Korean Chemical Engineering Research

  • 제43권6호
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  • Pages.675-682
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  • 2005
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  • 0304-128X(pISSN)
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  • 2233-9558(eISSN)
한국화학공학회 (The Korean Institute of Chemical Engineers)
권호 표지

메조포러스 분자체에 담지된 Pt/Pd 촉매상에서 납사분해 잔사유의 방향족 화합물 수소화 특성

Hydrogenation Characteristics of Aromatics in Residue Oil of Naphtha Cracking on Pt/Pd Impregnated Mesoporous Molecular Sieve

  • 최종화 (한국화학연구원 응용화학연구부) ;
  • 정순용 (한국화학연구원 응용화학연구부) ;
  • 오성근 (한양대학교 응용화학공학부)
  • 투고 : 2005.09.14
  • 심사 : 2005.11.11
  • 발행 : 2005.12.31
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초록

불화실리콘산($H_2SiF_6$)과 질산알루미늄의 혼합 수용액을 주형으로 사용되는 $C_{16}TMABr$(cethyltrimethylaminonium bromide)용액에 첨가하여 불화실리콘산의 hydrolysis 반응에 의해서 메조포러스 분자체(Al-MMS)를 합성하였다. 합성된 분자체를 분석한 결과 비표면적이 $981m^2/g$이고, 기공 크기가 $39{\AA}$ 부근에서 균일함을 보이는 메조포러스 분자체가 합성되었으며, $NH_3$-TPD 결과 산의 세기가 크지 않음을 알 수 있었다. 합성된 담체가 납사분해 잔사유에 포함되어 있는 방향족 화합물의 수소화 반응에 대한 촉매 담체로써 적용 가능한가를 조사하기 위해서 Pt 및 Pd의 금속 성분을 담지시킨 후, 납사 분해 잔사유에 많이 포함되어 있는 방향족 화합물인 나프탈렌을 모델화합물로 정하고 나프탈렌의 수소화 반응에 대한 온도별 전환율, 반응속도 상수, 활성화 에너지를 조사하였다. 또한, 다른 메조포러스 담체와 상용담체를 이용하여 촉매를 제조한 후 같은 방법으로 비교하였다. 그 결과 PtPd/Al-MMS 촉매가 우수한 탈방향족 활성과 황저항성을 나타내었으며, 다른 메조포러스 담체 및 상용 담체와 비교한 결과 활성이 우수하게 나타났다. 실제 납사분해 잔사유의 일종인 PGO(pyrolized gas oil)를 원료로 실험해 본 결과 활성이 우수하게 나타났으며 Pd/Al-MMS 촉매는 납사분해 잔사유에 포함된 방향족 화합물의 수소화 촉매로써 응용 가능성을 보였다.

Al containing mesoporous molecular sieve (Al-MMS) was synthesized by hydrolysis of $H_2SiF_6$ and $Al(NO_3)_3{\cdot}9H_2O$. The material obtained was characterized by XRD, $N_2$-physisorption. The specific surface area was $981m^2/g$, and the average pore size was uniformity $39{\AA}$. It was confirmed that the acidity of Al-MMS was milder than that of zeolite Y based on the results of $NH_3$-TPD. Active materials, Pt and Pd, were loaded on Al-MMS in order to examine the feasibility of using Al-MMS as a catalyst support in the hydrogenation of aromatic compounds included in the residue oil of a naphtha cracker. The hydrogenation activity of PtPd/Al-MMS has been studied by following the kinetics of the hydrogenation of naphthalene, and by comparing the kinetic parameters obtained with Pt and Pd catalysts supported on the other mesoporous material support and commercial conventional support materials. PtPd/Al-MMS catalyst shows the highest activity of hydrogenation and sulfur resistance. The high activity of PtPd/Al-MMS was confirmed again in the hydrogenation of PGO (pyrolized gas oil), which is residue oil obtained from a naphtha cracker. Therefore, PtPd/Al-MMS can be applied to the hydrogenation of aromatic compounds included in the residue oil of a commercial naphtha cracker commericially.

