DOI QR코드

DOI QR Code

Synthesis of Butenes through Butanol Dehydration over Catalyst Prepared from Water Treatment Sludge

정수 슬러지로부터 제조된 촉매 상에서 부탄올 탈수반응을 통한 부텐 제조

  • Kim, Goun (Department of Chemical Engineering, Kongju National University) ;
  • Bae, Junghyun (Department of Chemical Engineering, Kongju National University) ;
  • Choi, Hyeonhee (Department of Chemical Engineering, Kongju National University) ;
  • Lee, Choul-Ho (Department of Chemical Engineering, Kongju National University) ;
  • Jeon, Jong-Ki (Department of Chemical Engineering, Kongju National University)
  • Received : 2014.10.27
  • Accepted : 2014.12.09
  • Published : 2015.02.01

Abstract

The objective of this study is to evaluate the catalytic potential of the porous material prepared from water treatment sludge. The textural properties of the catalyst were studied using $N_2$ adsorption and desorption isotherms, scanning electron microscope, and X-ray diffraction. The pellet-type catalyst prepared using water treatment sludge is determined to be a material that contains mesopores as well as micropores. The specific surface area of the catalyst is $157m^2/g$. Acidic characteristics of the catalyst are analyzed by temperature-programmed desorption of ammonia and infrared spectroscopy of adsorbed pyridine. 2-Butanol dehydration reaction was carried out in a fixed bed catalytic reactor. Yields of 1-butene, trans-2-butene, and cis-2-butene at $350^{\circ}C$ were 25.6 wt%, 19.2 wt%, and 29.9 wt%, respectively. This catalytic activity of the catalyst based on water treatment sludge in 2-butanol dehydration is due to the acid sites composed of Bronsted acid sites and Lewis acid sites. It was confirmed that the catalyst based on water treatment sludge can be utilized to produce $C_4$ olefin through butanol dehydration.

본 연구의 목적은 정수 슬러지로부터 제조된 다공성 물질의 촉매 기능을 평가하기 위한 것이다. 촉매의 구조적 특성은 질소 흡착-탈착 등온선, 주사 전자 현미경 및 X선 회절을 이용하여 조사하였다. 정수 슬러지로부터 제조된 촉매는 메조 기공과 미세 기공을 동시에 보유하고 있으며, 촉매의 비표면적은 $157m^2/g$이다. 촉매의 산특성은 암모니아 승온탈착법과 피리딘 흡착 적외선 분광법으로 분석하였다. 고정층 촉매 반응기에서 2-부탄올의 탈수 반응을 수행한 결과, $350^{\circ}C$의 반응 온도에서 1-부텐, 트랜스-2-부텐 및 시스-2-부텐의 수율은 각각 25.6 wt%, 19.2 wt% 및 29.9 wt%이었다. 정수 슬러지로부터 제조된 촉매의 2-부탄올 탈수 반응 활성은 브뢴스테드 산점와 루이스 산점으로 이루어진 산점을 보유한 것에 기인한다. 부탄올의 탈수 반응에 의해 $C_4$ 올레핀을 제조하는 반응에서 정수 슬러지로부터 제조된 촉매의 활용 가능성을 확인하였다.

