载体性质对Pd催化剂加氢脱硫性能的影响

以Si O2、全硅MCM-41(Si-MCM-41)、通过机械混合Si-MCM-41与ZSM-5得到的Z-MCM-41-M以及通过在ZSM-5外部包覆MCM-41制备得到的Z-MCM-41四种材料为载体,制备了四种负载型Pd催化剂。采用XRD、HRTEM、N2吸附-脱附、NH3-TPD手段对Pd催化剂进行了表征;以二苯并噻吩(DBT)为模型化合物,在固定床反应器上对四种催化剂的加氢脱硫(HDS)活性、加氢路径选择性和加氢裂化活性进行了考察,研究了不同类型载体对Pd催化剂加氢脱硫性能的影响。结果表明,载体的性质会显著影响负载型Pd催化剂的加氢脱硫性能。载体的比表面积对负载型Pd催化剂加氢脱硫活性影响不大,但是HYD路径的选择性与载体的孔道结构有关;具有介孔孔道结构有利于加氢路径选择性的提高。酸性载体负载的Pd催化剂表现出较好加氢脱硫活性和加氢选择性,这与氢溢流有关。介孔材料的孔道结构与微孔沸石的酸性有机结合,所得到的Z-M CM-41复合材料是是潜在的贵金属Pd加氢脱硫催化剂优良载体,可有效提升其加氢脱硫活性。     

多级结构ZSM-5沸石分子筛的合成及其Mo基催化剂在甲烷无氧脱氢芳构化中的应用

以经盐酸预处理的碳纳米管为第二模板,在不添加其它有机溶剂的情况下,仅通过控制晶化条件,即采用变温水热晶化法合成具有多级结构的ZSM-5分子筛.通过x射线衍射、红外光谱测试、透射电镜和N2吸附对合成的分子筛进行了表征,结果表明,该合成分子筛呈近球形,是由纳米棒自组装形成的具有多级结构的亚微米球.该分子筛改性后用于甲烷无氧脱氢芳构化反应,显示出良好的催化性能,甲烷转化率最初达到19%,反应至24 h时甲烷转化率仍保持在10%左右,并且保持了较高的芳香物选择性(达到50%以上).     

ZSM-5 zeolite single crystals with b-axis-aligned mesoporous channels as an efficient catalyst for conversion of bulky organic molecules

The relatively small and sole micropores in zeolite catalysts strongly influence the mass transfer and catalytic conversion of bulky molecules. We report here aluminosilicate zeolite ZSM-5 single crystals with b-axis-aligned mesopores, synthesized using a designed cationicamphiphilic copolymer as a mesoscale template. This sample exhibits excellent hydrothermal stability. The orientation of the mesopores was confirmed by scanning and transmission electron microscopy. More importantly, the b-axis-aligned mesoporous ZSM-5 shows much higher catalytic activities for bulky substrate conversion than conventional ZSM-5 and ZSM-5 with randomly oriented mesopores. The combination of good hydrothermal stability with high activities is important for design of novel zeolite catalysts. The b-axis-aligned mesoporous ZSM-5 reported here shows great potential for industrial applications.     

A Pd@Zeolite Catalyst for Nitroarene Hydrogenation with High Product Selectivity by Sterically Controlled Adsorption in the Zeolite Micropores

The adsorption of molecules on metal nanoparticles can be sterically controlled through the use of zeolite crystals, which enhances the product selectivity in hydrogenations of reactants with more than one reducible group. Key to this success was the fixation of Pd nanoparticles inside Beta zeolite crystals to form a defined structure (Pd@Beta). In the hydrogenation of substituted nitroarenes with multiple reducible groups as a model reaction, the Pd@Beta catalyst exhibited superior selectivity for hydrogenation of the nitro group, outperforming both conventional Pd nanoparticles supported on zeolite crystals and a commercial Pd/C catalyst. The extraordinary selectivity of Pd@Beta was attributed to the sterically selective adsorption of the nitroarenes on the Pd nanoparticles controlled by the zeolite micropores, as elucidated by competitive adsorption and adsorbate displacement tests. Importantly, this strategy is general and was extended to the synthesis of selective Pt and Ru catalysts by fixation inside Beta and mordenite zeolites.     

