RUB-13分子筛的合成及其甲醇制烯烃催化性能

采用水热法合成RUB-13分子筛，探讨了有机模板剂（OSDA）、硅源、晶化温度和水硅比等制备条件对RUB-13分子筛晶体结构的影响，考察了RUB-13分子筛在甲醇制烯烃（MTO）反应中的催化性能。结果表明，采用1，2，2，6，6-五甲基哌啶（PMP）为有机模板剂、白炭黑为硅源，在晶化温度为170℃的条件下，选择H₂O/Si比为100和80时可分别合成出高纯度的低硅铝比（Si/Al=100）和高硅铝比（Si/Al=200）的RUB-13分子筛晶体，且晶粒呈棒状形貌。H-Al-B-RUB-13（Si/Al=200）分子筛用于催化甲醇制烯烃反应时，在400℃下表现出高的低碳烯烃选择性（C_2-5⁼选择性达97.8%，丙烯选择性为54.5%），优于传统的H-SAPO-34和H-ZSM-5分子筛催化剂。     

低硅铝比ZSM-48分子筛合成及其正构十二烷临氢异构催化性能研究

通过静态水热合成法,溴化六甲二铵作为结构导向剂合成出系列低硅铝比的ZSM48沸石分子筛(Si/Al100),所合成样品中最低硅铝比为38.6(ICP-AES),这将拓宽ZSM-48高硅沸石分子筛的应用范围。制备Pt负载双功能催化剂,用于正构十二烷临氢异构催化反应。结果表明,硅铝比的改变可以影响催化剂的活性,投料硅铝比为70的双功能催化剂具有最优的催化性能,但硅铝比改变对异构产物的分布没有明显的影响,其异构产物以支链在中间位的异构体为主。     

HZSM-5型分子筛硅铝比对一步法合成二甲醚的影响

以Cu/Zn/Al(摩尔比为6∶3∶1)甲醇合成催化剂与HZSM-5型分子筛混合,制备了一步法二甲醚合成催化剂。通过改用三种不同Si/Al摩尔比（摩尔比为25、38和50）的HZSM-5型分子筛,考察了催化剂中脱水组分（HZSM-5分子筛）的酸性对二甲醚合成的影响。结果表明,随着催化剂Si/Al摩尔比的降低,分子筛的酸性增强,使得CO单程转化率提高。当催化剂Si/Al＝38时,CO对二甲醚的选择性最高,可达到68.13％,其次是催化剂Si/Al＝50,选择性最差的是Si/Al＝25的催化剂。在553 K、 3 MPa和4 000 h－1的条件下,Si/Al＝25和Si/Al＝38的催化剂CO单程转化率和DME的选择性接近一致。在此条件下,两者的时空产率达到试验的最大值,分别为0.38 gDME/(gcat·h)和0.36 gDME/(gcat·h),在试验范围内,一步法合成二甲醚催化剂最佳的Si/Al摩尔比为25。     

双矿化剂对合成ZSM-5分子筛酸性和织构特征及其甲醇转化制丙烯催化性能的影响

采用静态水热法在F^--OH^-体系中,以四丙基氢氧化铵为模板剂、偏铝酸钠为铝源、正硅酸乙酯为硅源,合成了纳米SiO₂-ZSM-5分子筛,考察了F^-/Al₂O₃物质的量比对所合成的ZSM-5分子筛织构性质和甲醇转化制丙烯催化性能的影响。结果发现,随着初始溶胶F^-/Al₂O₃物质的量比的增大,产物中SiO₂的含量增大,ZSM-5分子筛的相对结晶度有所降低;同时,分子筛的比表面积和孔容减小、酸强度降低、酸量减少。对于甲醇转化制丙烯,最佳F^-/Al₂O₃物质的量比为12;此时,丙烯选择性高于45%,丙烯/乙烯（P/E）比值大于10。反应机理分析表明,过渡态择形选择性是控制烯烃选择性的重要因素。     

Zn/H-ZSM-5催化剂上的二甲醚芳构化反应

 考察了 H-ZSM-5 和 Zn/H-ZSM-5 催化剂的二甲醚芳构化性能. 结果表明, H-ZSM-5 分子筛催化剂酸性的增强和酸中心的增多有利于二甲醚芳构化. 当在 H-ZSM-5 催化剂中加入 2% Zn 时, 在 360 oC 下反应时总芳烃收率从 50.0% 增加至 66.2%, C8 芳烃收率从 28.6% 增加到 39.0%. 反应温度升高到 480 oC 时, 总芳烃收率增加至 78.0%.     

