石油学报(石油加工)ACTA PETROLEI SINICA(PETROLEUM PROCESSING SECTION)2004 OF STEAM TREATMENT AND PHOSPHOROUS ACID MODIFICATION OF HZSM-5 ON ITS PHYSICOCHEMICAL AND CATALYTIC PROPERTIESAbstract:Physicochemical and catalytic properties of phosphorous acid modified HZSM�5 ze olites treated with 100% steam at 673,873,and 1073*!K have been he structure of the samples was characterized by acidity and distributio n of the acidic sites were studied by IR using pyridine as probe molecule and te mperature programmed desorption (TPD) of state of phosph orus were studied by XPS,showing that P (Ⅲ) was oxidized to P (Ⅴ),a model for the surface structure of the modification is e textural properties of catalysts determined by nitrogen isothermal adsorption �desorption measurements suggest the isothermal type of all samples is a combin ation of type Ⅰ and type Ⅳ,all hysteresis loops resemble the H4�type in the IUPAC state of aluminum was characterized by 27 Al MAS N MR (Austin model) semi�empirical method and cluster model method have been employed to study the stability of two possible phosphor us modified zeolite geometries,the difference was the bridging oxygen of phosph orus coordination with aluminum or the terminal oxygen of phosphorus coordinatio n with result showed that the terminal oxygen coordination was more possible according to the heat of formation (HF).The �n��heptane cracking reaction was selected as probe reaction to investigate the activity of studied samples.�Keywords:HZSM�5 zeolites;steam treatment;phosphorous acid modificati on;texture;cracking activity 亚磷酸和水蒸气联合改性的HZSM-5的物化性质和催化性能研究吕仁庆 唐博 王震宇 王秋英 项寿鹤 摘 要:考察了由亚磷酸改性的HZSM-5在673、873和1073K温度下100%水蒸气处理样品的物化和催化性质.采用XRD表征了样品的结构.通过吸附吡啶红外光谱和NH3-TPD进行了酸性和酸分布研究.XPS的研究结果表明,P由+3价氧化成了+5价,并提出了可能的改性的表面结构模型.通过N2吸附-脱附等温线研究了样品的孔结构,样品的吸附-脱附等温线为Ⅰ型和Ⅳ型的复合型,滞后环为IUPAC分类的H4型.Al的状态由27Al MAS NMS表征.采用AM1(Austin Model Ⅰ)半经验量子化学方法和模型簇法筛选了磷改性可能的两种结构模型,其区别在于磷上的桥氧与铝配位还是端氧与铝配位,结果表明端氧与铝配位的可能性更大.以正庚烷裂化反应为探针反应考察了样品的活性.关键词:HZSM-5沸石;水热处理;亚磷酸改性;结构;裂化活性CLC Number: Document ID:AArticle ID:1001-8719(2004)01-0012-10 Foundation Item:国家自然科学基金(20233030)和石油大学中国石油天然气集团公司催化重点实验室资助项目Author Resume:吕仁庆(1969-),男,讲师,博士研究生,从事沸石催化研究;唐博(1964-),男,高级工程师,博士研究生,从事工业催化研究;王震宇(1974-),男,工程师,硕士,从事催化剂生产工作;王秋英(1964-),女,高级工程师,硕士,从事沸石催化研究:项寿鹤(1939-),男,教授,从事沸石合成与催化研究. 通讯联系人:吕仁庆 Author Unit:吕仁庆(南开大学,化学系,天津,300071) 唐博(南开大学,化学系,天津,300071) 王震宇(南开大学,催化剂厂,天津,300071) 王秋英(南开大学,催化剂厂,天津,300071) 项寿鹤(南开大学,化学系,天津,300071) References:〔1〕Scherzer FCC catalysts,scientific and technical aspects[J].Catal Rev-Sci Eng,1989,31(3):215-354.〔2〕Lischke G,Eckelt R,Jerschkewitz H-G,et and physicochemical characterization of P-modified H-ZSM-5[J].J Catal,1991,132(1):229-243.〔3〕Kaeding W W,Chu C,Young L B,et selective reactions with zeolite catalysts[J].J Catal,1981,69:392-398.〔4〕Jentys A,Rumplmayr G,Lerche r J groups in phosphorus-modified HZSM-5[J].Appl Catal,1989,53:299-312.〔5〕Chen N Y,Kaeding W W,Dwyer F aromatic reactions over shape-selective molecular sieve zeolite catalysts[J].J Am Chem 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