沸石分子筛表面酸性表征与研究进展
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摘要
作为固体酸,沸石分子筛是重要的石油炼制与化工催化剂,表面酸性的数量、类型以及强度等决定其催化性能。表征与研究沸石分子筛表面酸性对于设计和开发高性能沸石分子筛催化剂意义重大。沸石分子筛表面酸性表征方法主要有吸附指示剂滴定法、程序升温脱附法、核磁共振法和红外光谱法等。以沸石分子筛表面酸性表征方法为主线,综述近年来对沸石分子筛表面酸性的表征与研究进展,重点介绍红外光谱法在沸石分子筛表面酸性表征与研究中的应用。指出通过对沸石分子筛表面酸性进行表征,将获得的表面酸性与其相应的催化性能关联,从反应机理理解并建立分子筛表面酸性与催化性能之间的关系将是今后的研究重点。
As the solid acids,zeolites have been considered to be the most important catalysts for petrochemical processes. The amounts,types and strength of their surface acidity sites have crucial effects on their catalytic performance. Consequently,the characterization of and research on surface acidity of the zeolites are of great significance for the design and development of new zeolite catalysts with high performance. The characterization methods for surface acidity of the zeolites mainly have adsorption indicator titration,TPD,NMR and FT-IR. In this paper,the recent advance in characterization of and research on surface acidity of the zeolites was reviewed,and the method of FT-IR was mainly introduced. It was pointed out that the correlation between the surface acidity and corresponding catalytic performance was obtained. Based on reaction mechanism,the researches on the relationship between the surface acidity and catalytic performance of zeolites in future are focused on.
As the solid acids,zeolites have been considered to be the most important catalysts for petrochemical processes. The amounts,types and strength of their surface acidity sites have crucial effects on their catalytic performance. Consequently,the characterization of and research on surface acidity of the zeolites are of great significance for the design and development of new zeolite catalysts with high performance. The characterization methods for surface acidity of the zeolites mainly have adsorption indicator titration,TPD,NMR and FT-IR. In this paper,the recent advance in characterization of and research on surface acidity of the zeolites was reviewed,and the method of FT-IR was mainly introduced. It was pointed out that the correlation between the surface acidity and corresponding catalytic performance was obtained. Based on reaction mechanism,the researches on the relationship between the surface acidity and catalytic performance of zeolites in future are focused on.
引文
[1]徐如人,庞文琴.分子筛与多孔材料化学[M].北京:科学出版社,2004:1-10.
[2]陈南,沈健,魏田升,等.HY分子筛催化剂合成甲基丙烯酸甲酯的工艺条件优化[J].石化技术与应用,2010,28(1):15-17.Chen Nan,Shen Jian,Wei Tiansheng,et al.Process condition optimization of methyl methacrylate with HY molecular sieves catalyst[J].Petrochemical Technology&Application,2010,28(1):15-17.
[3]刘丽芝,郭洪臣.硅烷化改性ZSM-5分子筛用于催化脱蜡催化剂[J].石化技术与应用,2009,27(3):242-245.Liu Lizhi,Guo Hongchen.Silanizing-modified zeolite catalyst ZSM-5 for catalytic dewaxing[J].Petrochemical Technology&Application,2009,27(3):242-245.
[4]孙书红,王宁生,闫伟建.ZSM-5沸石合成与改性技术进展[J].工业催化,2007,15(6):6-10.Sun Shuhong,Wang Ningsheng,Yan Weijian.Advances in synthesis and modification of ZSM-5 zeolite[J].Industrial Catalysis,2007,15(6):6-10.
[5]刘春英,柳云骐,李清华,等.超微NaY分子筛的合成和催化芳烃转化性能[J].工业催化,2004,12(11):41-44.Liu Chunying,Liu Yunqi,Li Qinghua,et al.Synthesis of ultrafine NaY zeolite and its catalytic properties for aromatics conversion[J].Industrial Catalysis,2004,12(11):41-44.
[6]沈晓洁.沸石分子筛的发展及在石油化工中的应用[J].辽宁化工,1997,26(3):139-143.Shen Xiaojie.Development of zeolites and its application in petrochemical induatry[J].Liaoning Chemical Industry,1997,26(3):139-143.
