Preparation of Fe-Zr catalyst by microwave-hydrothermal method and its catalytic performance for the direct synthesis of light olefins from CO hydrogenation
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摘要: 以ZrO(NO3)2·2H2O和Fe(NO3)3·9H2O为原料,采用微波水热法制备了不同Fe2O3/ZrO2物质的量比的Fe-Zr催化剂,并经K改性,研究了其催化CO加氢一步法合成低碳烯烃性能。采用XRD、SEM、TEM和N2吸附-脱附等手段对其物相、形貌和比表面积等进行了表征。结果表明,与共沉淀法相比,微波水热制备的Fe-Zr催化剂颗粒粒径均一,具有相对较小的比表面积和较大的孔径;在CO加氢反应中,Zr助剂的添加显著改善了产物分布,Fe、Zr间适宜的相互作用和相对较大的孔径,有利于抑制CH4的生成,提高烯烃选择性。随着Fe2O3/ZrO2物质的量比的降低,Fe、Zr间相互作用逐渐增强,烯烃选择性和收率先增加后降低。当Fe2O3/ZrO2物质的量比为75:25时,在340 ℃、1.5 MPa、1 000 h-1和H2/CO物质的量比为2的条件下,烯烷比(O/P)达4.86,总烯烃收率达62.57 g/m3。Abstract: A series of Fe-Zr catalysts with different Fe2O3/ZrO2 molar ratios were prepared using ZrO(NO3)2·2H2O and Fe(NO3)3·9H2O as raw materials by means of microwave-hydrothermal method. Then,the catalysts were promoted with potassium by impregnation. The samples were characterized by XRD,SEM,TEM and N2 adsorption-desorption methods. The results showed that the catalysts prepared by microwave-hydrothermal method have a narrow particle size distribution,a lower BET specific surface area and a larger pore size compared with the traditional precipitation method. During the subsequent CO hydrogenation,it was shown that the product distribution was significantly improved with the addition of zirconium,and the suitable interaction between Fe-Zr and proper pore size were favorable for inhibiting the methane formation and enhance the olefin selectivity. With decreasing the Fe2O3/ZrO2 molar ratio,the interaction between Fe and Zr was strengthened,and the olefin selectivity and productivity first increased and then decreased. An olefin to paraffin ratio of 4.86 and light olefin productivity of 62.57 g/m3 could be obtained with a Fe2O3/ZrO2 molar ratio of 75:25 under conditions of H2/CO=2,340 ℃,1.5 MPa and 1 000 h-1.
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Key words:
- microwave-hydrothermal /
- Fe-Zr catalyst /
- CO hydrogenation /
- light olefins
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TORRES GALVIS H M, DE JONG K P. Catalysts for production of lower olefins from synthesis gas: A review[J]. ACS Catal, 2013, 3(9): 2130-2149. ZHANG Q H, DENG W P, WANG Y. Recent advances in understanding the key catalyst factors for Fischer-Tropsch synthesis[J]. J Energy Chem, 2013, 22(1): 27-38. TORRES GALVIS H M, BITTER J H, KHARE C B, RUITENBEEK M, IULIAN DUGULAN A, DE JONG K P. Supported iron nanoparticles as catalysts for sustainable production of lower olefins[J]. Science, 2012, 335(6070): 835-838. 董丽, 杨学萍. 合成气直接制低碳烯烃技术发展前景[J]. 石油化工, 2012, 41(10): 1201-1206. (DONG Li, YANG Xue-ping. New advances in direct production of light olefins from syngas[J]. Petrochemical Technology, 2012, 41(10): 1201-1206.) 胡徐腾, 李振宇, 黄格省. 非石油原料生产烯烃技术现状分析与前景展望[J]. 石油化工, 2012, 41(8): 869-875. (HU Xu-teng, LI Zhen-yu, HUANG Ge-sheng. Present situation and prospect of olefin production technology from non-petroleum raw materials[J]. Petrochemical Technology, 2012, 41(8): 869-875.) CALDERONE V R, SHIJU N R, CURULLA-FERRÉD, CHAMBREY S, KHODAKOV A, ROSE A, THIESSEN J, JESS A, ROTHENBERG G. De novo design of nanostructured iron-cobalt Fischer-Tropsch catalysts[J]. Angew Chem Int Ed, 2013, 125(16): 4493-4497. YANG C, ZHAO H B, HOU Y L, MA D. Fe5C2 nanoparticles: A facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis[J]. J Am Chem Soc, 2012, 134(38): 15814-15821. WANG C F, PAN X L, BAO X H. Direct production of light olefins from syngas over a carbon nanotube confined iron catalyst[J]. Chinese Science Bulletin, 2010, 55(12): 1117-1119. 王虎林, 杨勇, 王洪, 相宏伟, 李永旺. Zn对沉淀铁催化剂结构及其F-T合成性能的影响[J]. 