍ10(4)h(-1) led to increasing conversions with increasing temperatures in the range of 300~420 ℃, while the selectivity for maleic anhydride passed through a maximum value of ca. 39% at 370 ℃ in the oxidation of cyclopentene and a maximum value of ca. 30% at 400 ℃ in the oxidation of 1-pentene.

[References]

Winnacker K, Kuchler D, "Chemische Technologie," 4th ed., 5, 164, Carl Hanser Verlag, Munchen (1981)
Schleppinghoff B, Schulwitz B, Erdol Kohle Erdgas Petrochemie, 38, 209 (1985)
Griesbaum K, Honicke D, "Ullmanns Encyclopedia of Industrial Chemistry," 5th ed., A8, 227, VCH Verlagsgesellschaft, Heidelberg (1987)
Bockler R, Cordes G, Smolen H, Chem. Ing. Tech., 62, 447 (1990)
Griesbaum K, Honicke D, Erdol Kohle Erdgas, 35, 102 (1986)
Honicke D, Griesbaum K, Chem. Ing. Tech., 54, 497 (1982)
Honicke D, Buhrer R, Newrzella A, Erdol Kohle Erdgas Petrochemie, 37, 569 (1984)
Butt NS, Fish A, J. Catal., 5, 494 (1966)
Honicke D, Griesbaum K, Augenstein R, Yang Y, Chem. Ing. Tech., 59, 222 (1987)
Honicke D, Griesbaum K, Appl. Catal., 2, 177 (1982)
Ackman RG, J. Gas Chromatography, 4, 173 (1964)
Ackman RG, J. Gas Chromatography, 6, 497 (1968)
Centi G, Burattini M, Trifiro F, Appl. Catal., 32, 353 (1987)
Saleh RY, Wachs IE, Appl. Catal., 31, 87 (1987)
Butt NS, Fish A, J. Catal., 5, 494 (1966)
Miura M, Schultheis K, Griesbaum K, Appl. Catal. A: Gen., 87, 241 (1992)
Centi G, Golinelli G, Busca G, J. Phys. Chem., 94, 6813 (1990)
Centi G, Nieto JL, Lapalucci C, Bruckmann K, Serwicka EM, Appl. Catal., 46, 197 (1989)
Weiss F, Marion J, Metzger J, Cognion JM, Kinet. Catal., 14, 32 (1973)
Iovel I, Goldberg Y, Shymanska M, J. Chem. Soc.-Chem. Commun., 1079 (1990)
Izumi T, Kasahara A, Bull. Chem. Soc. Jpn., 48, 1673 (1975)
Kamel M, Ph.D. Dissertation, Karlsruhe Univ., Karlsruhe, Germany (1973)

[Referenced By]

[1] Winnacker K, Kuchler D, "Chemische Technologie," 4th ed., 5, 164, Carl Hanser Verlag, Munchen (1981)

[2] Schleppinghoff B, Schulwitz B, Erdol Kohle Erdgas Petrochemie, 38, 209 (1985)

[3] Griesbaum K, Honicke D, "Ullmanns Encyclopedia of Industrial Chemistry," 5th ed., A8, 227, VCH Verlagsgesellschaft, Heidelberg (1987)

[4] Bockler R, Cordes G, Smolen H, Chem. Ing. Tech., 62, 447 (1990)

[5] Griesbaum K, Honicke D, Erdol Kohle Erdgas, 35, 102 (1986)

[6] Honicke D, Griesbaum K, Chem. Ing. Tech., 54, 497 (1982)

[7] Honicke D, Buhrer R, Newrzella A, Erdol Kohle Erdgas Petrochemie, 37, 569 (1984)

[8] Butt NS, Fish A, J. Catal., 5, 494 (1966)

[9] Honicke D, Griesbaum K, Augenstein R, Yang Y, Chem. Ing. Tech., 59, 222 (1987)

[10] Honicke D, Griesbaum K, Appl. Catal., 2, 177 (1982)

[11] Ackman RG, J. Gas Chromatography, 4, 173 (1964)

[12] Ackman RG, J. Gas Chromatography, 6, 497 (1968)

[13] Centi G, Burattini M, Trifiro F, Appl. Catal., 32, 353 (1987)

[14] Saleh RY, Wachs IE, Appl. Catal., 31, 87 (1987)

[15] Butt NS, Fish A, J. Catal., 5, 494 (1966)

[16] Miura M, Schultheis K, Griesbaum K, Appl. Catal. A: Gen., 87, 241 (1992)

[17] Centi G, Golinelli G, Busca G, J. Phys. Chem., 94, 6813 (1990)

[18] Centi G, Nieto JL, Lapalucci C, Bruckmann K, Serwicka EM, Appl. Catal., 46, 197 (1989)

[19] Weiss F, Marion J, Metzger J, Cognion JM, Kinet. Catal., 14, 32 (1973)

[20] Iovel I, Goldberg Y, Shymanska M, J. Chem. Soc.-Chem. Commun., 1079 (1990)

[21] Izumi T, Kasahara A, Bull. Chem. Soc. Jpn., 48, 1673 (1975)

[22] Kamel M, Ph.D. Dissertation, Karlsruhe Univ., Karlsruhe, Germany (1973)