Creating mesopores in ZSM-48 zeolite by alkali treatment: Enhanced catalyst for hydroisomerization of hexadecane

ZSM-48 zeolites with various Si/Al ratios were hydrothermally synthesized in the H_2N(CH_2)_6NH_2(HDA)-containing media. The obtained samples were highly crystallized with minor mixed phases as evidenced by X-ray powder diffraction(XRD). The alkaline treated ZSM-48 zeolites maintained its structure under different concentrations of Na OH aqueous solution. Micropores remained unchanged while mesopores with wide pore size distribution formed after the alkaline treatment. The surface area increased from 228 to 288 m~2/g. The Br?nsted acid sites had little alteration while an obvious increase of Lewis acid sites was observed. The hydroisomerization of hexadecane was performed as the model reaction to test the effects of the alkali treatment. The conversion of hexadecane had almost no change, which was attributed to the preservation of the Br?nsted acid sites. While high selectivity to iso-hexadecane with an improved iso to normal ratio of alkanes was due to the mesopore formation and improved diffusivity.     

杂原子ZSM－5、ZSM－11和ZSM－48型分子筛的合成

在Na₂O-SiO₂-M_xO_y-H₂O体系中,以HMDA为模板剂用动态法和静态法合成了Ti-ZSM-48型分子筛,首次以85%(wt)HMDA+15%(wt)TPA⁺为模板剂用低温陈化的静态法合成了第四周期过渡金属杂原子M-ZSM-5型分子筛,并与以HMDA、TPA⁺为模板剂合成M-ZSM-5和以TBA⁺为模板剂合成M-ZSM-11进行了对比研究。利用XRD技术跟踪晶体生长过程,考查了模板剂、合成方法、pH值、Na⁺含量等因素对晶化动力学的影响,得出了合成各种杂原子分子筛的最佳条件。各种测试均表明杂原子进入了分子筛骨架。     

Synthesis of high-silica EU-1 zeolite in the presence of hexamethonium ions: a seeded approach for inhibiting ZSM-48

A seeded approach was developed to synthesize high-silica EU-1 zeolite via inhibiting the co-crystallization of ZSM-48 in the presence of hexamethonium (HM) ions. A systematic study was carried out to determine factors such as seed content and SiO(2)/Al(2)O(3) ratio, which influenced the crystallization of high-silica EU-1 and transformation of EU-1 into ZSM-48. Using EU-1 seeds, not only well-crystallized pure EU-1 zeolites with SiO(2)/Al(2)O(3) ratios more than 500 were synthesized, but also the co-crystalline of ZSM-48/EU-1 or pure ZSM-48 was obtained in control from silica-rich mixture gels. Furthermore, the kinetic features of the seeded synthesis of EU-1 zeolites with SiO(2)/Al(2)O(3) ratios of 55, 190, and 500 were examined. It was found that seeds played crucial roles in the decrease of apparent activation energy of EU-1 nucleation and inhibiting the transformation of EU-1 into ZSM-48. The HM and Al species performed synergistic roles to inhibit the formation ZSM-48 during high-silica EU-1 nucleation and crystal growth.     

Pyrolysis of n-pentane on ZSM-5 zeolite

Pyrolysis of n-pentane has been studied at the temperature range 653–753 K on ZSM-5 zeolite. High catalytic activity and selectivity of H-ZSM-5 zeolite was found. The yield of propane was about 80 wt. %. A mechanism of the process is proposed.

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H-ZSM-5 n- 653–153 . . 80%. n-.

     

一步法合成多级孔结构ZSM-5分子筛

多级孔结构ZSM-5分子筛的合成过程复杂。利用双模板剂,通过优化晶化条件(如晶化时间与晶化温度)和Si/Al物质的量比等一步水热晶化合成了具有多级孔结构的ZSM-5分子筛,并采用XRD、N₂吸附-脱附、吡啶红外吸脱附、SEM和TEM等方法对样品的晶体结构、孔道结构、表面酸性和形貌等进行了表征。结果表明,一步法合成多级孔结构ZSM-5分子筛的适宜条件是:晶化温度160-180℃,晶化时间24-96 h,反应物组成为SiO₂/Al₂O₃/Na₂O/CTAB/TPABr/H₂O=1/x/0.4/0.05/0.12/280,(x:50-240)。其中,晶化温度160℃、晶化时间48 h和以Si/Al物质的量比50的凝胶合成的样品具有有序的介孔(平均尺寸3.60 nm)结构、较高的结晶度和较强的酸性。     

