分子筛酸性对异丁烷/丁烯烷基化反应性能的影响研究进展

概述分子筛的酸性特点,介绍固体酸催化的异丁烷/丁烯烷基化反应机理,并对已用于异丁烷/丁烯烷基化反应的分子筛情况进行总结,重点阐述分子筛的酸性对烷基化反应性能的影响。结果表明,分子筛应有合适的酸强度,综合来看,中强B酸更有利于反应。今后的机理研究中应当关注L酸及酸位空间分布对烷基化反应的影响。

烯烃在酸性分子筛上的裂化反应研究进展

烯烃在酸性分子筛上的裂化反应能够将C_(4+)烯烃转化为高价值的乙烯和丙烯。调研了烯烃裂化反应的研究现状和发展趋势,对烯烃裂化反应机理、动力学、热力学和催化剂等方面的研究进展进行了详细归纳。在反应机理方面,对烯烃裂化反应中间体的类型和反应路径进行了详细的论述。在动力学方面,主要总结了不同β-裂解模式反应速率的差别。在热力学方面,重点介绍反应温度和压力对烯烃裂化反应产物平衡组成的影响。在催化剂方面,重点总结分子筛的孔结构、酸强度、酸量和酸位置等对烯烃裂化反应路径及产物分布的影响。通过对烯烃裂化反应研究现状的分析,指出烯烃裂化反应过程中乙烯/丙烯比较低的问题,并提出烯烃裂化反应技术在工艺和催化剂调控等方面的发展方向。

酸性分子筛上甲醇催化转化反应机理研究进展

概括了甲醇转化反应机理实验和理论研究方法,介绍了甲醇脱水预平衡阶段的主要机理模型和实验理论依据,重点综述了C-C键形成过程中涉及到的直接机理和"烃池"机理的实验与理论研究进展和存在的问题,探讨了分子筛孔道结构对"烃池"物种结构和反应历程的影响。

酸性沸石分子筛催化Knoevenagel缩合反应

在高硅 /铝比的酸性沸石分子筛HY上实现了Knoevenagel缩合反应 .Br nsted酸和Lewis酸均可催化Knoevenagel缩合反应 .考察了羰基化合物和活泼亚甲基化合物的反应活性顺序 .结果表明 ,羰基化合物的羰基极化程度越高 ,反应越容易进行 ;不同于碱催化时的Knoevenagel缩合反应 ,活泼亚甲基化合物的活泼氢的酸性并不是影响其反应活性的重要因素 .

二甲醚在酸性分子筛上的低温水解

考察了几种酸性分子筛MCM-41、SAPO-34、ZSM-5和MCM-22上二甲醚的低温水解反应性能。结果发现,分子筛的种类和硅铝比均影响着催化剂上二甲醚水解反应的催化活性,其顺序为:MCM-41<<SAPO-34<HZSM-5(n(Si)/n(Al)=25)<HZSM-5(n(Si)/n(Al)=19)<HZSM-5(n(Si)/n(Al)=13)<MCM-22(n(Si)/n(Al)=13)。150℃时,MCM-22(n(Si)/n(Al)=13)催化水解反应的甲醇收率为9.69mmol.g-1.h-1,水的转化率为36.11%。

酸性分子筛合成对叔丁基邻苯二酚

以邻苯二酚、异丁烯为原料,酸性分子筛为催化剂催化合成对叔丁基邻苯二酚,探讨了各工艺条件对反应结果的影响,确定了最优反应条件。反应温度140℃,反应时间8 h,物料配比n(邻苯二酚)/n(异丁烯)=1∶1.2,催化剂质量分数为20%,对叔丁基邻苯二酚收率均可达85%以上,催化剂可重复使用30次以上。

二次水热合成法制备ZSM-5分子筛膜及其渗透汽化性能

采用二次水热合成法在管状多孔莫来石支撑体上制备高耐酸性ZSM-5分子筛膜,系统地研究分子筛晶种和合成溶胶中H_2O/SiO_2摩尔比率对ZSM-5分子筛膜生长与渗透汽化性能的影响,采用X射线衍射、冷场扫描电子显微镜和电子能谱等表征技术分别对制备的ZSM-5分子筛及其ZSM-5分子筛膜的结构、形貌和Si/Al比进行表征。针对分离75℃、90%HAc/H_2O的水溶液,最优化条件下制备的ZSM-5分子筛膜表现出优良的渗透汽化性能,渗透通量和分离因子分别为0.98kg/(m2·h)和890。此外,本研究所采用制备耐酸性ZSM-5分子筛膜的方法表现出良好的重现性,重复制备的12根ZSM-5分子筛膜在75℃下分离90%HAc/H_2O的水溶液时,平均通量和分离系数分别为(0.85±0.15)kg/(m2·h)和650±290。再者,ZSM-5分子筛膜在45~75℃的温度范围内分离50%~95%HAc/H_2O水溶液时都表现出优良的渗透汽化性能。

