헤테로폴리산 촉매상에서 1-부텐에 의한 i-부탄의 알킬화반응

홍성희; 이화영; 송인규

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.2, 211-219, April, 1997

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헤테로폴리산 촉매상에서 1-부텐에 의한 i-부탄의 알킬화반응

Alkylation of Isobutane with 1-Butene over Heteropoly Acid Catalysts

홍성희, 이화영, 송인규

초록

1-부텐과 i-부탄의 알킬화반응에 의한 i-옥탄 생성반응을 Cs 혹은 NH₄가 치환된 H₃PW₁₂O₄₀ 촉매상에서 액상 및 기상으로 수행하였다. 액상알킬화반응의 경우 반응전 촉매의 전처리 온도가 헤테로폴리산 촉매의 반응성에 매우 중요한 역할을 하였다. 액상알킬화반응에서 치환염은 모산보다 매우 우수한 총수율과 i-옥탄 선택도를 보였으며, (NH₄)_2.5H_0.5PW₁₂O₄₀ 촉매는 Cs_2.5H_0.5PW₁₂O₄₀보다 1-옥탄 선택도면에서 더욱 효과적인 것으로 나타났다. 기상알킬화반응의 경우 Cs 혹은 NH₄가 치환된 H₃PW₁₂O₄₀ 촉매의 활성은 촉매의 산특성(산점의 비활성화)과 관련이 있었다. 기상알킬화반응에서 반응초기에는 촉매의 강한 산특성 때문에 C₅-C₇가 주로 생성되나 반응이 진행되면서 촉매 산점의 비활성화가 진행되어 C₈ 및 +C₉가 주로 생성되었다. 기상알킬화반응에서 대상 촉매중 Cs_2.5H_0.5PW₁₂O₄₀이 가장 우수한 총수율을 나타내었다.

Liquid or gas phase alkylation of isobutane with 1-butene for i-octane production was carried out over Cs- or NH₄-exchanged H₃PW₁₂O₄₀. Pretreatment temperature of the catalyst played an important role on the catalytic activity of heteropoly acids in the liquid phase alkylation. Cation-exchanged H₃PW₁₂O₄₀ showed a better total yield and i-octane selectivity than the mother acid in the liquid phase alkylation, and (NH₄)_2.5H_0.5PW₁₂O₄₀ was more efficient than Cs_2.5H_0.5PW₁₂O₄₀ in terms of i-octane selectivity. It was found that the acidic property (deactivation of acid sites) of the catalyst was closely related to the catalytic activity of Cs- or NH₄-exchanged H₃PW₁₂O₄₀ in the gas phase alkylation. C₅-C₇ were mainly formed in the early stage of gas phase alkylation due to the strong acidic property of the catalyst, whereas C₈ and +C₉ were mainly produced as the reaction proceeded due to the deactivation of acid sites. Cs_2.5H_0.5PW₁₂O₄₀ showed the highest total yield in the gas phase alkylation among the catalysts examined.

[References]