[7]Benesi H A,Winquist B H C.Surface acidity of solid catalysts[J].Advanced Synthesis&Catalysis,1978,(27):97-182.
[8]Kijenski J,Baiker A.Acidic sites on catalyst surfaces and their determination[J].Catalysis Today,1989,5(1):1-12.
[9]刘文欢,郭鹏,苏际,等.钛硅分子筛TS-1的酸性表征及酸催化性能[J].催化学报,2009,30(6):482-484.Liu Wenhuan,Guo Peng,Su Ji,et al.Acidity characterization and acid catalysis performance of titanium silicalite[J].Chinese Journal of Catalysis,2009,30(6):482-484.
[10]林伟,田辉平,王磊,等.不同分子筛负载镍催化剂的正辛烷异构化和芳构化性能[J].石油炼制与化工,2012,48(7):12-15.Lin Wei,Tian Huiping,Wang Lei,et al.Isomerization and aromatization of n-octane over various molecular sieves supported nickel catalyats[J].Petroleum Processing and Petrochemicals,2012,48(7):12-15.
[11]赵晓东,方向晨,贾立明,等.改性HZSM-5分子筛催化剂芳构化性能研究[J].工业催化,2012,20(3):48-52.Zhao Xiaodong,Fang Xiangchen,Jia Liming,et al.Study on aromatization performance of modified HZSM-5 zeolite catalyst[J].Industrial Catalysis,2012,20(3):48-52.
[12]金胜明,邱冠周,杨华明,等.海泡石制备HMS和AlSBA分子筛的研究[J].物理化学学报,2005,21(7):796-799.Jin Shengming,Qiu Guanzhou,Yang huaming,et al.Preparation of HMS and AlSBA mesoporous materials from sepiolite[J].Acta Physico-Chimica Sinica,2005,21(7):796-799.
[13]魏迎旭,王公慰,刘中民,等.SAPO分子筛的酸性及孔道分布对丁烷异构脱氢反应的影响[J].催化学报,2001,22(6):537-540.Wei Yingxu,Wang Gongwei,Liu Zhongmin,et al.Eeffects of acidity and pore structure of SAPO molecular sieves on dehydroisomerization of n-butane to isobutene over Pd/SAPO catalysts[J].Chinese Journal of Catalysis,2001,22(6):537-540.
[14]Sachtler W M H,Zhang Z C.Zeolite-supported transition metal catalysts[J].Advanced Synthesis&Catalysis,1993(39):129-220.
[15]Zhang W P,Ma D,Liu X C,et al.Perfluorotributylamine as a probe molecule for distinguishing internal and external acidic sites in zeolites by high-resolution1HMAS NMR spectroscopy[J].Chemical Communications,1999,(12):1091-1092.
[16]孙敏,贺振富.催化裂化催化剂常用择形分子筛的酸性研究[J].石油炼制与化工,2011,42(11):28-31.Sun Min,He Zhenfu.Study on the acidity of shape selective zeolite in FCC catalysts[J].Petroleum Processing and Petrochemicals,2011,42(11):28-31.
[17]刘勇,张维萍,谢素娟,等.用固体核磁共振研究HZSM-35分子筛的酸性[J].催化学报,2009,30(2):119-123.Liu Yong,Zhang Weiping,Xie Sujuan,et al.Acidity characterization of HZSM-35 zeolite by solid-state NMR[J].Chinese Journal of Catalysis,2009,30(2):119-123.
[18]Zhang W P,Han X W,Bao X H,et al.Characterization of the acid sites in dealuminated nanosized HZSM-5 zeolite with the probe molecule trimethylphosphine[J].Journal of Molecular Catalysis A,2003,194(1/2):107-113.
[19]Parry E P.An infrared study of pyridine adsorbed on acidic solids.Characterization of surface acidity[J].Journal of Catalysis,1963,2(5):371-379.
[20]唐保卫,郭泉辉,李娟.用密度泛函理论研究NO在HZSM-5分子筛不同酸性位的吸附[J].化学研究,2012,23(2):22-25.Tang Baowei,Guo Quanhui,Li Juan.Study of adsorption of nitrogen monoxide on different acid sites of molecular sieve H-ZSM-5 zeolite[J].Chemical Research,2012,23(2):22-25.