Abatement of hydrocarbons by acid ZSM-5 and BETA zeolites under cold-start conditions

Simulated cold-start tests have been carried out to evaluate the performance of H-ZSM-5 and H-BETA zeolites as hydrocarbon traps under simulated gasoline car exhaust gases, paying special attention to the effect of water on their behaviour. It is concluded that the hydrothermal treatment of the zeolites in the acidic form contributes to the better performance of these materials as hydrocarbon traps since the stabilization of the zeolites takes place. Moreover, the decrease of the surface acidity of the zeolites results in an increase of the Si/Al ratio, which contributes to the decrease of the water affinity for adsorption sites. Thus, the competition with hydrocarbon molecules in the exhaust for the adsorption sites is reduced which increases their trap efficiency. The stabilized H-ZSM-5 is the zeolite that showed the best performance with a propene offset temperature of 240 °C, which should be high enough for the three-way catalyst to carry out its role as catalytic converter.     

Ga改性ZSM-5分子筛催化丙烷芳构化性能研究

用离子交换法制备Ga改性ZSM-5双功能催化剂,并结合XRD、SEM、BET、NH₃-TPD、Py-IR及ICP、XPS等多种技术进行表征,考察分子筛硅铝比(Si/Al)和催化剂氧化还原预处理条件对分子筛的酸性质、Ga物种的存在状态及其丙烷芳构化催化性能的影响。研究表明,硅铝比不仅可以改变分子筛的酸性,也会影响分子筛中非骨架Ga物种与分子筛表面的相互作用程度,进而影响含Ga分子筛的丙烷芳构化性能。在质量空速1.0 h^-1、反应温度550℃ 下,Si/Al比为30的Ga-HZSM-5分子筛丙烷转化率和芳烃收率最高。Ga物种的引入可以提高丙烷的转化率和芳烃的选择性,并抑制烷烃、烯烃的裂解。H₂还原处理,将分子筛表面Ga₂O₃还原为低价的Ga⁺和GaH⁺₂物种,促进了Ga物种向分子筛微孔迁移;还原-氧化处理后,Ga⁺和GaH⁺₂物种氧化成GaO⁺,占据分子筛孔道离子交换位,显著提高了催化剂的芳构化活性。     

添加剂PVP和MTS对合成Beta分子筛结构与性能的影响

分别以铝酸钠和硅溶胶为铝源和硅源,四乙基氢氧化铵为模板剂,在水热条件下,考察了添加剂(聚乙烯吡咯烷酮(PVP)和甲基三乙氧基硅烷(MTS))对合成Beta分子筛结构与性能的影响,并通过XRD、TEM、BET、ICP、~(29)Si-NMR和NH_3-TPD等方法对合成样品进行了结构表征和作用机理讨论,同时以催化裂化异丙苯为模型反应评价其催化性能。结果表明,与传统Beta分子筛相比,加入PVP后所得样品具有更高结晶度和较高的硅铝物质的量比(25.68)以及较大的比表面积(772 m~2/g);而加入MTS后尽管具有较大比表面积(657 m~2/g)和较高硅铝物质的量比(25.76),但是结晶度却相对降低,且粒径减小(160-320 nm)。两种添加剂作用下所得样品均具有更多酸量,在催化裂化异丙苯的反应中表现出较高的催化活性。     

