脱除模板剂前后磷改性对β分子筛稳定性的影响
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摘要
对脱除模板剂前后的β分子筛进行磷改性,采用XRD、BET、NH_3-TPD、FT-IR、~(27)Al MAS NMR等手段对2种β分子筛样品进行物相、孔结构和酸性、骨架铝配位变化表征,考察脱除模板剂前后磷改性对β分子筛稳定性的影响。结果表明:与先磷改性后脱除模板剂相比,先脱除模板剂后磷改性,晶体内空间位阻减小,可增加磷与骨架四配位铝之间的可接近性,使得磷能更有效地与分子筛中骨架四配位铝键合作用,有效抑制了分子筛骨架脱铝,β分子筛水热结构稳定性有较大幅度提升。
The physicochemical properties of phosphorus modified β zeolite with and without removing were characterized by XRD,BET,NH_3-TPD,FT-IR,~(27)Al MAS NMR.The effect of phosphorus modification on the stability of β zeolite was investigated.Results show that compared with previously phosphorus modified after removing the template,removal the template after phosphorus modification causes the reduction of the space resistance of the crystal,which increases the accessibility of phosphorus atoms to framework aluminum species.Thus,phosphorus can be efficiently used to restrict the dealumination of zeolite framework,with significant improvement of the stability of β zeolite under hydrothermal conditions.
The physicochemical properties of phosphorus modified β zeolite with and without removing were characterized by XRD,BET,NH_3-TPD,FT-IR,~(27)Al MAS NMR.The effect of phosphorus modification on the stability of β zeolite was investigated.Results show that compared with previously phosphorus modified after removing the template,removal the template after phosphorus modification causes the reduction of the space resistance of the crystal,which increases the accessibility of phosphorus atoms to framework aluminum species.Thus,phosphorus can be efficiently used to restrict the dealumination of zeolite framework,with significant improvement of the stability of β zeolite under hydrothermal conditions.
引文
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[8]曾海生,崔惠玲,关乃佳.Al,Bi及P改性β分子筛的表面酸性及对烷基转移反应的影响[J].离子交换与吸附,1999,15(4):359-363.(ZEN Haisheng,CUI Huiling,GUAN Naijia.The influence of surface acid and alkyl transference by Al, Bi and phosphorus modificationβmolecular sieve[J].Ion Exchange and Adsorption,1999,15(4):359-363.)
[9]宋祥梅,李英霞,陈标华,等.磷改性β分子筛的酸性及其苯与丙烯烷基化催化性能[J].石油化工高等学校学报,2004,17(4):34-37.(SONG Xiangmei,LI Yingxia,CHEN Biaohua,et al.Acidity of phosphorus modifiedβzeolite and its catalytic performance for alkylation of benzene with propylene[J].Journal of Petrochemical Universities,2004,17(4):34-37.)
[10]王成强,欧阳颖,罗一斌.磷改性β分子筛对单环环烷烃开环反应性能的影响[J].石油炼制与化工,2016,47(8):7-12.(WANG Chengqiang,OUYANG Ying,LUO Yibin. Performances of phosphorus modified zeolite beta in cycloparaffinic ring-opening[J].Petroleum Processing and Petrochemicals,2016,47(8):7-12.)
[11]晁会霞,罗祥生,张凤美.高低温磷改性β分子筛及其烷基化反应性能研究[J].石油炼制与化工,2017,48(4):83-86.(CHAO Huixia, LUO Xiangsheng,ZHANG Fengmei.Study on high and low temperature phosphorus modifiedβmolecular sieves and their alkylation reactivity[J].Petroleum Processing and Petrochemicals,2017,48(4):83-86.)
[12]AHMAD G.Stability improvement of zeolite catalysts under hydrothermal conditions for their potential applications in biomass valorization and crude oil upgrading[J].Microporous and Mesoporous Materials,2017,249(1):42-54.