Ipatieff VN, Grosse AV, J. Am. Chem. Soc., 57, 1616 (1935)
Corma A, Martinez A, Catal. Rev.-Sci. Eng., 35, 483 (1993)
Weitkamp J, Chester AW, Zeolites, 5, 858 (1990)
Yamaguchi Y, Appl. Catal., 61, 1 (1991)
Chieche B, Finiels A, Gauthier C, Geneste P, J. Mol. Catal., 42, 229 (1987)
Okuhara T, Yamashita M, Na K, Misono M, Chem. Lett., 1451 (1994)
Chu YF, Chester AW, Zeolites, 6, 195 (1986)
Schmerling L, Ind. Eng. Chem. Res., 45, 1447 (1953)
Whitmore FC, J. Am. Chem. Soc., 54, 3274 (1939)
Schmerling L, J. Am. Chem. Soc., 68, 275 (1946)
Song IK, Lee JK, Song JC, Lee WY, J. Korean Ind. Eng. Chem., 5(3), 431 (1994)
이종국, 송인규, 이화영, 촉매, 11, 5 (1995)
Kim HC, Moon SH, Lee WY, Chem. Lett., 447 (1991)
Misono M, Proc. 10th Int. Cong. Catal., Budapest, Hungary, July (1992)
Misono M, New Frontiers in Catalysis; Elsevier, Amsterdam, 69 (1992)
Okuhara T, Nishimura T, Misono M, Stud. Surf. Sci. Catal., 101, 581 (1996)
Okuhara T, Nishimura T, Misono M, Chem. Lett., 155 (1995)
Izumi Y, Ogawa M, Nohara W, Urabe K, Chem. Lett., 1987 (1992)
Na K, Okuhara T, Misono M, J. Chem. Soc.-Faraday Trans., 91, 367 (1995)
Okuhara T, Nishimura T, Watanabe H, Misono M, J. Mol. Catal., 74, 247 (1992)
Tatamatsu S, Hibi S, Okuhara T, Misono M, Chem. Lett., 865 (1984)
Song IK, Kaba MS, Coulston G, Kourtakis D, Barteau MA, Chem. Mater., 8, 2352 (1996)
Rocchiccioli-Deltcheff C, Fournier M, Franck R, Thouvenot R, Inorg. Chem., 22, 207 (1983)
Izumi Y, Natsume N, Takamine H, Tamaoki I, Urabe K, Bull. Chem. Soc. Jpn., 62, 2159 (1989)
Essayem N, Kieger S, Coudurier G, Vedrine JC, Stud. Surf. Sci. Catal., 101, 591 (1996)

[Referenced By]

[1] Ipatieff VN, Grosse AV, J. Am. Chem. Soc., 57, 1616 (1935)

[2] Corma A, Martinez A, Catal. Rev.-Sci. Eng., 35, 483 (1993)

[3] Weitkamp J, Chester AW, Zeolites, 5, 858 (1990)

[4] Yamaguchi Y, Appl. Catal., 61, 1 (1991)

[5] Chieche B, Finiels A, Gauthier C, Geneste P, J. Mol. Catal., 42, 229 (1987)

[6] Okuhara T, Yamashita M, Na K, Misono M, Chem. Lett., 1451 (1994)

[7] Chu YF, Chester AW, Zeolites, 6, 195 (1986)

[8] Schmerling L, Ind. Eng. Chem. Res., 45, 1447 (1953)

[9] Whitmore FC, J. Am. Chem. Soc., 54, 3274 (1939)

[10] Schmerling L, J. Am. Chem. Soc., 68, 275 (1946)

[11] Song IK, Lee JK, Song JC, Lee WY, J. Korean Ind. Eng. Chem., 5(3), 431 (1994)

[12] 이종국, 송인규, 이화영, 촉매, 11, 5 (1995)

[13] Kim HC, Moon SH, Lee WY, Chem. Lett., 447 (1991)

[14] Misono M, Proc. 10th Int. Cong. Catal., Budapest, Hungary, July (1992)

[15] Misono M, New Frontiers in Catalysis; Elsevier, Amsterdam, 69 (1992)

[16] Okuhara T, Nishimura T, Misono M, Stud. Surf. Sci. Catal., 101, 581 (1996)

[17] Okuhara T, Nishimura T, Misono M, Chem. Lett., 155 (1995)

[18] Izumi Y, Ogawa M, Nohara W, Urabe K, Chem. Lett., 1987 (1992)

[19] Na K, Okuhara T, Misono M, J. Chem. Soc.-Faraday Trans., 91, 367 (1995)

[20] Okuhara T, Nishimura T, Watanabe H, Misono M, J. Mol. Catal., 74, 247 (1992)

[21] Tatamatsu S, Hibi S, Okuhara T, Misono M, Chem. Lett., 865 (1984)

[22] Song IK, Kaba MS, Coulston G, Kourtakis D, Barteau MA, Chem. Mater., 8, 2352 (1996)

[23] Rocchiccioli-Deltcheff C, Fournier M, Franck R, Thouvenot R, Inorg. Chem., 22, 207 (1983)

[24] Izumi Y, Natsume N, Takamine H, Tamaoki I, Urabe K, Bull. Chem. Soc. Jpn., 62, 2159 (1989)

[25] Essayem N, Kieger S, Coudurier G, Vedrine JC, Stud. Surf. Sci. Catal., 101, 591 (1996)