合成气直接转化制低碳烯烃催化剂设计及反应条件优化

采用水热法合成了相同粒径、不同硅铝比的ZSM-5分子筛,并通过浸渍法将Fe基（Fe-Cu-K）催化剂负载于ZSM-5上,系统考察了分子筛硅铝比变化对合成气制烯烃（FTO）反应的影响。结果表明,反应条件、分子筛酸性对CO转化率和低碳烯烃选择性有显著影响。当ZSM-5分子筛硅铝比为50时负载型催化剂有着最高的CO转化率（84.71%）和低碳烯烃选择性（32.08%）。H₂-TPR结果表明,硅铝比为50的Z50/FeCuK中Fe物相的还原度最高。原位漫反射红外光谱（DRIFTS）、热重差热分析（TG-DTA）、X射线粉末衍射（XRD）等结果表明,Z50/FeCuK催化剂表面吸附的碳酸盐和烃类吸附物种最多,且其反应后形成了较多的FeC_x晶相。最后对反应条件进行了优化,结果表明,温度为310 ℃,H₂/CO （volume ratio）=2和压力为1.0 MPa时FTO的催化性能最优。     

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。     

Methanol-to-Olefin Conversion over Zeolite Catalysts: Active Intermediates and Deactivation

Methanol-to-olefin (MTO) conversion over various zeolites with different topologies, Si/Al molar ratios, and crystallite sizes were investigated to verify the effects of pore shape and size, acidity, and external surface area on the catalytic activity, product selectivity, and deactivation. The IR and electron spin resonance (ESR) study of zeolite catalysts used in MTO also proceeded to deduce the active intermediates formed in their cages or pores. The zeolites with 8 membered-ring (MR) pore entrances such as CHA, ERI, LTA, and UFI commonly exhibited high selectivity to lower olefins due to their small entrances, but the CHA catalyst with the smallest cage maintained its activity longer than other 8MR zeolites. The slow condensation of polymethylbenzene (PolyMB) to polyaromatic hydrocarbons (PAH) on MOR zeolite with a high Si/Al molar ratio due to its low concentration of strong acid sites resulted in a slow deactivation. The extremely small crystallites of H-SAPO-34 and H-ZSM-5 less than 100 nm showed an adverse effect in MTO; while the large crystallites above 1,000 nm also exhibited poor catalytic performance because of their small external surface. The study of IR regarding the adsorbed and occluded materials on zeolites demonstrated the effect of pore shape and size on the active intermediates: the zeolites with larger pores and cages allowed the formation of alkylbenzenes with long alkyl groups which preferred to be condensated to PAH. The well-resolved hyperfine splitting of ESR spectra observed on H-SAPO-34 used in MTO clearly illustrated the presence of hexamethylbenzenium radical cations. The small intersections of phosphorous-modified H-ZSM-5 allowed the formation of tetramethylbenzenium radical cations in MTO. The formation of PolyMB radical cations, their role as active intermediates and the effect of topology, acidity, and crystallite size of zeolites on their deactivation were discussed.     

Effects of ammonium exchange and Si/Al ratio on the conversion of methanol to propylene over a novel and large partical size ZSM-5

One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene (MTP) over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity (45.9%) was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.     

ZSM-5的水热改性及其在合成气经二甲醚制汽油中的应用

对合成气经二甲醚制汽油两段等压反应系统中的ZSM-5分子筛催化剂进行原位水热处理,研究了不同温度下水蒸气处理ZSM-5分子筛的结构、表面酸性及催化反应性能。XRD、XRF、BET、NH₃-TPD 和 TPO等表征手段表明,水热处理温度为400℃时会使ZSM-5分子筛大部分非骨架铝脱除,酸中心数量减少,比表面积增加,提高了催化剂的活性及产物选择性。     

高硅Y沸石的合成研究进展

Y沸石的合成及在流化催化裂化中的应用在现代石油化学工业中具有里程碑意义. Y沸石的骨架硅铝比直接影响材料的热/水热稳定性及催化性能. 提高Y沸石的骨架硅铝比、 合理减少酸中心密度、 提高酸强度, 进而改善催化裂化反应性能一直是学术界和工业界关注的重要课题. 目前工业使用的高硅Y沸石均是通过复杂的后处理方法获得的. 与复杂的后处理方法相比, 直接合成高硅Y沸石是更理想的方式, 但其难度大, 为分子筛领域具有挑战性的课题. 本文系统总结了高硅Y沸石的直接合成研究进展, 分别对无机合成体系和有机模板剂合成体系进行综合评述, 并介绍了Y沸石的晶化机理研究进展.     

