硅铝比对HZSM-5分子筛催化正丁烷裂解反应性能的影响
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摘要
利用原位红外光谱法对不同硅铝比的HZSM-5分子筛催化剂进行表征,并在微反评价装置上对不同硅铝比分子筛催化正丁烷高温裂解活性进行评价,揭示了HZSM-5分子筛"硅铝比-活性位性质-催化性能"三者之间的关系。结果表明,硅铝比[n(SiO_2)/n(Al_2O_3)]分别为38和200的HZSM-5分子筛表面活性位类型、数目和强度均存在巨大差异。HZSM-5-38分子筛表面存在较多的强酸性的硅铝桥键羟基和非骨架铝羟基,而HZSM-5-200分子筛表面仅存在少量的弱酸性或不具酸性的微孔内邻位孤立硅羟基和外表面孤立硅羟基。HZSM-5-200分子筛表现出更高的低碳烯烃收率,因而较低的酸密度和酸强度有利于多产烯烃。
The HZSM-5 zeolites with different mole ratio of SiO_2/Al_2O_3 were characterized by in-situ FT-IR and their n-butane cracking activities were investigated in a continuous flow fixed-bed micro-reactor to reveal the relationship between Si/Al ratio,active sites and catalytic behavior.The results indicated that the kind,number,and strength of active sites of HZSM-5 zeolites with Si/Al ratio of 38 and 200 were significantly different.HZSM-5-38 zeolites have more acid bridging Si-O(H)-Al groups and nonskeleton aluminum hydroxyl with strong acidity,while,HZSM-5-200 zeolites only show several isolated hydroxyl groups with small amount of weakly acidic or non-acidic neighbouring silica hydroxyl groups in microporous.HZSM-5-200 zeolites result in higher yield of light olefins,indicating that lower acid density and strength is suitable for producing more olefins.
The HZSM-5 zeolites with different mole ratio of SiO_2/Al_2O_3 were characterized by in-situ FT-IR and their n-butane cracking activities were investigated in a continuous flow fixed-bed micro-reactor to reveal the relationship between Si/Al ratio,active sites and catalytic behavior.The results indicated that the kind,number,and strength of active sites of HZSM-5 zeolites with Si/Al ratio of 38 and 200 were significantly different.HZSM-5-38 zeolites have more acid bridging Si-O(H)-Al groups and nonskeleton aluminum hydroxyl with strong acidity,while,HZSM-5-200 zeolites only show several isolated hydroxyl groups with small amount of weakly acidic or non-acidic neighbouring silica hydroxyl groups in microporous.HZSM-5-200 zeolites result in higher yield of light olefins,indicating that lower acid density and strength is suitable for producing more olefins.
引文
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[12]Zecchina A,Bordiga S,Spoto G,et al.Silicalite characterization.2.IR spectroscopy of the interaction of carbon monoxide with internal and external hydroxyl groups[J].The Journal of Physical Chemistry,1992,96(12):4991-4997
[13]Wang Pengzhao,Zhang Wenfang,Zhang Qiang,et al.Comparative study of n-butane isomerization over SO2-4/ZrO2-Al2O3and HZSM-5zeolites at low reaction temperatures[J].Applied Catalysis A:General,2018(550):98-104
[14]Zhang Jingchen,Yin Wenkun,Shang Hongyan,et al.In situ FT-IR spectroscopy investigations of carbon nanotubes supported Co-Mo catalysts for selective hydrodesulfurization of FCC gasoline[J].Journal of Energy Chemistry,2008,17(2):165-170
[15]王斌,张强,李春义,等.催化裂化催化剂基质表面强弱Brnsted酸性位数目对小分子烯烃收率的影响[J].石油炼制与化工,2016,47(3):10-15
[16]Lombardo E A,Sill G A,Hall W K.The assay of acid sites on zeolites as measured by ammonia poisoning[J].Journal of Catalysis,1989,119(2):426-440
[2]张敏秀,张文芳,周柏成,等.La/Ni改性SO2-4/ZrO2-Al2O3催化正丁烷异构化反应性能研究[J].石油炼制与化工,2017,48(12):33-38
[3]Lu Jiangyin,Zhao Zhen,Xu Chunming,et al.Catalytic cracking of isobutane over HZSM-5,FeHZSM-5and CrHZSM-5catalysts with different SiO2/Al2O3ratios[J].Journal of Porous Materials,2008,15(2):213-220
[4]Wakui K,Satoh K,Sawada G,et al.Cracking of n-butane over alkaline earth-containing HZSM-5catalysts[J].Catalysis Letters,2002,84(3/4):259-264
[5]Hou Xu,Qiu Yuan,Zhang Xiangwen,et al.Analysis of reaction pathways for n-pentane cracking over zeolites to produce light olefins[J].Chemical Engineering Journal,2017,307:372-381
[6]刘利利.重石脑油催化裂解制烯烃的研究[D].天津:天津大学,2012
[7]Hou Xu,Qiu Yuan,Yuan Enxian,et al.SO2-4/TiO2promotion on HZSM-5for catalytic cracking of paraffin[J].Applied Catalysis A:General,2017(537):12-23
[8]Krannlia H,Haag H O,Gates B C.Monomolecular and bimolecular mechanisms of paraffin cracking:n-Butane cracking catalyzed by zeolite[J].Journal of Catalysis,1992,135(1),115-124
[9]陆江银.HZSM-5分子筛催化裂解丁烷制低碳烯烃催化剂的研究[D].北京:中国石油大学(北京),2005
[10]郭天祥.催化裂解多产低碳烯烃催化剂的研究[D].北京:北京化工大学,2011
[11]Barbera K,Bonino F,Bordiga S,et al.Structure-deactivation relationship for HZSM-5catalysts governed by framework defects[J].Journal of Catalysis,2011,280(2):196-205
[12]Zecchina A,Bordiga S,Spoto G,et al.Silicalite characterization.2.IR spectroscopy of the interaction of carbon monoxide with internal and external hydroxyl groups[J].The Journal of Physical Chemistry,1992,96(12):4991-4997
[13]Wang Pengzhao,Zhang Wenfang,Zhang Qiang,et al.Comparative study of n-butane isomerization over SO2-4/ZrO2-Al2O3and HZSM-5zeolites at low reaction temperatures[J].Applied Catalysis A:General,2018(550):98-104
[14]Zhang Jingchen,Yin Wenkun,Shang Hongyan,et al.In situ FT-IR spectroscopy investigations of carbon nanotubes supported Co-Mo catalysts for selective hydrodesulfurization of FCC gasoline[J].Journal of Energy Chemistry,2008,17(2):165-170
[15]王斌,张强,李春义,等.催化裂化催化剂基质表面强弱Brnsted酸性位数目对小分子烯烃收率的影响[J].石油炼制与化工,2016,47(3):10-15
[16]Lombardo E A,Sill G A,Hall W K.The assay of acid sites on zeolites as measured by ammonia poisoning[J].Journal of Catalysis,1989,119(2):426-440
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