키워드

참고문헌

  1. Huang, T. C. and Kang, B. C., 'The Thioresistance of Platinum/ Aluminum Borate Catalysis in Aromatic Hydrogenation,' Journal of molecular Catalysis A: Chemical, 103, 163-174(1995) https://doi.org/10.1016/1381-1169(95)00136-0
  2. Santikunaporn, M., Herrera, J. E. and Resasco, D. E., 'Ring Opening of Decaline and Tetralin on HY and PtIHY Zeolite Catalysts;' Journal of Catalysis, 228, 100-113(2004) https://doi.org/10.1016/j.jcat.2004.08.030
  3. Fujikawa, T., Idei, K. and Ebihara, T., 'Aromatic Hydrogenation of Distillates over Si02-Al203-Supported Noble Metal Catalysts;' Applied Catalysis A: General, 192, 253-261(2000) https://doi.org/10.1016/S0926-860X(99)00403-2
  4. Kimbara, N. and Charland, J., 'First Resolution of a Free Secondary Phosphine Chiral at Phosphorus and Stereospecific Formation and Structural Characterization of a Homochiral Secondary Phosphine-Borane Complex' Ind. Eng. Chern. Res., 35, 3874-3877 (1996) https://doi.org/10.1021/ie960175a
  5. Schmitz, A. D. and Song, C. S., 'Shape-Selective Isopropylation of Naphthalene. Reactivity of 2,6-diisopropylnaphthalene on Dealuminated Mordenites' Catalysis Today, 31, 19-25(1996) https://doi.org/10.1016/0920-5861(96)00031-4
  6. Winquist, B. H., 'Hydrogenation Catalyst and Process;' U.S. Patent No. 5,391,291(1995)
  7. John, W. w., 'Catalyst Containing Zeolite Beta:' U.S. Patent No. 5,536,687(1996)
  8. William, R D., 'Method for Removing Magnesium from Aluminum-Magnesium Alloys with Engineered Scavenger Compound;' U.S. Patent No. 5,500,100(1996)
  9. Beck, J. S., Vartuli, J. C., Roth, W. J., Leonowicz, M. E., Kresge, C. T., Schmitt, K. D., Chu, C. T., Olson, D. H., Sheppard, E. w., McCullen, S. B., Higgins, J. B. and Schlenker, J. L., 'A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates;' J. Arn. Chern. Soc., 114, 10834-10843(1992)
  10. Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. and Beck, J. S., 'Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-crystal Template Mechanism;' Nature, 359, 710-712(1992)
  11. Yue, Y., Sun, Y. and Gao, Z., 'Disordered Mesoporous KIT-l as a Support for Hydrodesulfurization Catalysts;' Catalysis letters, 47, 167-171(1997) https://doi.org/10.1023/A:1019084400340
  12. Corma, A., Martinez, A. and Martinez-Soria, V., 'Hydrogenation of Aromatics in Diesel Fuels on PtlMCM-41 Catalysts;' Journal of Catalysis, 169, 480-489(1997) https://doi.org/10.1006/jcat.1997.1737
  13. Park, K. C., Yrm, D. J. and Ihm, S. K., 'Characterstics of AlMCM-41 Supported Pt Catalysts: Effect of Al Distribution in AlMCM-41 on its Catalytic Activity in Naphthalene Hydrogenation:' Catalysis Today, 74, 281-290(2002) https://doi.org/10.1016/S0920-5861(02)00024-X
  14. Jeong, S. Y., Sub, J. W., Lee, J. M. and Kwon, 0. Y., 'Preparation of Silica-Based Mesoporous Materials for Fluorosilicon Compounds: Gelation of H2SiF6 in Ammonia Surfactant Solution;' Journal of Colloid and Interface Science, 192, 156-161 (1997) https://doi.org/10.1006/jcis.1997.4974
  15. Ahn, W. S., Kim, N. K. and Jeong, S. Y., 'Synthesis Characterization, and Catalytic Properties of Ti-containing Mesoporous Molecular Sieves Prepared using a Fluorosilicon Compound;' Catalysis Today, 68, 83-88(2001) https://doi.org/10.1016/S0920-5861(01)00294-2
  16. Kim, J. M., Jun, S. and Ryoo, R, 'Improvement of Hydrothermal Stability of Mesoporous Silica Using Salts: Reinvestigation for Time-Dependent Effects;' J. Phys. Chern. B, 103,6200-6205 (1999)
  17. Jeong, S. Y., Sub, J. W., Lee, J. M. and Kwon, 0. Y., 'Preparation of Silica-Based Mesoporous Materials for Fluorosilicon Compounds: Gelation of H2SiF6 in Ammonia Surfactant Solution;' Journal of Colloid and Interface Science, 192, 156-161 (1997) https://doi.org/10.1006/jcis.1997.4974
  18. Costa, C., Lopes, J. M., Lemos, F., Ramoa Ribeiro, F., 'Activity-Acidity Relationship in Zeolite Y: Part 2. Determination of the Acid Strength Distribution by Temperature Programmed Desorption of Ammonia:' J. Mol. Cat. A : Chemical, 144,221231(1999)
  19. Girgis, M. J. and Gates, B. C., 'Reactivities Reaction Networks and Kinetics in High-Pressure Catalytic Hydroprocessing' Ind. Eng. Chern. Res., 30, 2021-2058(1991) https://doi.org/10.1021/ie00057a001
  20. Koussathana, M., Vamvouk, D., Economon, H. and Verykios, X, 'Slurry-Phase Hydrogenation of Aromatic Compounds over Supported Noble Metal Catalysts:' Appl. etal., 77, 283-301(1991)
  21. Lin, S. D. and Song, C., 'Noble Metal Catalsis for Low- Temperature Naphthalene Hydrogenation in the Presence of Benzothiophene' Catal. Today, 31, 93-104(1996) https://doi.org/10.1016/0920-5861(96)00038-7
  22. Bouchy, M., Peureux-Denys, S., Dufresne, P. and Kasztelan, S., 'Hydrogenation and Hydrocracking of a Model Light Cycle Oil Feed. 2. Properties of a Sulfided Nickel-Molybdenum Hydrocracking Catalyst:' Ind. Eng. Chern. Res., 32, 1592-1602(1992)
  23. Zhan, X. D. and Guin, J. A., 'High-Pressure Hydrogenation of Naphthalene Using a Reduced Iron Catalyst:' Energy & Fuel, 8, 1384-1393(1994) https://doi.org/10.1021/ef00048a030