ZSM—5芳构化反应活性和稳定性的研究

ＺＳＭ－５以其独特的基于微孔结构特征的形状选择性和强酸中心，而成为具有酸催化择形性能的新型分子筛催化剂．ＺＳＭ－５分子筛表面酸性中心不但是反应的活性中心，同时也是积炭中心，这使得这类催化剂不仅具有很高的催化反应活性，同时也具有较高的结焦活性．催化剂表...     

纳米 ZSM-22分子筛的水热合成及在甲醇转化反应中的性能

分子筛结构的独特性和多样性使其在催化、吸附分离和离子交换等领域有着广泛应用.近年来,纳米分子筛制备和应用受到极大关注.与传统微米分子筛相比,纳米分子筛具有较小的晶粒尺寸、较大的外表面积和较高的表面活性,能显著提高其分离和催化性能.制备纳米晶体的常用方法有过量模板法、空间限定法、晶种法、离子热合成法及微反应器合成法等.目前,已合成出多种拓扑结构的纳米分子筛,包括 FAU, MFI, MEL和CHA等. ZSM-22是一种具有 TON拓扑结构的一维十元环直孔道分子筛(孔口尺寸为0.45 nm ×0.55 nm),在长链烷烃异构化和烯烃异构化等反应中表现出优异的催化活性.水热合成法是制备 ZSM-22分子筛最常用的方法,所得样品晶粒尺寸为2–15μm,但由于 ZSM-22分子筛是一种亚稳态结构,为了防止杂晶生成,合成通常是在剧烈搅拌(通常大于400 r/min)下进行.目前已有报道在较低转速下合成 ZSM-22分子筛,但产物仍为微米晶体;或在微波辅助水热合成条件下合成亚微米 ZSM-22分子筛,但晶体尺寸不可调且合成过程需要较高功率的微波反应器.因此,在水热条件下合成纯纳米 ZSM-22分子筛仍然是一个巨大挑战.本文在上述研究基础上采用改进的水热合成法成功合成出纳米 ZSM-22分子筛,考察了转速﹑硅铝比及乙醇共溶剂对晶粒尺寸的影响,比较了纳米和常规微米 ZSM-22分子筛的甲醇转化反应性能.结果表明,采用改进的水热合成法能够在较低转速下合成出纳米 ZSM-22分子筛,晶体尺寸在150–800 nm范围可调.通过考察转速对晶粒尺寸的影响,发现静态合成条件下无法形成 ZSM-22分子筛,表明 ZSM-22分子筛合成需要一定的转速.转速在10–50 r/min变化时,可以合成出不同晶体尺寸的 ZSM-22分子筛,且随转速提高, ZSM-22分子筛晶体尺寸先减小后增大,表明纳米 ZSM-22分子筛合成存在最佳转速.另外,配料硅铝比能显著影响 ZSM-22分子筛晶体尺寸,随配料硅铝比增加, ZSM-22分子筛晶体尺寸先减小后增大.通过在合成体系中添加乙醇作为共溶剂,考察了有机溶剂对 ZSM-22分子筛晶粒尺寸的影响,发现有机溶剂能显著增大 ZSM-22的晶体尺寸.将本文合成的纳米和常规微米 ZSM-22分子筛用于甲醇转化反应,考察了晶体尺寸对 ZSM-22分子筛甲醇转化反应性能的影响.发现与常规微米 ZSM-22分子筛相比,纳米 ZSM-22分子筛催化剂寿命显著提高,说明晶粒尺寸减小能有效减缓积碳导致的分子筛失活;同时,反应产物中乙烯和芳烃选择性有所提高,这是由于外表面积增大所致.此外,还考察了不同硅铝比 ZSM-22分子筛的甲醇转化反应性能.结果表明,分子筛硅铝比会影响催化剂寿命,但晶体尺寸对催化剂寿命影响更大. ZSM-22分子筛硅铝比增大有助于提高低碳烯烃选择性,减少芳烃生成.     