多级孔ZSM-5负载的钴催化剂的费-托合成催化性能

采用水蒸气辅助转晶(SAC)法合成了粒径均一(180 nm)的纳米ZSM-5颗粒,颗粒间堆积形成大量的开放介孔,与ZSM-5的微孔共同形成多级孔结构。以该材料为载体采用满孔浸渍法制备了负载量为15%(质量分数)的钴催化剂。采用XRD、SEM、TEM、N_2物理吸附-脱附等表征技术对多级孔ZSM-5载体及其负载催化剂的形貌和结构进行了表征,并对催化剂的费-托合成催化性能进行了测试。结果表明,相比于大颗粒的ZSM-5和商业ZSM-5,多级孔ZSM-5负载的钴催化剂的费-托合成活性最高,CH_4选择性最低,C_(5-20)产物的选择性高达68.9%,这归因于多级孔ZSM-5的介孔孔道有效地促进反应过程中产物的传质扩散以及ZSM-5微孔骨架上的酸中心促进了长链烃产物的二次加氢裂解。     

H(Fe)ZSM-5分子筛的合成、表征及其催化性能的研究

用水热法合成出含铁ZSM-5沸石,并对其物相、外貌、结构组成、吸附、表面酸性和催化活性等性能作了测试。ESR和XPS测定结果表明Fe~(3+)进入沸石骨架。实验结果表明,表面总酸性较弱,L酸位浓度较大的H(Fe)ZSM-5在甲醇转化反应中有利于低碳烃的齐聚和异构化,而酸性较强的HZSM-5易使低碳烯烃氢转移而生成大量的气态烃。     

复合分子筛催化微晶纤维素水解

采用水热晶化法制备了HY/ZSM-5复合分子筛。通过XRD、SEM、N2-吸附脱附、NH3-TPD及吡啶吸附红外光谱等手段表征催化剂的结构和性质。结果表明,HY与HZSM-5复合后HY型分子筛完全被HZSM-5紧密包裹,形成致密的核壳结构。与机械混合物相比,复合分子筛微孔比表面积及孔体积均有所减少,总酸量略高,弱酸量小,而强酸量大,Br9nsted酸量与之相似,而Lewis酸量有所减少。将所制备的HY/ZSM-5复合分子筛催化剂应用于以离子液体氯化1-乙基-3-甲基咪唑鎓([Emim]Cl)为溶剂的纤维素水解反应中,与HY催化的纤维素水解相比,HY/ZSM-5催化纤维素水解反应获得的最佳葡萄糖收率由28.04%提高到38.78%,葡萄糖选择性由28.91%提高至48.29%。     

Ni2P/HZSM5上噻吩加氢脱硫性能研究

采用程序升温还原方法制备了Ni2P/HZSM5催化剂。用X射线衍射 (XRD)、低温N2吸附（BET）、扫描电镜(SEM)等技术对催化剂样品的物相、比表面积、形貌等性质进行了表征。在连续微反系统中测定了Ni2P/HZSM5催化剂对噻吩加氢脱硫催化活性；研究了Ni2P负载量、前驱体中Ni/P摩尔比对催化剂的物相及性能的影响，考察了空速、反应温度、反应压力等操作条件对催化剂上噻吩加氢脱硫性能的影响。实验结果表明，Ni2P/HZSM5催化剂对噻吩加氢脱硫反应具有较高的活性和稳定性。随着Ni2P负载量、前驱体中Ni/P摩尔比的增加，催化剂的活性和稳定性先升高后降低。反应温度和体积空速对Ni2P/HZSM5催化剂的噻吩加氢脱硫性能有较明显的影响，反应压力和进料氢油比的影响相对较小。     