燃料化学学报, 2012, 40(1): 59-67. (WANG Hu-lin, YANG Yong, WANG Hong, XIANG Hong-wei, LI Yong-wang. Effects of Zn promoter on the structure and Fischer-Tropsch performance of iron catalyst[J]. Journal of Fuel Chemistry and Technology, 2012, 40(1): 59-67.) TORRES GALVIS H M, BITTER J H, DAVIDIAN T, RUITENBEEK M, IULIAN DUGULAN A, DE JONG K P. Iron particle size effects for direct production of lower olefins from synthesis gas[J]. J Am Chem Soc, 2012, 134(39): 16207-16215. ZHANG J L, FAN S B, ZHAO T S, LI W H, SUN Y H. Carbon modified Fe-Mn-K catalyst for the synthesis of light olefins from CO hydrogenation[J]. React Kinet Mech Cat, 2011, 102(2): 437-445. STEINER J, BAY K, WERNER V, AMANN J, BUNZEL S, MOβBACHER C, MÜLLER J, SCHWAB E, WEBER M. Iron-and manganese-comprising heterogeneous catalyst and process for preparing olefins by reacting carbon monoxide with hydrogen: US, 0112205A1[P]. 2011-5-12. FERRINI C. Process for the production of light olefins from synthesis gas: WO, 141374A1[P]. 2011-11-17. CARPENTER D. Method and apparatus for forming nano-particles: US, 7282167B2[P]. 2007-10-16. 汪根存, 张侃, 刘平, 惠海涛, 李文怀, 谭猗生. Fe-Mn催化剂浆态床合成低碳烯烃的反应性能[J]. 石油化工, 2012, 41(11): 1234-1238. (WANG Gen-cun, ZHANG Kan, LIU-Ping, HUI Hai-tao, LI Wen-huai, TAN Yi-sheng. Performance of Fe-Mn catalyst for preparation of light olefins in slurry bed reactor[J]. Petrochemical Technology, 2012, 41(11): 1234-1238.) ZHANG W, GAO R, SU G, YIN Y. Light olefins formation from syngas over ZrO2-ZnO catalysts[J]. Stud Surf Sci Catal, 1993, 75(3): 2793-2796. 张皓荐, 马宏方, 张海涛, 应卫勇, 房鼎业. Zr助剂对铁基催化剂F-T合成性能的影响[J]. 天然气化工(C1化学与化工), 2012, 37(2): 12-16. (ZHANG Hao-jian, MA Hong-fang, ZHANG Hai-tao, YING Wei-yong, FANG Ding-ye. Effect of Zr promoter on iron-based catalyst for Fischer-Tropsch synthesis[J]. Natural Gas Chemical Industry, 2012, 37(2): 12-16.) BONDIOLI F, FERRARI A M, LEONELLI C, SILIGARDI C, PELLACANI G C. Microwave-hydrothermal synthesis of nanocrystalline zirconia powders[J]. J Am Ceram Soc, 2001, 84(11): 2728-2730. KOMARNENI S, PIDUGU R, LI Q H, ROY R. Microwave-hydrothermal processing of metal powders[J]. J Mater Res, 1995, 10(7): 1687-1692. KATSUKI H, KOMARNENI S. Microwave-hydrothermal synthesis of monodispersed nanophase SymbolaA@-Fe2O3[J]. J Am Ceram Soc, 2001, 84(10): 2313-2317. OZKARA-AYDINOGLU S, ATAC O, GUL O F, KINAYYIGIT S, SAL S, BARANAK M, BOZ I. Alpha-olefin selectivity of Fe-Cu-K catalysts in Fischer-Tropsch synthesis: Effects of catalyst composition and process conditions[J]. Chem Eng J, 2012, 181: 581-589. DONG D C, HONG P J, DAI S S. Preparation of uniform α-Fe2O3 particles by microwave-induced hydrolysis of ferric salts[J]. Mater Res Bull, 1995, 30(5): 531-535. 吴东辉, 章忠秀, 施磊, 汪信. pH值对微波水热法制备纳米α-Fe2O3的控制作用[J]. 精细化工, 2003, 20(4): 212-214. (WU Dong-hui, ZHANG Zhong-xiu, SHI Lei, WANG Xin. Effect of pH value on preparation of nanon α-Fe2O3 by microwave hydrothermal method[J]. Fine Chemicals, 2003, 20(4): 212-214.) 徐文旸, 李瑞丰, 曹景慧, 窦涛, 马静红. 硅沸石-2在合成气制低碳烯烃中的催化作用[J]. 燃料化学学报, 1989, 17(2): 104-111. (XU Wen-yang, LI Rui-feng, CAO Jing-hui, DOU Tao, MA Jing-hong. Catalytic property of silicalite-2 for making light olefins from syngas[J]. Journal of Fuel Chemistry and Technology, 1989, 17(2): 104-111.) 马中义, 杨成, 董庆年, 魏伟, 陈建刚, 李文怀, 孙予罕. 不同形态ZrO2负载Co催化剂上CO+H2吸附与反应行为研究[J]. 高等学校化学学报, 2005, 26(5): 902-906. (MA Zhong-yi, YANG Cheng, DONG Qing-nian, WEI Wei, CHEN Jian-gang, LI Wen-huai, SUN Yu-han. Adsorption and reaction behavior over Co catalysts supported by different zirconia polymorphs[J]. Chemical Journal of Chinese Universities, 2005, 26(5): 902-906.)
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