Keywords

References

  1. Lee, J. K., Beak, S. G., Kim, Z. C., Lee, J. I. and Pyo, B. S., "A Study on Producing Inorganic Fertilizer from the Sludge of Water Supply Plant," J. KOWREC, 8(1), 103-108(2000).
  2. Koo, J. K., Lim, J. S., Moon, Y. T. and Lee, I. B., "A Study on the Artificial Culture Soil Using Alum Sludge," J. KOWREC, 7, 1-12(1999).
  3. Kim, J. M., Kim, M. K., Lee, J. M., Lee, C. H., Lee, S. W., Choi, D. J. and La, J. M., "Method of Manufacturing a Building Material Composition Eco-friendly," Korea Patent No. 10-1041094(2011).
  4. Kang, K. C., Kim, Y. H., Kim, J. M., Lee, C. H. and Rhee, S. W., "Synthesis of $AlPO_4$-type Mesoporous Materials using Alum Sludge," Appl. Chem. Eng., 22(2), 173-177(2011).
  5. Hwang, H. U., Kim, J. H. and Kim, Y. J., "Recycling of Waterworks Sludge in Red Clay Bricks Manufacturing," J. Kor. Soc. Environ. Eng., 31(3), 217-222(2009).
  6. Seredych, M., Strydom, C. and Bandosz, T. J., "Effect of Fly Ash Addition on the Removal of Hydrogen Sulfide from Biogas and Air on Sewege Sludge-based Composite Adsorbents,"Waste Manage., 28, 1983-1992(2008). https://doi.org/10.1016/j.wasman.2007.08.020
  7. Yuan, W. and Bandosz, T. J., "Removal of Hydrogen Sulfide from Biogas on Sludge-derived Adsorbents," Fuel, 86, 2736-2746(2007). https://doi.org/10.1016/j.fuel.2007.03.012
  8. Hwang, H. U., Kim, J. H. and Kim, Y. J., "Recycling of Waterworks Sludge in Red Clay Bricks Manufacturing," J. Kor. Soc. Environ. Eng., 3, 217-222(2009).
  9. Jeong, S., Kim, H., Bae, J., Kim, D. H., Peden, C. H. F., Park, Y. K. and Jeon, J. K., "Synthesis of Betenes Through 2-butanol Dehydration over Mesoporous Materials Produced from Ferrierite," Catal. Today, 185(1), 191-197(2012). https://doi.org/10.1016/j.cattod.2011.09.017
  10. Ko, M. S., Jeon, J. K., Cho, J., Lee, S. J. and Lee, J. H., "Process of the Selectivity Production of 1-Butene through Positional Isomerization from 2-Butenes," Korean Chem. Eng. Res., 46(4), 692-696(2008).
  11. Macht, J., Baertsch, C. D., May-Lozano, M., Soled, S. L., Wang, Y. and Iglesia, E., "Support Effect on Bronsted Acid Site Densities and Alcohol Dehydration Turnover Rates on Tungsten Oxide Domains," J. Catal., 227, 479-491(2004). https://doi.org/10.1016/j.jcat.2004.08.014
  12. Herrera, J. E., Kwak, J. H., Hu, J. Z., Wang, Y., Peden, C. H. F., Macht, J. and Iglesia, E., "Synthesis, Sharacterization and Catalytic Function of Novel Highly Dispersed Tungsten Oxide Catalysts on Mesoporous Silica," J. Catal., 239, 200-211(2006). https://doi.org/10.1016/j.jcat.2006.01.034
  13. Herrera, J. E., Kwak, J. H., Hu, J. Z., Wang, Y. and Peden, C. H. F., "Effect of Novel Supports on the Physical and Catalytic Properties of Tungstophosphoric Acid for Alcohol Dehydration Reactions," Top. Catal., 49, 259-267(2008). https://doi.org/10.1007/s11244-008-9081-4
  14. West, R. M., Braden, D. J. and Dumesic, J. A., "Dehydration of Butanol to Butene over Solid Acid Catalysts in High Water Environments," J. Catal., 262, 134-143(2009). https://doi.org/10.1016/j.jcat.2008.12.009
  15. Macht, J., Carr, R. T. and Iglesia, E., "Functional Assessment of the Strength of Solid Acid Catalysts," J. Catal., 264, 54-66(2009). https://doi.org/10.1016/j.jcat.2009.03.005