[21]Barone G,Casella G,Giuffrida S,et al.H-ZSM-5 modified zeolite:Quantum chemical models of acidic sites[J].The Journal of Chemical Physics,2007,111(35):13033-13043.
[22]Kotra J,Kubelkova L.Studies in Surface Science and Catalysis[M].Schweizer:Elsevier Science,1995:509-515.
[23]Knozinger H,Huber S.IR spectroscopy of small and weakly interacting molecular probes for acidic and basic zeolites[J].Journal of Chemical Society,1998,94(15):2047-2059.
[24]孙雪芹,王林,张爱萍,等.Na含量对USY分子筛酸性和焦炭选择性的影响研究[J].应用化工,2012,41(10):1841-1843.Sun Xueqin,Wang Lin,Zhang Aiping,et al.Study on the effect of Na content on acidity and coke selective of USY[J].Applied Chemical Industry,2012,41(10):1841-1843.
[25]段宏昌,李雪礼,张海涛,等.不同类型稀土Y型分子筛催化性能研究[J].化学工程与装备,2012,(10):5-7.Duan Hongchang,Li Xueli,Zhang Haitao,et al.Bu tong lei xing xi tu Y xing fen zi shai cui hua xing neng yan jiu[J].Chemical Engineering&Equipment,2012,(10):5-7.
[26]张玉红,薛炼,马爱增.Pt/KL芳构化催化剂中载体酸碱性的作用[J].石油炼制与化工,2009,40(3):1-5.Zhang Yuhong,Xue Lian,Ma Aizeng.Role of acidity and basicity of zeolite support in Pt/KL catalysts for aromatization of alkane[J].Petroleum Processing and Petrochemicals,2009,40(3):1-5.
[27]张振莉,周亚松,李长喜,等.HZSM-5/Hβ复合分子筛的正辛烷临氢异构化和芳构化性能[J].燃料化学学报,2008,36(2):160-165.Zhang Zhenli,Zhou Yasong,Li Changxi,et al.Hydroisomerization and aromatization of n-octane over HZSM-5/Hβcomposite zeolite[J].Journal of Fuel Chemistry and Technology,2008,36(2):160-165.
[28]曾拥军,于海江,施力.Y型分子筛负载磷钨酸催化剂的结构和性能[J].化学反应工程与工艺,2007,23(6):542-546.Zeng Yongjun,Yu Haijiang,Shi Li.Structure and catalytic activity of phosphotungstic acid supported on Y-zeolite[J].Chemical Reaction Engineering and Technology,2007,23(6):542-546.
[29]李斌,李士杰,李能,等.FCC催化剂中REHY分子筛的结构与酸性[J].催化学报,2005,26(4):301-306.Li Bin,Li Shijie,Li Neng,et al.Structure and acidity of REHY zeolite in FCC catalyst[J].Chinese Journal of Catalysis,2005,26(4):301-306.
[30]陈洪林,申宝剑,潘惠芳.ZSM-5/Y复合分子筛的酸性及其重油催化裂化性能[J].催化学报,2004,25(9):715-720.Chen Honglin,Shen Baojian,Pan Huifang.Acidity and catalytic performance of ZSM-5/Y composite zeolite for heavy oil cracking[J].Chinese Journal of Catalysis,2004,25(9):715-720.
[31]余少兵,李永红,陈洪钫.改性对β分子筛酸性的影响[J].化工学报,2004,55(6):913-918.Yu Shaobing,Li Yonghong,Chen Hongfang.Effect of modification on acidity ofβzeolite[J].Journal of Chemical Industry and Engineering(China),2004,55(6):913-918.
[32]王奎,康小洪,钱婉华,等.沉积硝酸铝结合水热处理改性分子筛HY(Al)的酸性与催化反应性能[J].石油学报(石油加工),2002,18(5):92-95.Wang Kui,Kang Xiaohong,Qian Wanhua,et al.Acidity and catalytic performance of HY(Al)prepared by aluminum nitrate deposition togerther with hydrothermal treatment of HY[J].Acta Petrolei Sinica(Petroleum Processing Section),2002,18(5):92-95.
