Effect of different alkali metal salts on the crystal size and the crystallization rate of ZSM 5 zeolite was detailedly investigated in this paper. The samples prepared by adding the different alkali metal salts were ...Effect of different alkali metal salts on the crystal size and the crystallization rate of ZSM 5 zeolite was detailedly investigated in this paper. The samples prepared by adding the different alkali metal salts were characterized by using XRD, TEM, TG DSC, BET and IR techniques. The XRD results showed that, for the nanosized ZSM 5 zeolite, the characteristic peaks broadened on the XRD patterns in comparison with the microsized ZSM 5 zeolite. The SEM results verified that the crystal size of zeolites prepared by adding different alkali metal salts had different results, and adding NaCl, NaC2H3O2 and KCl showed the better effect of reducing crystal size, which are about of 40～ 60nm size. The crystallization curve of adding the different alkali metal salts suggested that the crystallization rate was significantly affected by the anions in the alkali metal salt besides the cations. Moreover, the crystal size likewise depended on the anion in the alkali metal salt. In addition, the BET results suggested that the nanosized ZSM 5 zeolite possessed a larger outer surface area in comparison with the microsized ZSM 5 zeolite. The thermostability of the samples was determined by TG DSC technique, indicating that the nanosized ZSM 5 zeolite had a poor thermostability as compared with the microsized ZSM 5 zeolite. The possible difference of the samples with different crystal sizes on IR spectra was also given.展开更多
The porosity of H‐ZSM‐5zeolite is known to facilitate the diffusion of molecules in the methanol‐to‐aromatics(MTA)reaction.The activity and selectivity of the H‐ZSM‐5catalyst in the MTAreaction has been studied ...The porosity of H‐ZSM‐5zeolite is known to facilitate the diffusion of molecules in the methanol‐to‐aromatics(MTA)reaction.The activity and selectivity of the H‐ZSM‐5catalyst in the MTAreaction has been studied as a function of crystal size.ZSM‐5zeolites with different crystal sizeswere successfully synthesized by conventional hydrothermal methods.Tailoring ZSM‐5particle sizewas easily controlled by changes to the sol‐gel composition,and in particular,the deionized waterto tetrapropylammonium hydroxide ratio,and crystallization time.The structure of the H‐ZSM‐5zeolites were characterized by X‐ray diffraction and the morphology of the zeolite particles wasdetermined by scanning electron microscopy.N2adsorption‐desorption measurements establishedchanges to the textural properties,and compositional properties were characterized by X‐ray fluorescencespectroscopy.Acidity measurements of the catalysts were measured by pyridine‐adsorbedFourier transform infrared spectroscopy and the temperature‐programmed desorption of ammonia.After subjecting the catalysts to the MTA reaction,the total amount of coke formed on the spentdeactivated catalysts was determined by thermal gravimetric analysis.The results show that theSiO2/Al2O3molar ratios and acidic properties of the H‐ZSM‐5samples are similar,however,thenano‐sized hierarchical ZSM‐5zeolite with an additional level of auxiliary pores possesses a higher展开更多
The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite wa...The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity（WHSV） of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.展开更多
ZSM‐22 zeolite with different crystal lengths was prepared using a modified hydrothermal method. Rotation speed, Si/Al molar ratio and co‐solvent have important effects on the crystal size of ZSM‐22. The nanosized ...ZSM‐22 zeolite with different crystal lengths was prepared using a modified hydrothermal method. Rotation speed, Si/Al molar ratio and co‐solvent have important effects on the crystal size of ZSM‐22. The nanosized zeolite samples were characterized by X‐ray diffraction, X‐ray fluorescence, nitrogen adsorption, scanning electron microscopy, temperature‐programmed desorption of am‐monia and solid state nuclear magnetic resonance. The catalytic performance of nanosized ZSM‐22 was tested using the conversion of methanol. Compared to conventional ZSM‐22, the nanosized ZSM‐22 zeolite exhibited superior selectivity to ethylene and aromatics and lower selectivity to propylene. Stability against deactivation was clearly shown by the nanosized ZSM‐22 zeolite. A higher external surface area and smaller particle size make this nanosized ZSM‐22 zeolite attractive for catalytic applications.展开更多