PtSnNa/SUZ-4:丙烷脱氢反应的高效催化剂

丙烷脱氢制丙烯是优化利用炼厂气和油田伴生气资源的一条重要途径.随着丙烯需求量的逐步增加,丙烷脱氢制丙烯日益受到重视.负载型PtSn/γ-Al2O3催化剂具有优良的丙烷脱氢活性和选择性,但在高温、低氢压的反应条件下,催化剂易积炭而失活.近年来,选用了微孔分子筛如ZSM-5和介孔分子筛如SBA-15和MCM-41作为PtSn催化剂的载体,结果表明,具有规整孔道结构的负载型PtSn/分子筛催化剂的丙烷脱氢反应稳定性明显优于PtSn/γ-Al2O3催化剂.SUZ-4分子筛与ZSM-5分子筛结构相似且孔径相当,所不同的是ZSM-5由十元环交叉孔道组成,而SUZ-4由十元环和八元环孔道垂直相交组成.我们用微型催化反应装置结合XRD、BET比表面积和孔体积测试、NH3吸附-程序升温脱附(NH3-TPD)、氢化学吸附、热重分析(TG)、H2程序升温还原(H2-TPR)和程序升温氧化(TPO)等多种物理化学手段研究了负载型PtSnNa/SUZ-4和PtSnNa/ZSM-5催化剂的结构和丙烷脱氢反应性能,以及这两种催化剂在丙烷脱氢反应中催化性能差异的原因.实验结果显示,在丙烷脱氢反应中,负载型PtSnNa/SUZ-4催化剂上丙烯选择性和反应稳定性明显优于PtSnNa/ZSM-5催化剂,说明载体一定程度上会影响催化剂上丙烷脱氢反应性能.XRD,BET比表面积和孔体积测试等表征手段结果表明,SUZ-4和ZSM-5的孔体积和比表面积比较接近,载体的结构又类似,且两者的积碳量也相近,故载体的基本性质和积碳量的差异不是引起催化剂性能差异的原因.NH3-TPD结果表明,H-SUZ-4的酸强度明显强于H-ZSM-5.由于浸渍法制备负载型PtSn催化剂所用前体为具有强酸性的混合溶液(H2PtCl6+SnCl4),存在于SUZ-4分子筛孔道内表面的强酸中心不利于上述前体与SUZ-4分子筛孔道内表面结合.ZSM-5分子筛孔道内表面比较弱的强酸中心,促进了催化剂前体在ZSM-5分子筛孔道内表面的分散与结合.和ZSM-5为载体的催化剂相比,PtSnNa/SUZ-4上Pt粒子大部分分散在载体的外表面,从而金属上的积碳不易引起催化剂的失活.故多孔材料上Pt的分布是影响催化活性差异的主要原因.为进一步证明多孔材料上Pt的分布是影响催化活性差异的主要原因,我们通过二苯并噻吩预处理催化剂的手段证明Pt粒子在分子筛孔内外的分布情况.由于二苯并噻吩的尺寸比较大(0.8 nm)不能进入到分子筛的孔道内(SUZ-4:0.56 nm,ZSM-5:0.56 nm),所以载体孔道外的部分Pt会被二苯并噻吩预处理而失去活性,而孔道内的Pt不会因为预处理仍具有催化活性.实验结果表明,PtSnNa/SUZ-4经过二苯并噻吩预处理后,催化活性大大降低;而PtSnNa/ZSM-5经过二苯并噻吩预处理后,催化活性几乎没有变化.说明PtSnNa/SUZ-4上Pt粒子大部分分散在载体的外表面,从而金属上的积碳不易引起催化剂的失活.     

Low-temperature activation of methane over rare earth metals promoted Zn/HZSM-5 zeolite catalysts in the presence of ethylene

At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons (C2–C4) and aromatics (C6–C10), through its reaction over rare metals modified Zn/HZSM-5 zeolite catalysts without undesirable carbon oxides formation. Methane can get 37.3% conversion over the above catalysts under low temperature, and the catalysts show a longer lifetime than usual metal supported HZSM-5 zeolite catalysts without adding any rare earth metals. The effects of methane activation over various rare earth metal promoted Zn/HZSM-5 catalysts on the products and influences of several reaction conditions such as temperature, catalyst lifetime and molar ratio of CH4/C2H4 have been discussed.     