Formation of superacid centers in the structure of zeolite ZSM-5

The structural changes and acid characteristics of the zeolite ZSM-5 modified with titanium and sulfur were studied. The modifier components were chemically bonded to the zeolite structure. The acid characteristics of zeolite changed and superacid centers appeared. A physicochemical study showed that treatment of zeolite with titanium tetrachloride and sulfuryl chloride did not change its structure and molecular-sieve properties.     

Localization of the copper-containing component in the pore volume of zeolite ZSM-5

The distribution of the copper-containing component in the pore volume of zeolite ZSM-5 has been investigated by H₂ and N₂ adsorption at 77 K and IR spectroscopy. Samples were synthesized by ion exchange and incipient wetness impregnation. Copper-containing clusters are mostly located on the surface of the mesopores formed by packed zeolite nanocrystallites. This causes partial blocking of the volume of microporous channels for N₂ molecules, but these channels remain accessible for H₂ molecules. It has been deduced that no considerable amount of copper located in the structural channels of the zeolite. According to IR spectroscopic data, the sorption of copper ions in the Cu/ZSM-5 catalysts takes place on extraframe-work aluminum, which forms Al-OH-Al bridges and terminal Al-OH groups, and on terminal Si-OH groups located on the zeolite crystal surface.     

Use of diffusion barriers in the preparation of supported zeolite ZSM-5 membranes

Zeolite ZSM-5 membranes were prepared by in situ crystallization on porous α-Al₂O₃ disks that contained a diffusion barrier to limit excessive penetration of siliceous species into the alumina pores. The barrier was introduced into the alumina pores by impregnating the porous disk with a 1:1 molar mixture of furfuryl alcohol (FA) and tetraethylorthosilicate (TEOS), polymerizing the mixture retained in the disk, and carbonizing the resulting polymer at 600°C in N₂. Following carbonization, a partial carbon burn-off was carried out by catalyzed oxidation in 2% O₂N₂ at 600°C to generate a carbon-free region near the surface of the support. After zeolite crystallization, the remaining carbon and the organic structure directing agent were removed by calcination in air, at 500°C. It was found that pure carbon does not support zeolite growth while the solid obtained from a mixture of FA and TEOS does, due to the presence of dispersed silica. Membranes synthesized using barriers have n-butane flux and n-butane/isobutane selectivity 2.7 × 10⁻³ mol m⁻² s⁻¹ and 45, respectively, at 185°C, which are, respectively, ca. 1.6 and 4 times as large as those of membranes prepared without the use of barriers. Electron probe microanalysis (EPMA) and X-ray diffraction (XRD) revealed that the internal layer of the barrier-pretreated membrane has smaller thickness and higher crystallinity accounting for the increased flux and selectivity.     

Control of Al distribution in ZSM-5 by conditions of zeolite synthesis

Concentration of Al-O-(Si-O)1,2-Al sequences located in one ring and forming cationic sites for divalent cations in ZSM-5 can be controlled in a wide range of their concentrations by the variation of the source of aluminium and silicon used for synthesis of this zeolite.     

Single-template synthesis of zeolite ZSM-5 composites with tunable mesoporosity

Hierarchically structured composites (TUD-C) with ZSM-5 crystals embedded in a well-connected mesoporous matrix were synthesized by using only one organic templating/scaffolding molecule (TPAOH).     