用不同浓度的盐酸溶液对纳米ZSM-5分子筛进行脱铝改性,采用X-射线衍射(XRD)、X-射线荧光光谱(XRF)、扫描电子显微镜(SEM)、氮气物理吸附、傅里叶变换红外光谱(FTIR)、^(27)Al MAS NMR和NH_3程序升温脱附(NH_3-TPD)等方法对酸处理前后的...用不同浓度的盐酸溶液对纳米ZSM-5分子筛进行脱铝改性,采用X-射线衍射(XRD)、X-射线荧光光谱(XRF)、扫描电子显微镜(SEM)、氮气物理吸附、傅里叶变换红外光谱(FTIR)、^(27)Al MAS NMR和NH_3程序升温脱附(NH_3-TPD)等方法对酸处理前后的样品进行了表征,并考察了盐酸浓度对改性前后纳米ZSM-5分子筛的结构、酸性及其催化对二氯苯(p-DCB)异构化反应性能的影响。结果表明,通过改变盐溶液的浓度可以选择性地脱除ZSM-5分子筛的非骨架铝及骨架铝,形成二次介孔,并对分子筛的酸性进行调变。改性后的纳米ZSM-5分子筛在对二氯苯异构化反应中的催化活性略有降低,但是间二氯苯的选择性得到显著提高。展开更多
通过向合成ZSM-5分子筛的初始凝胶中加入Fenton试剂作为羟基自由基(·OH)引发剂,在90℃下合成了系列不同晶化时间的超细纳米ZSM-5分子筛(NZ5-Fx)。作为对比,采用传统模板法在170℃下晶化合成了纳米ZSM-5分子筛(NZ5-T)。采用XRD、SEM...通过向合成ZSM-5分子筛的初始凝胶中加入Fenton试剂作为羟基自由基(·OH)引发剂,在90℃下合成了系列不同晶化时间的超细纳米ZSM-5分子筛(NZ5-Fx)。作为对比,采用传统模板法在170℃下晶化合成了纳米ZSM-5分子筛(NZ5-T)。采用XRD、SEM、TEM、N_(2)物理吸附、^(29)Si MAS NMR、^(27)Al MAS NMR、EPR、NH_(3)-TPD和Py-IR等方法对分子筛进行了表征,并研究了·OH的引入对所合成的NZ5-Fx系列ZSM-5分子筛的物化性质及甲醇制汽油(MTG)催化反应性能的影响。结果表明,与样品NZ5-T相比,·OH促进下低温合成的NZ5-Fx系列ZSM-5分子筛具有更小的晶粒尺寸、更大的介孔孔容,位于孔道交叉处的骨架Al原子所占的比例更高,而且具有更加温和的酸性,在催化MTG反应中表现出更异优的催化性能。以纳米ZSM-5分子筛样品NZ5-F12d为MTG反应的催化剂,甲醇转化率为96.2%时,汽油的选择性高达66.5%。展开更多
文摘Effect of different alkali metal salts on the crystal size and the crystallization rate of ZSM 5 zeolite was detailedly investigated in this paper. The samples prepared by adding the different alkali metal salts were characterized by using XRD, TEM, TG DSC, BET and IR techniques. The XRD results showed that, for the nanosized ZSM 5 zeolite, the characteristic peaks broadened on the XRD patterns in comparison with the microsized ZSM 5 zeolite. The SEM results verified that the crystal size of zeolites prepared by adding different alkali metal salts had different results, and adding NaCl, NaC2H3O2 and KCl showed the better effect of reducing crystal size, which are about of 40～ 60nm size. The crystallization curve of adding the different alkali metal salts suggested that the crystallization rate was significantly affected by the anions in the alkali metal salt besides the cations. Moreover, the crystal size likewise depended on the anion in the alkali metal salt. In addition, the BET results suggested that the nanosized ZSM 5 zeolite possessed a larger outer surface area in comparison with the microsized ZSM 5 zeolite. The thermostability of the samples was determined by TG DSC technique, indicating that the nanosized ZSM 5 zeolite had a poor thermostability as compared with the microsized ZSM 5 zeolite. The possible difference of the samples with different crystal sizes on IR spectra was also given.
基金supported by the National Natural Science Foundation of China (21676300)~~
文摘The porosity of H‐ZSM‐5zeolite is known to facilitate the diffusion of molecules in the methanol‐to‐aromatics(MTA)reaction.The activity and selectivity of the H‐ZSM‐5catalyst in the MTAreaction has been studied as a function of crystal size.ZSM‐5zeolites with different crystal sizeswere successfully synthesized by conventional hydrothermal methods.Tailoring ZSM‐5particle sizewas easily controlled by changes to the sol‐gel composition,and in particular,the deionized waterto tetrapropylammonium hydroxide ratio,and crystallization time.The structure of the H‐ZSM‐5zeolites were characterized by X‐ray diffraction and the morphology of the zeolite particles wasdetermined by scanning electron microscopy.N2adsorption‐desorption measurements establishedchanges to the textural properties,and compositional properties were characterized by X‐ray fluorescencespectroscopy.Acidity measurements of the catalysts were measured by pyridine‐adsorbedFourier transform infrared spectroscopy and the temperature‐programmed desorption of ammonia.After subjecting the catalysts to the MTA reaction,the total amount of coke formed on the spentdeactivated catalysts was determined by thermal gravimetric analysis.The results show that theSiO2/Al2O3molar ratios and acidic properties of the H‐ZSM‐5samples are similar,however,thenano‐sized hierarchical ZSM‐5zeolite with an additional level of auxiliary pores possesses a higher
基金Project(21276067)supported by the National Natural Science Foundation of China
文摘The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity（WHSV） of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.