[33]刘国珍.CoAPSO-5分子筛的合成与性能[J].燃料化学学报,1998,26(6):559-562.Liu Guozhen.Synthesis and properties of CoAPSO-5 zeolite[J].Journal of Fuel Chemistry and Technology,1998,26(6):559-562.
[34]刘国珍.杂原子AlPO4-5分子筛的酸性及异构化性能[J].太原理工大学学报,1998,29(5):533-536.Liu Guozhen.Acidity and isomerization property of hetero atom AlPO4-5 molecular sieves[J].Journal of Taiyuan University of Technology,1998,29(5):533-536.
[35]Corma A.From microporous to mesoporous molecular sieve materials and their use in catalysis[J].Chemical Reviews,1997,97(6):2373-2420.
[36]Thibault-Starzyk F,Stan I,Pérez-Ramírez J,et al.Quantification of enhanced acid site accessibility in hierarchical zeolites——The accessibility index[J].Journal of Catalysis,2009,264(1):11-14.
[37]Xue Z,Ma J,Li R,et al.Accessibility and catalysis of acidic sites in hierarchical ZSM-5 prepared by silanization[J].Micropor Mesopor Mater,2012,151(15):271-276.
[2]陈南,沈健,魏田升,等.HY分子筛催化剂合成甲基丙烯酸甲酯的工艺条件优化[J].石化技术与应用,2010,28(1):15-17.Chen Nan,Shen Jian,Wei Tiansheng,et al.Process condition optimization of methyl methacrylate with HY molecular sieves catalyst[J].Petrochemical Technology&Application,2010,28(1):15-17.
[3]刘丽芝,郭洪臣.硅烷化改性ZSM-5分子筛用于催化脱蜡催化剂[J].石化技术与应用,2009,27(3):242-245.Liu Lizhi,Guo Hongchen.Silanizing-modified zeolite catalyst ZSM-5 for catalytic dewaxing[J].Petrochemical Technology&Application,2009,27(3):242-245.
[4]孙书红,王宁生,闫伟建.ZSM-5沸石合成与改性技术进展[J].工业催化,2007,15(6):6-10.Sun Shuhong,Wang Ningsheng,Yan Weijian.Advances in synthesis and modification of ZSM-5 zeolite[J].Industrial Catalysis,2007,15(6):6-10.
[5]刘春英,柳云骐,李清华,等.超微NaY分子筛的合成和催化芳烃转化性能[J].工业催化,2004,12(11):41-44.Liu Chunying,Liu Yunqi,Li Qinghua,et al.Synthesis of ultrafine NaY zeolite and its catalytic properties for aromatics conversion[J].Industrial Catalysis,2004,12(11):41-44.
[6]沈晓洁.沸石分子筛的发展及在石油化工中的应用[J].辽宁化工,1997,26(3):139-143.Shen Xiaojie.Development of zeolites and its application in petrochemical induatry[J].Liaoning Chemical Industry,1997,26(3):139-143.
[7]Benesi H A,Winquist B H C.Surface acidity of solid catalysts[J].Advanced Synthesis&Catalysis,1978,(27):97-182.
[8]Kijenski J,Baiker A.Acidic sites on catalyst surfaces and their determination[J].Catalysis Today,1989,5(1):1-12.
[9]刘文欢,郭鹏,苏际,等.钛硅分子筛TS-1的酸性表征及酸催化性能[J].催化学报,2009,30(6):482-484.Liu Wenhuan,Guo Peng,Su Ji,et al.Acidity characterization and acid catalysis performance of titanium silicalite[J].Chinese Journal of Catalysis,2009,30(6):482-484.
[10]林伟,田辉平,王磊,等.不同分子筛负载镍催化剂的正辛烷异构化和芳构化性能[J].石油炼制与化工,2012,48(7):12-15.Lin Wei,Tian Huiping,Wang Lei,et al.Isomerization and aromatization of n-octane over various molecular sieves supported nickel catalyats[J].Petroleum Processing and Petrochemicals,2012,48(7):12-15.