全氢菲在分子筛催化剂上环烷环开环反应的研究

在小型固定流化床(FFB)装置上考察了Y与ZSM-5分子筛催化剂以及Y分子筛催化剂上温度、剂油比对全氢菲裂化环烷环开环反应的影响。结果表明,全氢菲在分子筛催化剂上通过环烷环开环反应生成环己烷、十氢萘等单环或双环环烷烃;单环或双环环烷烃进一步侧链断裂生成2-甲基戊烷、甲基己烷等异构烷烃等,异构化生成二甲基环戊烷、甲乙基环戊烷等烷基环戊烷,氢转移生成苯、甲苯、二甲苯等烷基苯,进行深度氢转移反应生成萘、烷基萘等双环芳烃;另外,全氢菲也会通过脱氢缩合生成菲、芘等三环以上芳烃甚至焦炭等。由于扩散和吸附性能的影响,其裂化开环反应的选择性在Y分子筛催化剂上比在ZSM-5分子筛催化剂上高。因此,全氢菲环烷环开环与脱氢缩合反应的相对比例(s(NRO)/s(DHC))在Y分子筛催化剂上较高;在Y分子筛催化剂上,温度为475~550 ℃、剂油比为3.0~9.0,反应温度升高或者剂油比增加,双分子氢转移以及脱氢缩合反应增强,导致环烷环开环反应产物选择性降低。     

Investigation of Metal State in Metal-containing Zeolite Catalysts by DTA and ESR Methods

Thermal stability and its influence on the catalytic activity in CO oxidation of Cu, Pd and Pd-Cu zeolite systems were investigated. The increasing of catalytic activity in the first cycle of reaction is connected with the thermal decomposition of complexions and consequently with the changing of metal state in catalyst in the case of Cu/ZSM-5catalyst. This activity does not relate to initial zeolite with complex ions, but to the metal ions with the decreasing ligands number in the coordination sphere of metal ion. According to the EPR spectrum the copper ions form clusters in zeolite channels due to the spin changed interaction. It was established ESR method that 1.8% Cu/ZSM-5 catalyst in a reduced form has copper (I and II) ions by. The Pd/ZSM-5 catalysts with different metal content have high catalytic activity below the temperature decomposition in contrary to Cu-containing zeolites. On the one hand, it may be connected with the partial reduction of Pd ions during CO oxidation and, on the other hand, with the ability of Pd ions to form the respective label complexes with reagents as additional ligands. The same character of relation between thermal stability and catalytic activity for Pd-Cu/ZSM-5 catalyst was observed. This revised version was published online in August 2006 with corrections to the Cover Date.     

理性设计核-壳Rh@沸石催化材料用于二烯烃选择加氢反应

Selective hydrogenation of dienes and alkynes to monoenes is an important topic of research in the fields of pharmacology and organic synthesis. Catalyst design plays a key role in this process, where a general principle involves controlling the steric diene adsorption by modifying the surface of the metal nanoparticles. For example, upon introducing Bi species into Rh nanoparticles, the resulting RhBi/SiO₂ showed 90% selectivity to 2-hexene, with 95% conversion of 1, 4-hexadiene under ambient conditions, because of the suppressed adsorption of the internal C＝C bond. However, the catalyst activity decreased remarkably; that is, the activity of the unmodified Rh/SiO₂ was about 27 times higher than that of RhBi/SiO₂. Controlled steric adsorption of the diene molecules could also be achieved by the constructing porous channels around the metal nanoparticles. For example, metal-organic framework (ZIF-8) or mesoporous silica (MCM-41) encapsulated noble metals showed high selectivity for the hydrogenation of terminal C＝C bonds. However, these catalysts had poor durability under the thermal/hydrothermal reaction/regeneration conditions. In contrast, zeolites have superior durability under harsh reaction conditions, but they are rarely used in semi-hydrogenation reactions. We recently found that metal nanoparticles fixed within zeolite crystals (e.g., ZSM-5 and Beta) efficiently catalyze the selective hydrogenation of molecules bearing multiple reducible groups. Thus inspired, we developed a catalyst by fixing Rh nanoparticles within zeolite crystals via an inter-zeolite transformation method. The Rh@CHA catalyst was synthesized by introducing Rh species into the parent Y zeolite (Rh@Y) and transformation of the Y zeolite to chabazite (CHA zeolite) under hydrothermal conditions. X-ray diffraction patterns, N₂ sorption isotherms, scanning/transmission electron microscopy images, and model reactions (hydrogenation of probe molecules) confirmed the successful fixation of the Rh nanoparticles inside the CHA zeolite crystals. As expected, the Rh@CHA catalyst was highly selective for the hydrogenation of dienes. For example, Rh@CHA showed a 2-hexene selectivity of 86.7%, with 91.2% conversion of 1, 4-hexadiene. In contrast, the generally supported Rh nanoparticle catalyst (Rh/CHA) showed a low 2-hexene selectivity of 37.2% under identical reaction conditions. Considering that Rh@CHA and Rh/CHA comprise the same CHA zeolite crystals and have similar Rh nanoparticle sizes, the remarkably high selectivity of Rh@CHA is assigned to the steric adsorption of dienes on the Rh surface controlled by the micropores of the CHA zeolite. This work demonstrates that a zeolite-fixed metal core-shell structure is a powerful tool for developing efficient catalysts to be used in diene hydrogenation.     