基金supported by the National Natural Science Foundation of China (21506202)~~
文摘ZSM‐22 zeolite with different crystal lengths was prepared using a modified hydrothermal method. Rotation speed, Si/Al molar ratio and co‐solvent have important effects on the crystal size of ZSM‐22. The nanosized zeolite samples were characterized by X‐ray diffraction, X‐ray fluorescence, nitrogen adsorption, scanning electron microscopy, temperature‐programmed desorption of am‐monia and solid state nuclear magnetic resonance. The catalytic performance of nanosized ZSM‐22 was tested using the conversion of methanol. Compared to conventional ZSM‐22, the nanosized ZSM‐22 zeolite exhibited superior selectivity to ethylene and aromatics and lower selectivity to propylene. Stability against deactivation was clearly shown by the nanosized ZSM‐22 zeolite. A higher external surface area and smaller particle size make this nanosized ZSM‐22 zeolite attractive for catalytic applications.
文摘纳米ZSM-5分子筛由于其特殊的孔道和表面性质,显示出优异的吸附与催化性能,但粒径小于100 nm的ZSM-5分子筛极易发生团聚。以正硅酸乙酯为硅源、偏铝酸钠为铝源、四丙基氢氧化铵为模板剂,合成硅铝物质的量比分别为25、50、100、200和400的纳米ZSM-5分子筛。通过X射线衍射(XRD)、扫描电镜(SEM)、N_(2)物理吸附-脱附、^(27)Al固体核磁共振(^(27)Al MAS NMR)表征,结果表明,在硅铝物质的量比为25~400范围,均可合成粒径小于100 nm的ZSM-5分子筛。同时随着硅铝物质的量比增加,分子筛结晶度变强,分散性变好,比表面积和孔容增加,非骨架铝减少。
文摘用不同浓度的盐酸溶液对纳米ZSM-5分子筛进行脱铝改性,采用X-射线衍射(XRD)、X-射线荧光光谱(XRF)、扫描电子显微镜(SEM)、氮气物理吸附、傅里叶变换红外光谱(FTIR)、^(27)Al MAS NMR和NH_3程序升温脱附(NH_3-TPD)等方法对酸处理前后的样品进行了表征,并考察了盐酸浓度对改性前后纳米ZSM-5分子筛的结构、酸性及其催化对二氯苯(p-DCB)异构化反应性能的影响。结果表明,通过改变盐溶液的浓度可以选择性地脱除ZSM-5分子筛的非骨架铝及骨架铝,形成二次介孔,并对分子筛的酸性进行调变。改性后的纳米ZSM-5分子筛在对二氯苯异构化反应中的催化活性略有降低,但是间二氯苯的选择性得到显著提高。
文摘通过向合成ZSM-5分子筛的初始凝胶中加入Fenton试剂作为羟基自由基(·OH)引发剂,在90℃下合成了系列不同晶化时间的超细纳米ZSM-5分子筛(NZ5-Fx)。作为对比,采用传统模板法在170℃下晶化合成了纳米ZSM-5分子筛(NZ5-T)。采用XRD、SEM、TEM、N_(2)物理吸附、^(29)Si MAS NMR、^(27)Al MAS NMR、EPR、NH_(3)-TPD和Py-IR等方法对分子筛进行了表征,并研究了·OH的引入对所合成的NZ5-Fx系列ZSM-5分子筛的物化性质及甲醇制汽油(MTG)催化反应性能的影响。结果表明,与样品NZ5-T相比,·OH促进下低温合成的NZ5-Fx系列ZSM-5分子筛具有更小的晶粒尺寸、更大的介孔孔容,位于孔道交叉处的骨架Al原子所占的比例更高,而且具有更加温和的酸性,在催化MTG反应中表现出更异优的催化性能。以纳米ZSM-5分子筛样品NZ5-F12d为MTG反应的催化剂,甲醇转化率为96.2%时,汽油的选择性高达66.5%。