[11]赵晓东,方向晨,贾立明,等.改性HZSM-5分子筛催化剂芳构化性能研究[J].工业催化,2012,20(3):48-52.Zhao Xiaodong,Fang Xiangchen,Jia Liming,et al.Study on aromatization performance of modified HZSM-5 zeolite catalyst[J].Industrial Catalysis,2012,20(3):48-52.
[12]金胜明,邱冠周,杨华明,等.海泡石制备HMS和AlSBA分子筛的研究[J].物理化学学报,2005,21(7):796-799.Jin Shengming,Qiu Guanzhou,Yang huaming,et al.Preparation of HMS and AlSBA mesoporous materials from sepiolite[J].Acta Physico-Chimica Sinica,2005,21(7):796-799.
[13]魏迎旭,王公慰,刘中民,等.SAPO分子筛的酸性及孔道分布对丁烷异构脱氢反应的影响[J].催化学报,2001,22(6):537-540.Wei Yingxu,Wang Gongwei,Liu Zhongmin,et al.Eeffects of acidity and pore structure of SAPO molecular sieves on dehydroisomerization of n-butane to isobutene over Pd/SAPO catalysts[J].Chinese Journal of Catalysis,2001,22(6):537-540.
[14]Sachtler W M H,Zhang Z C.Zeolite-supported transition metal catalysts[J].Advanced Synthesis&Catalysis,1993(39):129-220.
[15]Zhang W P,Ma D,Liu X C,et al.Perfluorotributylamine as a probe molecule for distinguishing internal and external acidic sites in zeolites by high-resolution1HMAS NMR spectroscopy[J].Chemical Communications,1999,(12):1091-1092.
[16]孙敏,贺振富.催化裂化催化剂常用择形分子筛的酸性研究[J].石油炼制与化工,2011,42(11):28-31.Sun Min,He Zhenfu.Study on the acidity of shape selective zeolite in FCC catalysts[J].Petroleum Processing and Petrochemicals,2011,42(11):28-31.
[17]刘勇,张维萍,谢素娟,等.用固体核磁共振研究HZSM-35分子筛的酸性[J].催化学报,2009,30(2):119-123.Liu Yong,Zhang Weiping,Xie Sujuan,et al.Acidity characterization of HZSM-35 zeolite by solid-state NMR[J].Chinese Journal of Catalysis,2009,30(2):119-123.
[18]Zhang W P,Han X W,Bao X H,et al.Characterization of the acid sites in dealuminated nanosized HZSM-5 zeolite with the probe molecule trimethylphosphine[J].Journal of Molecular Catalysis A,2003,194(1/2):107-113.
[19]Parry E P.An infrared study of pyridine adsorbed on acidic solids.Characterization of surface acidity[J].Journal of Catalysis,1963,2(5):371-379.
[20]唐保卫,郭泉辉,李娟.用密度泛函理论研究NO在HZSM-5分子筛不同酸性位的吸附[J].化学研究,2012,23(2):22-25.Tang Baowei,Guo Quanhui,Li Juan.Study of adsorption of nitrogen monoxide on different acid sites of molecular sieve H-ZSM-5 zeolite[J].Chemical Research,2012,23(2):22-25.
[21]Barone G,Casella G,Giuffrida S,et al.H-ZSM-5 modified zeolite:Quantum chemical models of acidic sites[J].The Journal of Chemical Physics,2007,111(35):13033-13043.
[22]Kotra J,Kubelkova L.Studies in Surface Science and Catalysis[M].Schweizer:Elsevier Science,1995:509-515.
[23]Knozinger H,Huber S.IR spectroscopy of small and weakly interacting molecular probes for acidic and basic zeolites[J].Journal of Chemical Society,1998,94(15):2047-2059.
[24]孙雪芹,王林,张爱萍,等.Na含量对USY分子筛酸性和焦炭选择性的影响研究[J].应用化工,2012,41(10):1841-1843.Sun Xueqin,Wang Lin,Zhang Aiping,et al.Study on the effect of Na content on acidity and coke selective of USY[J].Applied Chemical Industry,2012,41(10):1841-1843.
[25]段宏昌,李雪礼,张海涛,等.不同类型稀土Y型分子筛催化性能研究[J].化学工程与装备,2012,(10):5-7.Duan Hongchang,Li Xueli,Zhang Haitao,et al.Bu tong lei xing xi tu Y xing fen zi shai cui hua xing neng yan jiu[J].Chemical Engineering&Equipment,2012,(10):5-7.
