Applied Chemistry for Engineering, Vol.26, No.2, 217-223, April, 2015
DTO 반응에서 촉매수명과 경질 올레핀 선택도에 미치는 SAPO-34의 산 처리 효과
Effects of Acid Treatment of SAPO-34 on the Catalytic Lifetime and Light Olefin Selectivity during DTO Reaction
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초록
DTO (dimethyl ether to olefin) 반응에서 촉매 성능을 향상하기 위하여 염산에 의한 SAPO-34 시료의 산 처리 영향을 연구했다. 먼저 TEAOH (tetraethylammonium hydroxide)와 DEA (diethylamine)를 구조유도제로 사용하여 정육면체 형태를 갖는 균일한 크기의 SAPO-34 시료를 수열 합성했다. 제조된 촉매는 염산의 농도 및 처리 시간을 변수로 하여 개조되었다. 그 결과, 우수하게 개조된 시료는 외부 표면의 침식과 함께 총 비표면적 및 마이크로 세공부피가 증가하였으며, 산점량이 다소 감소하는 것으로 나타났다. 특히, 개조된 SAPO-0.2 M (3 h) 시료 상에서의 DTO 반응에서 촉매수명과 경질 올레핀 선택성은 모체 SAPO-34 시료와 비교하여 크게 향상되었다. 이것은 코크 형성에 의한 비활성화가 주로 결정 외부 표면의 기공 입구에서 상대적으로 빠르게 진행된다는 것을 의미한다. 따라서 산 처리는 SAPO-34 촉매의 외부 표면을 개조함으로써 촉매의 성능을 향상할 수 있는 단순한 방법임을 확인했다.
Effects of the post-acid treatment of SAPO-34 sample by hydrochloric acid were investigated to enhance the catalytic performance in DTO reaction. Uniformly sized SAPO-34 samples with cubic-like morphology were prepared by hydrothermal method using TEAOH and DEA as the structure directing agents. It was modified in terms of the HCl concentration and treating
time. As a result, the total surface area and micropore volume for the well modified samples increased and the total acid site was somewhat decreased along with the erosion of the external surface. Especially, the catalytic lifetime and light olefins selectivity for acid treated SAPO-0.2 M (3 h) samples were considerably enhanced compared with those of untreated SAPO-34 samples. It indicates that the deactivation by coke formation proceeds mainly at the pore entrance on the external surface. Therefore, the acid treatment was confirmed to be a simple method which can significantly improve the catalytic performance by modifying the external surface of SAPO-34 catalyst.
- Ren T, Patel MK, Blok K, Energy, 33(5), 817 (2008)
- Ren T, Patel M, Blok K, Energy, 31(4), 425 (2006)
- Stocker M, Micropor. Mesopor. Mater., 29, 3 (1999)
- Keil FJ, Micropor. Mesopor. Mater., 29, 49 (1999)
- Chen JQ, Bozzano A, Glover B, Fuglerud T, Kvisle S, Catal. Today, 106(1-4), 103 (2005)
- Das D, Ravichandran G, Chakrabarty DK, Catal. Today, 36(3), 285 (1997)
- Park JY, Lee YJ, Jun KW, Bae JW, Viswanadham N, Kim YH, J. Ind. Eng. Chem., 15(6), 847 (2009)
- Mirzaei AA, Habibpour R, Kashi E, Appl. Catal. A: Gen., 296, 222 (2005)
- Karimi A, Ahmadi R, Zadeh HRB, Jolodar AJ, Barkhordarion A, Petroleum and Coal, 49, 36 (2007)
- Yaghobi N, Ghoreishy MHR, J. Nat. Gas Chem., 17, 8 (2008)
- Semelsberger TA, Borup RL, Greene HL, J. Power Sources, 156(2), 497 (2006)
- Jang EM, Baek YS, Oh YS, Trans. Korean Hydrogen New Energy Soc., 19, 445 (2008)