Effect of the Si/Al ratio of HZSM-5 zeolite on the production of dimethyl ether before and after ultrasonication

A series of as-synthesized HZSM-5 zeolites with different Si/Al ratios (25, 90, 120, 240 and 400) were post-treated by ultrasonication for an optimum time of 60 min. The morphology, acidity and textural properties of HZSM-5 were characterized with XRD, SEM, N₂ adsorption and NH₃-TPD techniques. The catalytic performance was evaluated by dehydration of methanol to dimethyl ether (DME), which is a promising gaseous automotive fuel in future. It was found that the Si/Al ratio of HZSM-5 had considerable impacts on its catalytic performance for dehydration of methanol to DME. Its activity increased with decreasing Si/Al ratio from 400 to 25. Ultrasonication of HZSM-5 could significantly improve its catalytic performance.     

Dimethylether production on zeolite catalysts activated by Cl-, F- and/or ultrasonication

The chlorinated and fluorinated zeolite catalysts were prepared by the impregnation of zeolites( H-ZSM-5,H-MOR or H-Y) using two halogen precursors( ammonium chloride and ammonium fluoride) in this study. The influence of ultrasonic irradiation was evaluated for optimizing both halogen precursors for production of dimethylether( DME) via methanol dehydration in a fixed bed reactor. The catalysts were characterized by SEM,XRD,BET and NH3-TPD. The reaction conditions were temperatures from 100 to 300 ℃ and a WHSV = 15. 9 h-1. All halogenated catalysts showhigher catalytic activities at all reaction temperatures studied. However, the halogenated zeolite catalysts prepared under ultrasonic irradiation showhigher performance for DME formation. The chlorinated zeolite catalysts show higher activity and selectivity for DME production than the respective fluorinated versions.     

Influence of the ZSM-5 Support Acidity on the Catalytic Performance of Pd/ZSM-5 in Lean Methane Oxidation

Although zeolites are characterized by their special acidic properties, there is still no clear consensus on the effect of zeolite support acidity on the catalytic activity of supported Pd catalyst in methane oxidation. Herein, a series of Pd/H-ZSM-5 and Pd/Silicalite-1 catalysts was prepared by the deposition-precipitation method and used in lean methane oxidation. The effect of ZSM-5 support acidity on the catalytic performance of Pd/ZSM-5 was investigated. The results indicate that with the decrease of Si/Al ratio(x), viz., the increase of acid sites in H-ZSM-5(x), the catalytic activity of Pd/H-ZSM-5(x) increases substantially; the activity of various catalysts in the lean methane oxidation decreases in the order of Pd/H-ZSM-5(28)>Pd/H-ZSM-5(48)>Pd/H-ZSM-5(88)>Pd/H-ZSM-5(204)>Pd/Silicalite-1. Furthermore, various characterization measures reveal that the catalytic activity of Pd/H-ZSM-5(x) in lean methane oxidation is mainly related to the Lewis acid sites in the H-ZSM-5 support, whereas less relevant to the Brønsted acid sites. The abundant Lewis acid sites in H-ZSM-5 are capable to enhance the interaction between the Pd species and H-ZSM-5 support, which can inhibit the agglomeration of Pd particles and improve the dispersion of Pd species, and thus boost the catalytic activity of Pd/H-ZSM-5 in methane oxidation.     

Offretite Zeolite Single Crystals Synthesized by Amphiphile-Templating Approach

Offretite zeolite synthesis in the presence of cetyltrimethylammonium bromide (CTABr) is reported. The offretite crystals were synthesized with a high crystallinity and hexagonal prismatic shape after only 72 h of hydrothermal treatment at 180 °C. The CTABr has dual-functions during the crystallization of offretite, viz. as structure-directing agent and as mesoporogen. The resulting offretite crystals, with a Si/Al ratio of 4.1, possess more acid sites than the conventional offretite due to their high crystallinity and hierarchical structure. The synthesized offretite is also more reactive than its conventional counterpart in the acylation of 2-methylfuran for biofuel production under non-microwave instant heating condition, giving 83.5% conversion with 100% selectivity to the desired product 2-acetyl-5-methylfuran. Hence, this amphiphile synthesis approach offers another cost-effective and alternative route for crystallizing zeolite materials that require expensive organic templates.