[26]张玉红,薛炼,马爱增.Pt/KL芳构化催化剂中载体酸碱性的作用[J].石油炼制与化工,2009,40(3):1-5.Zhang Yuhong,Xue Lian,Ma Aizeng.Role of acidity and basicity of zeolite support in Pt/KL catalysts for aromatization of alkane[J].Petroleum Processing and Petrochemicals,2009,40(3):1-5.
[27]张振莉,周亚松,李长喜,等.HZSM-5/Hβ复合分子筛的正辛烷临氢异构化和芳构化性能[J].燃料化学学报,2008,36(2):160-165.Zhang Zhenli,Zhou Yasong,Li Changxi,et al.Hydroisomerization and aromatization of n-octane over HZSM-5/Hβcomposite zeolite[J].Journal of Fuel Chemistry and Technology,2008,36(2):160-165.
[28]曾拥军,于海江,施力.Y型分子筛负载磷钨酸催化剂的结构和性能[J].化学反应工程与工艺,2007,23(6):542-546.Zeng Yongjun,Yu Haijiang,Shi Li.Structure and catalytic activity of phosphotungstic acid supported on Y-zeolite[J].Chemical Reaction Engineering and Technology,2007,23(6):542-546.
[29]李斌,李士杰,李能,等.FCC催化剂中REHY分子筛的结构与酸性[J].催化学报,2005,26(4):301-306.Li Bin,Li Shijie,Li Neng,et al.Structure and acidity of REHY zeolite in FCC catalyst[J].Chinese Journal of Catalysis,2005,26(4):301-306.
[30]陈洪林,申宝剑,潘惠芳.ZSM-5/Y复合分子筛的酸性及其重油催化裂化性能[J].催化学报,2004,25(9):715-720.Chen Honglin,Shen Baojian,Pan Huifang.Acidity and catalytic performance of ZSM-5/Y composite zeolite for heavy oil cracking[J].Chinese Journal of Catalysis,2004,25(9):715-720.
[31]余少兵,李永红,陈洪钫.改性对β分子筛酸性的影响[J].化工学报,2004,55(6):913-918.Yu Shaobing,Li Yonghong,Chen Hongfang.Effect of modification on acidity ofβzeolite[J].Journal of Chemical Industry and Engineering(China),2004,55(6):913-918.
[32]王奎,康小洪,钱婉华,等.沉积硝酸铝结合水热处理改性分子筛HY(Al)的酸性与催化反应性能[J].石油学报(石油加工),2002,18(5):92-95.Wang Kui,Kang Xiaohong,Qian Wanhua,et al.Acidity and catalytic performance of HY(Al)prepared by aluminum nitrate deposition togerther with hydrothermal treatment of HY[J].Acta Petrolei Sinica(Petroleum Processing Section),2002,18(5):92-95.
[33]刘国珍.CoAPSO-5分子筛的合成与性能[J].燃料化学学报,1998,26(6):559-562.Liu Guozhen.Synthesis and properties of CoAPSO-5 zeolite[J].Journal of Fuel Chemistry and Technology,1998,26(6):559-562.
[34]刘国珍.杂原子AlPO4-5分子筛的酸性及异构化性能[J].太原理工大学学报,1998,29(5):533-536.Liu Guozhen.Acidity and isomerization property of hetero atom AlPO4-5 molecular sieves[J].Journal of Taiyuan University of Technology,1998,29(5):533-536.
[35]Corma A.From microporous to mesoporous molecular sieve materials and their use in catalysis[J].Chemical Reviews,1997,97(6):2373-2420.
[36]Thibault-Starzyk F,Stan I,Pérez-Ramírez J,et al.Quantification of enhanced acid site accessibility in hierarchical zeolites——The accessibility index[J].Journal of Catalysis,2009,264(1):11-14.
[37]Xue Z,Ma J,Li R,et al.Accessibility and catalysis of acidic sites in hierarchical ZSM-5 prepared by silanization[J].Micropor Mesopor Mater,2012,151(15):271-276.