NiMo/Al_2O_3 catalyst containing nano-sized zeolite Y for deep hydrodesulfurization and hydrodenitrogenation of diesel

Two mixed-matrix NiMo/Al2O3 catalysts containing nano-and micro-sized zeolite Y have been prepared to explore the size effect of zeolite Y particle on the hydrodesulfurization(HDS)and hydrodenitrogenation(HDN)activities of fluid catalytic cracking(FCC)diesel.They were characterized by SEM,BET,XRD,H2-TPR,NH3-TPD and HRTEM.The results show that the catalyst containing nano-sized zeolite Y possesses larger average pore diameter,higher pore volume,weaker and lesser acid sites,more easily reducible metal phases,shorter MoS2 slabs and more slab layers than the catalyst containing micro-sized zeolite Y.The catalysts were also evaluated with a high-pressure fixed-bed reactor using real FCC diesel as feed.The results display that the catalyst containing nano-sized zeolite Y bears higher HDS and HDN activities and exhibits higher relative rate constant for the removal of total sulfur or nitrogen than the one containing micro-sized zeolite.     

Cu-Pd/MCM-22催化剂上二甲醚低温水解反应

 考察了分子筛的类型、硅铝比及Cu和Pd改性对分子筛催化剂上二甲醚低温水解活性的影响. 结果表明,酸性的MCM-22和HZSM-5分子筛催化剂具有较高的二甲醚水解活性,且其活性随着分子筛硅铝比的增加而降低. 这表明分子筛的类型及酸性对催化剂性能有重要影响,具有超笼结构的MCM-22分子筛上B酸中心的良好可接近性,使得该分子筛催化剂的水解活性较相同硅铝比的HZSM-5分子筛高. 与改性前相比, Cu和Pd改性后的MCM-22催化剂显示出更高的二甲醚水解活性.     

沸石载体结构对甲烷无氧芳构化性能的影响

考察了担载MoO₃的沸石催化剂上甲烷的无氧芳构化性能,并与沸石结构相关联.结果表明,孔径与苯分子动态直径相当的ZSM-5、ZSM-8、ZSM-11和β沸石等是甲烷无氧芳构化催化剂的良好载体,其中3%MoO₃/HZSM-11具有最高的甲烷芳构化活性和稳定性,973K下的转化率和苯选择性分别为8.0%和90.9%;6%MoO₃/HZSM-8与7%MoO₃/H-β芳构化性能相当.以HMCM-41和HSAPO-34为载体时芳构化活性很低,以HMOR、HX和HY为载体时仅有少量乙烯生成,而以HSAPO-5和HSAPO-11为载体时未检测到烃类生成.     

Pd/Hβ-zeolite catalysts for catalytic combustion of toluene: Effect of SiO2/Al2O3 ratio

The effect of pure and high silica Hβ zeolites on the catalytic performance of toluene combustion over Pd/H/3 catalyst was evaluated.Pure and high silica β zeolites were prepared by direct synthesis procedures,then 0.1 wt% of palladium was impregnated on different Hβ zeolites via incipient wetness technique using palladium nitrate as the Pd source.The Pd/Hβ catalysts were characterized by XRD,N2 adsorption/desorption,H2O adsorption,NH3-TPD,H2-TPR and XPS techniques.With increasing the SIO2/Al2O3 ratio of β zeolite,the activity of the Pd/Hβ catalysts for toluene combustion increased clearly and the pure silica β zeolite supported Pd catalyst showed the best catalytic activity.The superior catalytic performance of Pd/β catalyst prepared from pure silica β zeolite was attributed to its high hydrophobicity and the preserving ability for PdO active species.     

