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Received July 18, 2006
Accepted July 26, 2006
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제올라이트와 분자체 촉매에서 메탄올 전환 반응의 기구
Mechanism of Methanol Conversion over Zeolite and Molecular Sieve Catalysts
전남대학교 응용화학공학부, 500-757 광주시 북구 용봉동 300
School of Applied Chemical Engineering, Chonnam National University, 300, Yongbong-dong, Puk-gu, Gwangju 500-757, Korea
gseo@chonnam.ac.kr
Korean Chemical Engineering Research, August 2006, 44(4), 329-339(11), NONE Epub 6 September 2006
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Abstract
원유가 급등으로 메탄올에서 저급 올레핀을 제조하는 공정에 대한 관심이 높아지고 있다. 제올라이트와 SAPO 분자체 촉매에서 메탄올의 탄화수소로 전환 반응을 저급 올레핀 생성 단계에 중점을 두고 고찰하였다. 구조가 명확한 중간체를 근거로 하는 직접(direct) 반응기구와 구조가 애매한 탄화수소 뭉치를 활성점으로 보는 탄화수소 활성체(hydrocarbon pool) 반응기구의 합리성을, 메탄올 전환 반응의 유도기간, 생성물의 선택성, 활성 저하 등과 연계지어 비교하였다. 탄화수소 활성체의 구조 규명과 메탄올 전환 반응에서 촉매 활성점으로서 기능에 대한 1999년 이후 연구 결과를 검토하였으며, 메탄올에서 저급 올레핀을 생산하는 공정에 대한 전망도 기술하였다.
The production of lower olefins from methanol becomes an attractive process because of the rapid increase in crude oil price. This paper reivews the conversion mechanisms of methanol to hydrocarbons over zeolite and SAPO molecular sieve catalysts to understand the formation steps of lower olefins from methanol. The feasibility of the conversion mechanisms such as the direct mechanism based on well-defined intermediates and the hydrocarbon pool mechanism involving hydrocarbon moieties as an active centers is discussed with reepect to the induction period, the selectivity for products and the deactivation phenomena of the methanol conversion. The literature appeered since 1999 for the structure of the hydrocarbon pool and its catalytic role in the methanol conversion are summariged, and the prospect for the methanol-to-olefins process is described.
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Chang CD, Catal. Rev.-Sci. Eng., 26, 323 (1984)
Seo G, Prog. Ind. Chem., 27(1), 15 (1987)
Keil FJ, Microporous Mesoporous Mater., 29, 49 (1999)
Stocker M, Microporous Mesoporous Mater., 29, 3 (1999)
Maxwell IE, Stork WHJ, Stud. Surf. Sci. Catal., 137, 747 (2001)
Park JW, Kim JH, Seo G, Polym. Degrad. Stabil., 76, 495 (2002)
Liu ZM, Sun CL, Wang GW, Wang QX, Cai GY, Fuel Process. Technol., 62(2-3), 161 (2000)
Haw JF, Song W, Marcus DM, Nicholas JB, Accounts Chem. Res., 36, 317 (2003)
Mikkelsen Ø, Rønning PO, Kolboe S, Microporous Mesoporous Mater., 40, 95 (2000)
Hunger M, Catal. Today, 97(1), 3 (2004)
Dahl IM, Kolboe S, Catal. Lett., 20, 329 (1993)
Arstad B, Kolboe S, J. Am. Chem. Soc., 123(33), 8137 (2001)
Olsbye U, Bjorgen M, Svelle S, Lillerud KP, Kolboe S, Catal. Today, 106(1-4), 108 (2005)
Song WG, Haw JF, Nicholas JB, Heneghan CS, J. Am. Chem. Soc., 122(43), 10726 (2000)
Haw JF, Nicholas JB, Song WG, Deng F, Wang ZK, Xu T, Heneghan CS, J. Am. Chem. Soc., 122(19), 4763 (2000)
Song WG, Fu H, Haw JF, J. Phys. Chem. B, 105(51), 12839 (2001)
Song WG, Fu H, Haw JF, J. Am. Chem. Soc., 123(20), 4749 (2001)
Song WG, Nicholas JB, Haw JF, J. Phys. Chem. B, 105(19), 4317 (2001)
Sassi A, Wildman MA, Haw JF, J. Phys. Chem. B, 106(34), 8768 (2002)
Sassi A, Wildman MA, Ahn HJ, Prasad P, Nicholas JB, Haw JF, J. Phys. Chem. B, 106(9), 2294 (2002)
Park TY, Froment GF, Ind. Eng. Chem. Res., 40(20), 4187 (2001)
Alwahabi SM, Froment GF, Ind. Eng. Chem. Res., 43(17), 5112 (2004)
Wu XC, Abraha MG, Anthony RG, Appl. Catal. A: Gen., 260(1), 63 (2004)