- Song WG, Marcus DM, Fu H, Ehresmann JO, Haw JF, J. Am. Chem. Soc., 124(15), 3844 (2002)
- Zhu J, Cui Y, Nawaz Z, Wang Y, Wei F, Chin. J. Chem. Eng., 18(6), 979 (2010)
- Ko TS, Seo G, Korean Chem. Eng. Res., 28, 163 (1990)
- Parlitz B, Schreier E, Zubowa HL, Eckelt R, Lieske E, Lischke G, Fricke R, J. Catal., 155(1), 1 (1995)
- Popova M, Minchev C, Kanazirev V, Appl. Catal. A: Gen., 169(2), 227 (1998)
- Lee YJ, Baek SC, Jun KW, Appl. Catal. A: Gen., 329, 130 (2007)
- Seo G, Min BG, Korean Chem. Eng. Res., 44(4), 329 (2006)
- Haw JF, Song W, Marcus DM, Nicholas JB, Acc. Chem. Res., 36, 317 (2003)
- Haw JF, Marcus DM, Topics Catal., 34, 41 (2005)
- Nazmutdinov AG, Sarkisova VS, Vodenkova NN, Nesterov IA, Nesterova TN, Pet. Chem., 46(6), 428 (2006)
- Verboekend D, Vile G, Perez-Ramirez J, Adv. Funct. Mater., 22(5), 916 (2012)
- Xiaoling L, Yan W, Xujin W, Yafei Z, Yanjun G, Qinghu X, Jun X, Feng D, Tao D, Chin. J. Catal., 33, 1889 (2012)
- Yan ZM, Ding MA, Zhuang JQ, Liu XC, Liu XM, Han XW, Bao XH, Chang FX, Xu L, Liu ZM, J. Mol. Catal. A-Chem., 194(1-2), 153 (2003)
- Moreno S, Poncelet G, Micropor. Mater., 12, 197 (1997)
- Muller M, Harvey G, Prins R, Micropor. Mesopor. Mater., 34, 135 (2000)
- Lee SG, Yoo BK, Je HS, Ryu TG, Park CS, Kim YH, Trans. Korean Hydrogen New Energy Soc., 22, 232 (2011)
- Aguayo AT, Gayubo AG, Atutxa A, Olazar M, Bilbao J, J. Chem. Technol. Biotechnol., 74(11), 1082 (1999)
- Wang P, Yang D, Hu J, Xu J, Lu G, Catal. Today, 212, 62 (2013)
- Shalmani FM, Halladj R, Askari S, Powder Technol., 221, 395 (2012)
- Nishiyama N, Kawaguchi M, Hirota Y, Van Vu D, Egashira Y, Ueyama K, Appl. Catal. A: Gen., 362(1-2), 193 (2009)
- Kim HS, Lee SG, Kim YH, Lee DH, Lee JB, Park CS, J. Nanomater., 2013, 1 (2013)
- Hemelsoet K, Nollet A, Vandichel M, Lesthaeghe D, Speybroeck VV, Waroquier M, Chem. Cat. Chem., 1, 373 (2009)
- Li JZ, Wei YX, Liu GY, Qi Y, Tian P, Li B, He YL, Liu ZM, Catal. Today, 171(1), 221 (2011)
- Speybroeck VV, Hemelsoet K, de Wispelaere K, Qian Q, van der Mynsbrugge J, de Sterck B, Weckhuysen BM, Waroquier M, Chem. Cat. Chem., 5, 173 (2013)
- Chen D, Moljord K, Holmen A, Micropor. Mesopor. Mater., 164, 239 (2012)
- Lee SG, Kim HS, Kim YH, Kang EJ, Lee DH, Park CS, J. Ind. Eng. Chem., 20(1), 61 (2014)
- Izadbakhsh A, Farhadi F, Khorasheh F, Sahebdelfar S, Asadi M, Yan ZF, Micropor. Mesopor. Mater., 126, 1 (2009)
- Sinha AK, Seelan S, Appl. Catal. A: Gen., 270(1-2), 245 (2004)
- Liu G, Tian P, Zhang Y, Li J, Xu L, Meng S, Liu Z, Micropor. Mesopor. Mater., 114, 416 (2008)
- Kang EJ, Lee DH, Kim HS, Choi KH, Park CS, Kim YH, Appl. Chem. Eng., 25(1), 34 (2014)
- Alvaro-Munoz T, Marquez-Alvarez C, Sastre E, Catal. Today, 179(1), 27 (2012)