Confined space synthesis. A novel route to nanosized zeolites

Confined space synthesis is a novel method in zeolite synthesis. It involves crystallization of the zeolite inside the pore system of an inert mesoporous matrix. In this way it is possible to prepare nanosized zeolites with a controlled size distribution by proper choice of the inert matrix. Here, confined space synthesis was adopted to prepare nanosized ZSM-5, zeolite Beta, zeolite X, and zeolite A with tailored crystal size distributions using mesoporous carbon blacks as inert matrices. All zeolites were characterized by X-ray powder diffraction, transmission electron microscopy, and nitrogen adsorption/desorption prior to and after removal of the carbon matrix. ZSM-5 with Si/Al ratios of 50, 100, and infinity (silicalite-1) were synthesized with controlled average crystal sizes in the range 20-75 nm. Nanosized zeolite Beta (7-30 nm), zeolite X (22-60 nm), and zeolite A (25-37 nm) were prepared similarly. Removal of the carbon matrix by controlled combustion allows a convenient method for isolation of the pure and highly crystalline zeolites. Therefore, confined space synthesis appears to be an attractive method for preparation of zeolites with a controlled size distribution.     

十氢萘在分子筛催化剂上的开环反应研究

在小型固定流化床(FFB)装置中研究了Y分子筛与ZSM-5分子筛催化剂上的十氢萘裂化开环反应性能,考察了温度和剂油比对Y分子筛开环反应催化性能的影响。结果表明,十氢萘在分子筛催化剂上通过环烷环开环反应生成丙烷、丙烯、丁烷、丁烯、甲基戊烷和环戊烷、环己烷等非芳烃以及苯、C_1~4烷基取代苯等单环芳烃,并通过脱氢缩合反应生成四氢萘、萘、甲基萘和菲、芘等多环芳烃甚至焦炭等。由于扩散和吸附性能的影响,ZSM-5分子筛催化剂的裂化开环反应选择性比Y分子筛催化剂的高,因此,十氢萘环烷环开环与脱氢缩合反应的相对比例(NRO/DHC)在ZSM-5分子筛催化剂上较高。在Y分子筛催化剂上,温度为450~550 ℃、剂油比为3~9,反应温度升高或者剂油比增加,双分子氢转移以及脱氢缩合反应增强,从而导致环烷环开环产物选择性降低。     

Distribution of copper- and nickel-containing modifier components in the pore space of HZSM-5 zeolite

The distribution of copper- and nickel-containing components in the pore space of HZSM-5 zeolite was quantitatively studied. It was found that the detailed distribution of a modifier in the micropore and mesopore volumes of the zeolite depends on both the chemical nature of the modifier and the conditions of supporting and the regime of M²⁺ polycondensation in the pore space of the zeolite. The experimental data on the low-temperature adsorption of nitrogen on Cu(n)ZSM-5 catalysts can be interpreted as the result of the partial filling of the zeolite micropore space (10 vol %) and the finest mesopores with D < 3 nm with the modifier. In the case of Ni(n)ZSM-5 catalysts, the penetration of the modifier into zeolite channels (micropores) in detectable amounts was not found, and it was arranged in mesopores on the surface of zeolite crystallites. The reason for differences between modifier distributions in the pore structure of the zeolite was explained from the standpoint of different structures of copper and nickel polyhydroxo complexes in impregnating solutions after polycondensation. It was found that, in the Cu(n)ZSM-5 and Ni(n)ZSM-5 catalysts, the modifier component contained copper and nickel only in a doubly charged state and mainly octahedral oxygen environments. In this case, three-dimensional nanoparticles or coarsely dispersed particles of CuO were not detected in the pore space of the support, whereas the presence of a small amount of sufficiently large NiO crystals with a coherent-scattering region of 80–100 nm was detected in Ni(n)ZSM-5, and these crystals occurred on the surface of zeolite crystals. It was found that the apparent density of a copper-or nickel-containing component arranged in the pore space of the zeolite was lower than the density of the bulk CuO and NiO phases by a factor of ～3 and 4, respectively, because of the size effect.