  16. Bedia, J., Ruiz-Rosas, R., Rodriguez-Mirasol, J. and Cordero, T., "Kinetic Study of the Decomposition of 2-Butanol on Carbon-Based Acid Catalyst," AIChE J., 56(6), 1557-1568(2010). https://doi.org/10.1002/aic.12056
  17. Zhang, D., Al-Hajri, R., Barri, S. A. and Chadwick, D., "One-step Dehydration and Isomerisation of n-Betanol to iso-Butene over Zeolite Catalysts," Chem. Commun., 46, 4088-4090(2010). https://doi.org/10.1039/c002240c
  18. Bae, J., Park, N., Lee, C. H., Park, Y. K. and Jeon, J. K., "Adsorption Performance of Basic Gas over Pellet-type Adsorbents Prepared from Water Treatment Sludge," Korean Chem. Eng. Res., 51, 352-357(2013). https://doi.org/10.9713/kcer.2013.51.3.352
  19. Park, N., Bae, J., Lee, C. H. and Jeon, J. K., "Extrution of Pellettype Adsorbents Employed with Alum Sludge and $H_2S$ Removal Performance," Clean Technol., 19(2), 121-127(2013). https://doi.org/10.7464/ksct.2013.19.2.121
  20. Choi, H. H., Bae, J. H., Kim, D. H., Park, Y. K. and Jeon, J. K., "Butanol Dehydration over $V_2O_5$-$TiO_2$/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition," Materials, 6, 1718-1729(2013). https://doi.org/10.3390/ma6051718
  21. Choi, H. H., Lee, E. O., Jin, M. S., Park, Y. K., Kim, J. M. and Jeon, J. K., "Catalytic Properties of Highly Ordered Crystalline Nanoporous Tungsten Oxide in Butanol Dehydration," J. Nanosci. Nanotechnol., 14, 8828-8833(2014). https://doi.org/10.1166/jnn.2014.9952
  22. Kim, H. J., Jeong, S. Y., Kim, D. H., Park, Y. K. and Jeon, J. K., "Preparation of Highly Dispersed Tungsten Oxide on MCM-41 by Atomic Layer Deposition and Its Application to Butanol Dehydration," J. Nanosci. Nanotechnol., 12, 6074-6079(2012). https://doi.org/10.1166/jnn.2012.6290
  23. Rouquerol, J., Avnir, D., Fairbridge, C. W., Everet, D. H., Haynes, J. H., Pernicone, N., Ramsay, J., Sing, K. S. and Unger, K. K., "Recommendations for the Characterization of Porous Solids," Pure Appl. Chem., 66, 1739-1758(1994).
  24. Yun, S. Y., Lee, E. O., Park, Y. K., Jeong, S. Y., Han, J. S., Jeong, B. H. and Jeon, J. K., "Selective Hydroisomerization of n-Dodecane over Platinum supported on Zeolites," Res. Chem. Intermed., 37, 1215-1223(2011). https://doi.org/10.1007/s11164-011-0386-8
  25. Yurdakoc, M., Akcay, M., Tonbul, Y. and Yurdakoc, K. "Acidity of Silica-Alumina Catalysts by Amine Titration using Hammett Indicators and FT-IR Study of Pyridine Adsorption," Turk. J. Chem., 23, 319-328(1999).
  26. Palomino, G. T., Pascual, J. J. C., Delgado, M. R., Parra, J. B. and Arean, C. O., "FT-IR Studies on the Acidity of Gallium-Substituted Mesoporous MCM-41 Silica," Mater. Chem. Phys., 85, 145-150(2004). https://doi.org/10.1016/j.matchemphys.2003.12.020
  27. Zaki, M. I., Hasan, M. A., Al-Sagheer, F. A. and Pasupulety, L., "In situ FTIR Spectra of Pyridine Adsorbed on $SiO_2$-$Al_2O_3$, $TiO_2$, $ZrO_2$ and $CeO_2$: General Considerations for the Identification of Acid Sites on Surfaces of Finely Divided Metal Oxides," Colloids Surf. A: Physicochem. Eng. Asp., 190, 261-274(2001). https://doi.org/10.1016/S0927-7757(01)00690-2