硅铁ZSM-48沸石的CO加氢催化性能

考察了硅铁ＺＳＭ－４８负载铁、钾催化剂在ＣＯ加氢制备低碳烯烃反应中的催化性能。结果表明,Ｆｅ（Ⅲ）离子同晶取代Ｓi（Ⅳ）后,不仅使沸石分子筛的表面能量分布更加趋 于均匀,而且明显促进了活性组分铁的还原和减弱了催化剂表面吸附氢的能力,从而大大提高了反应活性和选择性。硅铁ＺＳＭ－４８负载过量的铁、钾都不利于ＣＯ加氢合成低碳烯烃,其负载量的量侍值分别为８％和１．９％。另外,硅铁ＺＳＭ－４８的焙烧温度和焙烧     

Catalytic transformation of methane over in-loaded ZSM-5 zeolite in the presence of ethene

Methane is shown to react with ethene over In-loaded ZSM-5 to higher hydrocarbons such as propene and toluene at around 673 K. Such methane conversion is not catalyzed by proton-exchanged ZSM-5 (H-ZSM-5) under the same conditions, only C2H4 being converted to higher hydrocarbons. By using 13C-labeled methane (13CH4) as a reactant, the reaction paths for the formation of propene, benzene and toluene were examined. 13C-labeled propene (13CC2H6) is formed by the reaction of 13CH4 with C2H4. The lack of 13C-labeled benzene revealed that propene is not transformed to benzene, which instead originates entirely from C2H4. The 13C atom is inserted both into the methyl group and benzene ring in the toluene formed. This indicates that toluene is formed by two reaction paths; the reaction of 13CC2H6 with butenes formed by the dimerization of C2H4 and the reaction of benzene with 13CH4. The existence of the latter path was proved by the direct reaction of 13CH4 with benzene. The reaction of methane with benzene was also carried out in a continuous flow system over In-loaded ZSM-5. The reaction afforded 7.6% and 0.9% yields of toluene and xylenes, respectively, at 623 K.     

ZSM-5分子筛的脱硅改性及加氢改质性能

考察了水热与碱联合处理过程中两者的先后顺序对ZSM-5分子筛酸性和孔结构的影响,并与单独的水热和碱处理进行了比较。结果表明,水热后的碱处理对ZSM-5分子筛具有骨架脱硅、骨架补铝和清除非骨架铝物种三重作用,而碱处理后的水热处理具有骨架脱铝和部分骨架稳定化双重作用。与先水热处理再碱处理相比,先碱处理后的水热处理在优化分子筛酸性和产生介孔方面更加有效。基于水热-碱联合处理的HZSM-5分子筛所制备的催化剂对催化裂化汽油的加氢改质表现出适中的异构化活性、较高的烯烃芳构化活性以及最高的稳定性。     

一种用于合成ZSM－48沸石分子筛的新体系

一种用于合成ＺＳＭ－４８沸石分子筛的新体系李建权，刘光焕，董晋湘（太原工业大学精细化工研究所，太原０３００２４）关键词捏合法，极浓体系，ＺＳＭ－４８沸石，合成，表征长期以来，沸石合成一直是在模拟天然沸石形成的条件下进行的．通常的反应体系是一过饱和状态...     

纯相ZSM-11分子筛在双模板剂水热体系中的合成及表征研究(英）

在水热体系中利用双模板剂合成了纯相ZSM 11分子筛,并考察了合成条件的影响。同时利用多种表征手段对产品的物理化学性质进行了表征。     

Rapid crystallization and morphological adjustment of zeolite ZSM-5 in nonionic emulsions

Zeolite ZSM-5 was synthesized for the first time in a nonionic emulsion composed of polyoxyethylated alkylphenol, butanol, cyclohexane and tetraethylammonium hydroxide (TEAOH)-containing zeolite synthesis mixture. The crystallization kinetics in the emulsion was investigated and the ZSM-5 product was characterized in detail by XRD, SEM, FT-IR, TG, N₂ adsorption and CHN analysis techniques. Compared with the conventionally hydrothermal synthesis with the same structure directing agent TEAOH, the emulsion system allows rapid crystallization of ZSM-5. The ZSM-5 product exhibits unusual agglomerated structure and possesses larger specific surface area. The FT-IR, TG results plus CHN analysis show the encapsulation of a trace of emulsion components in the emulsion ZSM-5. Control experiments show the emulsion system exerts the crystallization induction and morphological adjustment effects mainly during the aging period. The effects are tentatively attributed to the confined space domains, surfactant-water interaction as well as surfactant-growing crystals interaction existing in the emulsion.     

Ambient xenon sampling using an Ag/ZSM-5 zeolite

Journal of Radioanalytical and Nuclear Chemistry - An ambient xenon sampling system using Ag/ZSM-5 was designed, and its performance was tested. The xenon collection efficiency of the system was...