고정층 반응기를 사용하여 상압에서 에탄올로부터 방향족화합물 제조에 관한 ZSM-5 제올라이트의 금속성분 및 실리카/알루미나 비의 영향을 고찰하였으며, 반응온도, 중량공간속도(WHSV), 반응물인 에탄올에 물 및 메탄올 첨가 영향도 검토하였다. 촉매로는 Si/Al2 비율이 23~280 범위의 상용 ZSM-5에 Zn, La, Cu, Ga 성분을 함침시켜 촉매 활성 및 안전성 테스트에 사용하였다. 촉매의 특성분석을 위해 암모니아 승온탈착 실험(NH3-TPD)과 질소 흡-탈착실험을 수행하였다. 실험결과, 방향족화합물의 선택도에 관한 ZSM-5에 함침한 금속성분과 ZSM-5의 Si/Al2비에 크게 영향을 받았는데, 함침금속은 Zn-La > Zn > La > Cu > Ga 순으로 감소하였으며, ZSM-5의 적절한 산점을 가진 Si/Al2=50, 80에서 가장 우수하였다. 최적 반응온도(437 ℃)와 공간속도(0.8 h^(-1))에서 방향족화합물의 선택도는 초기 72%에서 30시간 이후 56%로 서서히 감소하는 경향을 나타내었다.

The catalytic conversion of ethanol to aromatic compounds ETA was studied over ZSM-5 heterogeneous catalysts. The effect of reaction temperature, weight hourly space velocity (WHSV), and addition of water and methanol, which are the potential impurities of bio-ethanol, on the catalytic performance was investigated in a fixed bed reactor. Commercial ZSM-5 catalysts having different Si/Al2 ratios of 23 to 280 and modified ZSM-5 catalysts by addition of metal (Zn, La, Cu, and Ga) were used for the activity and stability tests in ETA reaction. The catalysts were characterized with ammonia temperature programmed desorption (NH3-TPD) and nitrogen adsorption-desorption techniques. The results of catalytic performance revealed that the optimal Si/Al2 ratio of ZSM-5 is about 50~80 and the selectivity to aromatic compounds decreases in the order of Zn/La > Zn > La > Cu > Ga for the modified ZSM-5 catalysts. Among these catalysts from the ETA reaction, Zn-La/ZSM-5 showed the best catalytic performance for the ETA reaction. The selectivity to aromatic compounds was 72% initially and 56% after 30 h over the catalysts at reaction temperature of 437 ℃ and WHSV of 0.8 h^(-1).

Ethanol to Aromatics Metal Impregnation ZSM-5 Silica Alumina Ratio Ethanol Aromatics

Tret’yakova VF, Makarfi YI, Tret’yakov KV, Frantsuzova NA, Talyshinskii RM, Catalysis in Industry., 2, 402 (2010)
Ni YM, Sun AM, Wu XL, Hu JL, Li T, Li GX, Chin. J. Chem. Eng., 19(3), 439 (2011)
Makarfi YI, Yakimova MS, Lermontov AS, Erofeev VI, Koval LM, Tretiyakov VF, Chem. Eng. J., 154(1-3), 396 (2009)
Roh HS, Platon A, Wang Y, King DL, Catal. Lett., 110(1-2), 1 (2006)
Ni Y, Peng W, Sun A, Mo W, Hu J, Li T, Li G, J. Ind. Eng. Chem., 16(4), 503 (2010)
Farkas AP, Solymosi F, Surf. Sci., 601, 193 (2007)
Conte M, Lopez-Sanchez JA, He Q, Morgan DJ, Ryabenkov Y, Bartley JK, Carley AF, Taylor SH, Kiely CJ, Khalid K, Hutchings GJ, Catalysis Science & Technology., 2, 105 (2012)
Akhtar MN, Al-Yassir N, Al-Khattaf S, Cejka J, Catal. Today, 179(1), 61 (2012)
Liu H, Yang S, Hu J, Shang F, Li Z, Xu C, Guan J, Kan Q, Fuel Process. Technol., 6, 195 (2012)
Inaba M, Murata K, Saito M, Takahara I, React. Kinet. Catal. Lett., 88, 135142 (2006)
Hoang TQ, Zhu X, Danuthai T, Lobban LL, Resasco DE, Mallinson RG, Energy Fuels., 24, 3804 (2010)
Ghiaci M, Abbaspur A, Arshadi M, Aghabarari B, Appl. Catal. A: Gen., 316(1), 32 (2007)
Seo G, Min BG, Korean Chem. Eng. Res., 44(4), 329 (2006)
Kecskemeti A, Barthos R, Solymosi F, J. Catal., 258(1), 111 (2008)
Barthos R, Szechenyi A, Solymosi F, J. Phys. Chem. B, 110(43), 21816 (2006)
Ni Y, Sun A, Wu X, Hai G, Hu J, Li T, Li G, Microporous Mesoporous
Yang Y, Sun C, Du J, Yue Y, Hua W, Zhang C, Shen W, Xu H, Catal.Commun., 24, 44 (2012)
Zhang L, Liu HJ, Li XJ, Xie SJ, Wang YZ, Xin WJ, Liu SL, Xu LY, Fuel Process. Technol., 91(5), 449 (2010)
Korobitsyna LL, Velichkina LM, Vosmerikov AV, Radomskaya VI, Astapova ES, Ryabova NV, Agapyatova OA, Russian Journal of Inorganic Chemistry., 53, 169 (2008)
Juttu GG, Smith RS, “Catalyst for Aromatization of Alkanes, Process of Making and Process of Using Thereof ,” United States Patent 7,186,872 B2 (2007)
Ding C, Wang X, Guo X, Zhang S, Catal. Commun., 9, 487 (2007)
Williams CL, Chang CC, Do P, Nikbin N, Caratzoulas S, Vlachos DG, Lobo RF, Fan W, Dauenhauer PJ, American Chemical Society., 2, 935 (2012)