[13]van BOKHOVEN JA, KONINGSBERGER DC,KUNKELER P,et al.Stepwise dealumination of zeoliteβat specific T-sites observed with 27 Al MAS and 27 Al MQ MAS NMR[J].J Am Chem Soc,2000,122:842-847.
[2]杨小明,罗京娥.磷氧化物改性对HZSM-5沸石物化性质及择形催化性能的影响[J].石油炼制与化工,2001,32(11):48-51.(YANG Xiaoming,LUO Jinge.Effect of phosphorus oxide modification on physical and chemical properties and morphology of HZSM-5zeolite[J].Petroleum Processing and Petrochemicals,2001,32(11):48-51.)
[3]张剑秋.降低汽油烯烃含量的催化裂化新材料探索[D].北京:石油化工科学研究院,2001.
[4]徐佩若,朱志华,戴迎春,等.磷改性HY分子筛催化剂的酸性和催化活性的研究[J].石油学报(石油加工),1993,9(1):41-47.(XU Peiruo,ZHU Zhihua,DAI Yingchun,et al.Study on the acid and catalytic activity of phosphorus modification HY molecular sieve catalyst[J].Acta Petrolei Sinica(Petroleum Processing Section),1993,9(1):41-47.)
[5]PEKKAT,TUULAT P.Modification of ZSM-5zeolite with trimethyl phosphite Part 1 Structure and acidity[J].Microporous and Mesoporous Materials,1998,20:363-369.
[6]VEDRINE J C,AUROUX A,DEJAIFVE P,et al.Catalytic and physical properties of phosphorus-modified ZSM-5zeolite[J].J Catal,1982,73:147-160.
[7]RAHMAN A, LMAY G, ADNOT A, et al.Spectroscopic and catalytic study of P-modified ZSM-5[J].J Catal,1988,112:453-463.
[8]曾海生,崔惠玲,关乃佳.Al,Bi及P改性β分子筛的表面酸性及对烷基转移反应的影响[J].离子交换与吸附,1999,15(4):359-363.(ZEN Haisheng,CUI Huiling,GUAN Naijia.The influence of surface acid and alkyl transference by Al, Bi and phosphorus modificationβmolecular sieve[J].Ion Exchange and Adsorption,1999,15(4):359-363.)
[9]宋祥梅,李英霞,陈标华,等.磷改性β分子筛的酸性及其苯与丙烯烷基化催化性能[J].石油化工高等学校学报,2004,17(4):34-37.(SONG Xiangmei,LI Yingxia,CHEN Biaohua,et al.Acidity of phosphorus modifiedβzeolite and its catalytic performance for alkylation of benzene with propylene[J].Journal of Petrochemical Universities,2004,17(4):34-37.)
[10]王成强,欧阳颖,罗一斌.磷改性β分子筛对单环环烷烃开环反应性能的影响[J].石油炼制与化工,2016,47(8):7-12.(WANG Chengqiang,OUYANG Ying,LUO Yibin. Performances of phosphorus modified zeolite beta in cycloparaffinic ring-opening[J].Petroleum Processing and Petrochemicals,2016,47(8):7-12.)
[11]晁会霞,罗祥生,张凤美.高低温磷改性β分子筛及其烷基化反应性能研究[J].石油炼制与化工,2017,48(4):83-86.(CHAO Huixia, LUO Xiangsheng,ZHANG Fengmei.Study on high and low temperature phosphorus modifiedβmolecular sieves and their alkylation reactivity[J].Petroleum Processing and Petrochemicals,2017,48(4):83-86.)
[12]AHMAD G.Stability improvement of zeolite catalysts under hydrothermal conditions for their potential applications in biomass valorization and crude oil upgrading[J].Microporous and Mesoporous Materials,2017,249(1):42-54.
[13]van BOKHOVEN JA, KONINGSBERGER DC,KUNKELER P,et al.Stepwise dealumination of zeoliteβat specific T-sites observed with 27 Al MAS and 27 Al MQ MAS NMR[J].J Am Chem Soc,2000,122:842-847.