Gayubo AG, Vivanco R, Alonso A, Valle B, Aguayo AT, Ind. Eng. Chem. Res., 44(17), 6605 (2005)
Keil FJ, Hinderer J, Garayhi AR, Catal. Today, 50(3-4), 637 (1999)
Chen D, Rebo HP, Holmen A, Chem. Eng. Sci., S4, 3465 (1999)
Chen D, Rebo HP, Gronvold A, Moljord K, Holmen A, Microporous Mesoporous Mater., 35, 121 (2000)
Dewaele O, Geers VL, Froment GF, Marin GB, Chem. Eng. Sci., 54(20), 4385 (1999)
Soundararajan S, Dalai AK, Berruti F, Fuel, 80, 1187 (2001)
Seo G, Song YS, Byun DH, Ha BH, Korean Chem. Eng. Res., 26(6), 591 (1988)
Seo G, Ryoo R, J. Catal., 124, 224 (1990)
Seo G, Kim DC, Ko TS, Park TJ, Korean Chem. Eng. Res., 29(4), 494 (1991)
Rhee K, Cho M, Jeong B, Seo G, J. Korean Chem. Soc., 34(4), 360 (1990)
Djieugoue MA, Prakash AM, Kevan L, J. Phys. Chem. B, 104(27), 6452 (2000)
Chen D, Moljord K, Fuglerud T, Holmen A, Microporous Mesoporous Mater., 29, 191 (1999)
Wilson S, Barger P, Microporous Mesoporous Mater., 29, 117 (1999)
Dahl IM, Modtad H, Akporiaye D, Wendelbo R, Microporous Mesoporous Mater., 29, 185 (1999)
Ko TS, Seo G, Korean Chem. Eng. Res., 28(2), 163 (1990)
Ko TS, Seo G, Korean Chem. Eng. Res., 29(3), 263 (1991)
Dubois DR, Obrzut DL, Liu J, Thundimadathil J, Adekkanattu PM, Guin JA, Punnoose A, Seehra MS, Fuel Process. Technol., 83, 203 (2003)
Venkatathri N, Catal. Commun., 7, 773 (2006)
Franklin IL, Beale AM, Sankar G, Catal. Today, 81(4), 623 (2003)
Gayubo AG, Aguayo AT, Alonso A, Atutxa A, Bilbao J, Catal. Today, 106(1-4), 112 (2005)
Aguayo AT, Gayubo AG, Vivanco R, Alonso A, Bilbao J, Ind. Eng. Chem. Res., 44(19), 7279 (2005)
Wang W, Seiler M, Hunger M, J. Phys. Chem. B, 105(50), 12553 (2001)
Wang W, Jiang Y, Hunger M, Catal. Today, 113, 101 (2006)
Carlson LK, Isbester PK, Munson EJ, Solid State Nucl. Magn. Reson., 16, 93 (2000)
Dahl IM, Kolboe S, J. Catal., 149(2), 458 (1994)
Dahl IM, Kolboe S, J. Catal., 161(1), 304 (1996)
Arstad B, Nicholas JB, Haw JF, J. Am. Chem. Soc., 126(9), 2991 (2004)
Marcus DM, Song WG, Abubakar SM, Jani E, Sassi A, Haw JF, Langmuir, 20(14), 5946 (2004)
Haw JF, Marcus DM, Top. Catal., 34, 41 (2005)
Guisnet M, J. Mol. Catal. A-Chem., 182, 367 (2002)
Patcas FC, J. Catal., 231(1), 194 (2005)
Masuda T, Asanuma T, Shouji M, Mukai SR, Kawase M, Hashimoto K, Chem. Eng. Sci., 58(3-6), 649 (2003)
Tago T, Iwakai K, Morita K, Tanaka K, Masuda T, Catal. Today, 105(3-4), 662 (2005)
Chen JQ, Bozzano A, Glover B, Fuglerud T, Kvisle S, Catal. Today, 106(1-4), 103 (2005)
Bjorgen M, Olsbye U, Petersen D, Kolboe S, J. Catal., 221(1), 1 (2004)
Wang W, Buchholz A, Seiler M, Hunger M, J. Am. Chem. Soc., 125(49), 15260 (2003)
Lesthaeghe D, Speybroeck VV, Marin GB, Waroquier M, Chem. Phys. Lett., 417, 309 (2006)
Jiang YJ, Wang W, Marthala VRR, Huang J, Sulikowski B, Hunger M, J. Catal., 238(1), 21 (2006)
Seiler M, Schenk U, Hunger M, Catal. Lett., 62(2-4), 139 (1999)
Hunger M, Seiler M, Buchholz A, Catal. Lett., 74(1-2), 61 (2001)
Han X, Yan Z, Zhang W, Bao X, Curr. Org. Chem., 5, 1017 (2001)
Svelle S, Bjorgen M, Kolboe S, Kuck D, Letzel M, Olsbye U, Sekiguchi O, Uggerud E, Catal. Lett., 109, 25 (2006)
Svelle S, Aravinthan S, Bjorgen M, Lillerud KP, Kolboe S, Dahl IM, Olsbye U, J. Catal., 241, 243 (2006)
Lesthaeghe D, Speybroeck VV, Marin GB, Waroquier M, Angew. Chem.-Int. Edit., 45, 1714 (2006)
Marcus DM, McLachlan KA, Wildman MA, Ehresmann JO, Kletnieks PW, Haw JF, Angew. Chem.-Int. Edit., 45, 3133 (2006)
