선택적 촉매 산화 반응에 의한 황화 수소의 제거; II. TiO<sub>2</sub>/SiO<sub>2</sub>촉매 상에서 황화 수소의 선택적 산화 반응

천승우; 박대원; 우희철; 홍성수; 정종식

Journal of the Korean Industrial and Engineering Chemistry, Vol.7, No.4, 645-652, August, 1996

Export Citation

선택적 촉매 산화 반응에 의한 황화 수소의 제거; II. TiO₂/SiO₂촉매 상에서 황화 수소의 선택적 산화 반응

Removal of H₂S by Selective Catalytic Oxidation Ⅱ. Selective Oxidation of H₂S on TiO₂/SiO₂ Catalysts

천승우, 박대원, 우희철, 홍성수, 정종식

초록

본 연구는 H₂S를 TiO₂/SiO₂ 촉매상에서 산소와의 직접 산화 반응을 통해 원소 황의 형태로 제거하는 반응에 관한 것이다. 순수한 TiS₂와 Ti(SO₄)₂를 사용한 반응 실험과 순수한 TiO₂에 대한 주기적 온도 조작 실험 결과로부터 TiO₂는 황 회수 공정에서 사용되는 촉매의 비활성화의 주원인으로 알려진 sulfation이나 sulfidation에 대해 매우 안정한 것으로 나타났다. TiO₂/SiO₂ 촉매에서 TiO₂의 담지랑이 증가함에 따라 H₂S의 전화율이 증가하였고, 원소 황의 선택도는 아주 소폭으로 감소하였다. 반응 실험 결과 O₂/H₂S의 비가 증가할수록 원소 황의 선택도는 크게 감소하였다. 10 wt.% TiO₂/SiO₂ 촉매는 화학 양론비의 조성(H₂S=5 vol.% O₂=2.5 vol.%)의 반응물에 10 vol.%의 수증기를 첨가한 경우 활성과 선택도가 감소하였으나 여전히 80% 이상의 원소 황 수율을 유지하고 있었다.

Selective catalytic oxidation of H₂S to elemental sulfur using TiO₂/SiO₂2 catalysts was investigated in this study. The reaction test with pure TiS₂ and Ti(SO₄)₂ and cyclic temperature operation revealed that TiO₂ had a good resistance to sulfation and sulfidation, which are known as the main cause of catalytic deactivation in sulfur recovery process. With the increase of TiO₂ loading amount in TiO₂/SiO₂ catalysts, the conversion of H₂S increased and the selectivity of elemental sulfur was very slightly decreased. As the ratio of O₂/H₂S increased, the selectivity to elemental sulfur was drastically decreased. In the presence of 10 vol.% water vapor to a stoichiometric mixture of H₂S and O₂(H₂S= 5 vol.% O=2.5 vol.% ), both activity and selectivity of 10 wt.% TiO₂/SiO₂ catalyst are decreased, but it still showed more than 80% of sulfur yield.

[References]

Othmer K, "Encyclopedia of Chemical Technology," 3rd Ed., 22, 276, Wiley-Interscience, Publisher, New York (1983)
Lagas JA, Berben PH, Oil Gas J., 10, 68 (1988)
Kettner R, Liermann N, Oil Gas J., 11, 63 (1983)
Kettner R, Lubcke T, Liermann N, European Patent, 78690 (1982)
Chopin T, Hebrard JL, Quemere E, European Patent, 422999 (1990)
Lagas JA, Barsboom J, Heijcoop G, Hydrocarb. Process., April, 40 (1989)
Nisselrooy PFMT, Lagas JA, Catal. Today, 16, 263 (1993)
Goar EN, MacDougall RS, Lagas JA, Oil Gas J., 28, 45 (1994)
Berben PH, Scholten A, Titular NK, Brahma N, VanderWal WJJ, Geus JW, "Catalyst Deactivation 1987," ed. B. Delmon and G.F. Froment, 34, 123, Elsevier, Amsterdam (1991)
Huisman HM, vanderBerg P, Mos R, VanDillen AJ, Geus JW, "Environmental Catalysis," ed. J.N. Armor, 393, ACS Marple, New York (1994)
vandenBrink PJ, Scholten A, vanDillen AJ, Geus JW, "Catalyst Deactivation 1991," ed. C.H. Bartholomew and J.B. Butt, 68, 515, Elsevier, Amsterdam (1991)
Morrow BA, Mcfrane RA, Lion M, Lavalley JC, J. Catal., 107, 232 (1987)
Coward RS, Skarat WM, Oil Gas J., April(8), 86 (1985)
Dupin T, Voirin R, Hydrocarb. Process., 61, 189 (1982)
Saur O, Bensitel M, MohammedSaad A, Lavalley JC, Tripp CP, Morrow B, J. Catal., 99, 104 (1986)
Chun SW, Park DW, Woo HC, Hong SS, Chung JS, J. Korean Ind. Eng. Chem., 6(5), 959 (1995)
Othmer K, "Encyclopedia of Chemical Technology, 3rd ed., 23, 167, Wiley-Interscience, Publishers, New York (1983)
Gamson BW, Elins RH, Chem. Eng. Prog., 49, 203 (1953)

[Referenced By]

[1] Othmer K, "Encyclopedia of Chemical Technology," 3rd Ed., 22, 276, Wiley-Interscience, Publisher, New York (1983)

[2] Lagas JA, Berben PH, Oil Gas J., 10, 68 (1988)

[3] Kettner R, Liermann N, Oil Gas J., 11, 63 (1983)

[4] Kettner R, Lubcke T, Liermann N, European Patent, 78690 (1982)

[5] Chopin T, Hebrard JL, Quemere E, European Patent, 422999 (1990)

[6] Lagas JA, Barsboom J, Heijcoop G, Hydrocarb. Process., April, 40 (1989)

[7] Nisselrooy PFMT, Lagas JA, Catal. Today, 16, 263 (1993)

[8] Goar EN, MacDougall RS, Lagas JA, Oil Gas J., 28, 45 (1994)

[9] Berben PH, Scholten A, Titular NK, Brahma N, VanderWal WJJ, Geus JW, "Catalyst Deactivation 1987," ed. B. Delmon and G.F. Froment, 34, 123, Elsevier, Amsterdam (1991)

[10] Huisman HM, vanderBerg P, Mos R, VanDillen AJ, Geus JW, "Environmental Catalysis," ed. J.N. Armor, 393, ACS Marple, New York (1994)

[11] vandenBrink PJ, Scholten A, vanDillen AJ, Geus JW, "Catalyst Deactivation 1991," ed. C.H. Bartholomew and J.B. Butt, 68, 515, Elsevier, Amsterdam (1991)

[12] Morrow BA, Mcfrane RA, Lion M, Lavalley JC, J. Catal., 107, 232 (1987)

[13] Coward RS, Skarat WM, Oil Gas J., April(8), 86 (1985)

[14] Dupin T, Voirin R, Hydrocarb. Process., 61, 189 (1982)

[15] Saur O, Bensitel M, MohammedSaad A, Lavalley JC, Tripp CP, Morrow B, J. Catal., 99, 104 (1986)

[16] Chun SW, Park DW, Woo HC, Hong SS, Chung JS, J. Korean Ind. Eng. Chem., 6(5), 959 (1995)

[17] Othmer K, "Encyclopedia of Chemical Technology, 3rd ed., 23, 167, Wiley-Interscience, Publishers, New York (1983)

[18] Gamson BW, Elins RH, Chem. Eng. Prog., 49, 203 (1953)