Synthesis of ZSM‐5 by hydrothermal method with pre‐mixing in a stirred‐tank reactor

This work proposed a synthesis route of ZSM‐5 via the hydrothermal method with premixing in a stirred tank reactor (STR). Effects of various operating conditions, including pre‐mixing time, molar ratio of SiO₂/Al₂O₃, TPAOH (organic template agents) concentration, NaCl (alkali metal cations) concentration, crystallization temperature, and crystallization reaction time, on the average particle size (PS) and particle size distribution (PSD) were investigated. It was found that the pre‐mixing time in the STR significantly affect the formation of proto‐nuclei in premixing process and crystal growth in hydrothermal reaction process, and consequently influence the PS and PSD of the prepared ZSM‐5. ZSM‐5 with good thermal stability, a PS of 380 nm, PSD of 0.17–0.9 µm, pore diameter of 2.31 nm, pore volume of 0.19 cm³ · g^?1 and specific surface area of 337.25 m² · g^?1 were obtained under the optimal conditions of a crystallization reaction time of 24 h, a crystallization temperature of 130 °C, a molar ratio of SiO₂/Al₂O₃ of 200, a TPAOH concentration of 3.5 mol · L^?1, NaCl concentration of 0.3 mol · L^?1, and a pre‐mixing time of 5 h. This work indicated that the operating conditions including premixing time have a significant effect on its PS and PSD.     

纳米ZSM-5分子筛受限空间合成

采用中孔碳纳料管为惰性基体,通过限定空间尺寸法合成n(SiO2)/n(Al2O3)=100,平均晶粒度为27nm的纳米ZSM-5分子筛。合成产物分别采用X射线粉末衍射(XRD)、红外光谱(IR)、透射电镜(TEM)、扫描电镜(SEM)进行表征,并对水解时间、碳源等影响因素进行了研究。结果表明,合成的分子筛具有典型的ZSM-5骨架结构和纳米尺寸,并且由于小尺寸效应该样品呈球形聚集态。采用碳纳米管的纯化方法,较长的水解时间、合适的中孔碳源和铝源均有利于纳米分子筛的合成。     

固态离子交换制备的Mg-ZSM-5沸石催化剂的酸性和催化行为

采用固态反应方法制备了一系列不同镁含量的Ｍｇ－ＺＳＭ－５沸石催化剂，并用Ｘ光衍射、ＴＰＤ和ＩＲ技术测试了这些催化剂的结构和表面酸性。结果表明，经固态反应处理后，沸石的结构和结晶度未发生变化，而表面Ｂ酸中心随催化剂中镁含量增加而显著减少，Ｌ酸中心则略有增加。对甲苯甲基化催化性能考察结果表明，改性后的沸石催化剂显著改善了初始活性和寿命，对位选择性从原来２４％增加到８０％—９０％。这些结果进一步表明，固态反应是沸石改性的有效和方便的方法之一。     

ZSM—5沸石中非骨架铝对沸石裂化性能影响的初步探讨

用固体核磁共振和红外光谱等手段，研究了ＺＳＭ－５沸石经水热焙烧产生的非骨架铝对沸石结构性能和催化性能的影响。结果表明，水热焙烧产生的非骨架铝通过氟硅酸洗涤可部分除去；非骨架铝既存在于沸石内表面，也存在于沸石的外表面，覆盖了沸石的部分酸性中心。同时，用脉冲微反及轻油微反考察了非骨架铝对沸石裂化性能的影响。结果表明，非骨架铝的存在使沸石的裂化活性降低，但烯烃选择性增高，说明沸石中非骨架铝对提高沸石烯烃     

Performance of H‐ZSM‐5‐supported bimetallic catalysts for the combustion of polluting volatile organic compounds in air

The performance of H‐ZSM‐5‐supported bimetallic catalysts with chromium as the base metal in the combustion of ethyl acetate and benzene is reported. A reactor operated from 100 to 500 °C at a gas hourly space velocity (GHSV) of 32 000 h^?1 was used for study of the activity. A combination of 1.0 wt% chromium and 0.5 wt% copper yielded a catalyst (Cr_1.0Cu_0.5/Z) with improved conversion and carbon dioxide yield. Cr₂O₃ (Cr³⁺) and CuO (Cu²⁺) were the predominant metal species in the catalyst. In agreement with the Mars–van Krevelen model, improved reducibility of Cr³⁺ in the presence of Cu²⁺ led to an improvement in activity. The copper content in Cr_1.0Cu_0.5/Z also favored the formation of deep combustion products. Condensation and subsequent growth of coke precursors in the catalyst pores led to the formation of a softer and less aromatic coke fraction while dehydrogenation activity on acid sites formed a harder and more aromatic coke fraction. The use of Cr_1.0Cu_0.5/Z favored the formation of lower molecular weight intermediates, leading to reduction in formation of softer coke. Copyright © 2005 Society of Chemical Industry     

Transalkylation of toluene with C9 aromatic hydrocarbons over ZSM5 zeolites

The transalkylation reactions of a mixture of toluene and C₉⁺ aromatics were studied over HZSM5 catalysts of varying SiO₂:Al₂O₃ ratios (30–800) as well as over a NiHZSM5 catalyst. As the SiO₂: Al₂O₃ ratio is increased, the rate of transalkylation is decreased. Among the C₉ aromatics that were present in the feed, the ethyl toluenes were extensively de-ethylated to toluene. The shape-selective characteristics of the ZSM5 zeolite were revealed through the relative order of reactivity of the three trimethyl benzene isomers 1.2.4>1.2.3>1.3.5. The stable life of the catalyst can be prolonged by the incorporation of nickel. The influences of process parameters such as temperature, pressure, space velocity and H₂: hydrocarbon ratio are also presented. It was observed that the transalkylation of C₉ aromatics with toluene to yield xylenes occurs mainly on the external surface of the ZSM5 crystals. The disproportionation of toluene to yield benzene and xylene, however, takes place predominantly in the pore system.     

分子筛ZSM-5对海藻酸钠热分解的影响

本研究采用热重分析法研究了分子筛ZSM-5填充海藻酸钠在空气中的热分解过程,升温速率分别为5K/min、10K/min、15K/min、20K/min和30K/min,温度范围为室温（298K）至1250K,并利用TGA曲线分析了复合材料的热分解特性。热重分析结果显示,热分解反应最剧烈的温度介于450～650K之间,热分解动力学分析表明,该热分解过程为一级反应,可通过最大失重速率温度法和Ozawa等失重率法分别计算求得活化能和频率因子。结果表明,活化能和频率因子随着失重率的增加而增大,分子筛ZSM-5的加入有利于海藻酸钠的热分解。     

M-ZSM-48的合成与物化性能研究

研究了杂原子Ｍ－ＺＳＭ－４８（Ｍ＝Ｂ，Ｇｅ，Ｃｒ或Ｖ）型分子筛在水热体系中的合成条件，并用多种物理化学方法研究了分子筛的比表面、表面酸性、吸附性和热性能等物化性能。结果表明，杂原子进入分子筛骨架，对其性能具有显著影响。     

Performance of 3%Mo/ZSM‐5 catalyst in the presence of water during methane aromatization in supersonic jet expansion

The influence of water in the CH₄ feed on the performance of 3%Mo/ZSM‐5 catalyst during methane direct aromatization under supersonic jet expansion (SJE) condition was investigated. We observed that both surface Mo₂O_xC_y and β‐Mo₂C species are catalytically active for methane aromatization under SJE condition. The presence of water can promote the removal of surface carbon before the generation of aromatic‐type and/or graphitic carbon. In appropriate amount, water can improve the stability of surface Mo₂O_xC_y, and hence resulting in better catalytic performance. The study provided valuable information relevant to the direct utilization of methane hydrate. © 2010 American Institute of Chemical Engineers AIChE J, 2011