Alkylation of toluene with tert-butyl alcohol over HPW-modified Hβ zeolite

An Hβ-supported heteropoly acid （H3PW12O40 （HPW）/Hβ） catalyst was successfully prepared by wetness impregnation, and investigated in the alkylation of toluene with tert-butyl alcohol for the synthesis of 4-tert-butyltoluene （PTBT）. X-ray diffraction, scanning electron microscopy, transmis- sion electron microscopy, fourier-transform infrared spectroscopy, inductively coupled plas- ma-optical emission spectrometry, the brunauer emmett teller （BET） method, tempera- ture-programmed NH3 desorption, and pyridine adsorption infrared spectroscopy were used to characterize the catalyst. The results showed that loading HPW on Hβ effectively increased the B acidity and decreased the pore size of Hβ. The B acidity of HPW/Hβ was 142.97 μmol/g, which is 69.74% higher than that of Hβ （84.23 μmol/g）. The catalytic activity of the HPW/Hβ catalyst was much better than that of the parent Hβ zeolite because of its high B acidity. The toluene conversion over HPW/Hβ reached 73.1%, which is much higher than that achieved with Hβ （54.0%）. When HPW was loaded on Hβ, the BET surface area of Hβ decreased from 492.5 to 379.6 m2/g, accompa- nied by a significant decrease in the pore size from 3.90 to 3.17 nm. Shape selectivity can therefore play an important role and increase the product selectivity of the HPW/Hβ catalyst compared with that of the parent Hβ. PTBT （kinetic diameter 0.58 nm） can easily diffuse through the narrowed pores of HPW/Hβ, but 3-tert-butyltoluene （kinetic diameter 0.65 nm） diffusion is restricted because of steric hindrance in these narrow pores. This results in high PTBT selectivity over HPW/Hβ （around 81%）. The HPW/Hβ catalyst gave a stable catalytic performance in reusability tests.

蒽与叔丁醇Friedel-Crafts烷基化反应

分子筛催化剂是一种高效、环保、绿色的具有特定空间结构的固体酸催化剂,被广泛应用于石油化工和有机合成等领域。利用离子交换方法合成了一种酸性微孔β分子筛催化剂,并且研究了该分子筛催化剂催化蒽与叔丁醇的Friedel-Crafts烷基化反应,通过GC-MS、FT-IR、1H-NMR、元素分析等手段对反应产物进行了细致的表征。在此基础上,对蒽与叔丁醇的Friedel-Crafts烷基化反应机理进行了初步的探讨。结果表明,所合成的酸性分子筛催化剂具有较高的催化活性,异辛烷不仅仅作为反应溶剂,还能与分子筛形成叔丁基碳正离子促进反应进行,反应主要生成2-叔丁基蒽和2,6-二叔丁基蒽两种产物,具有很好的工业应用前景。

Effects of acid pretreatment on Fe-ZSM-5 and Fe-beta catalysts for N_2O decomposition

Two series of ZSM-5 and beta zeolites were pretreated in 1.0 mol/L HNO3 solution at room temper-ature for various time periods. The catalytic performances of their Fe-exchanged products in N2O decomposition were evaluated. The Fe-zeolite catalysts were characterized using N2 adsorp-tion-desorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, ultra-violet-visible spectroscopy, temperature-programmed desorption of NH3, and scanning and trans-mission electron microscopies. For the ZSM-5 zeolite, acid leaching primarily takes place on the crystal surface and the particle size is reduced, therefore the pore channels are shortened. However, because of the good stability of MFI zeolites, the acid does not greatly penetrate the pore channels and new mesopores are not created. For the beta zeolite, because the amorphous material is in-clined to dissolve（deagglomerate）, some of the micropores are slightly dilated. The improved cata-lytic activities can be explained by the increased active Fe loading as a result of structural changes.

One‐step aldol condensation reaction of dimethoxymethane and methyl acetate over supported Cs/ZSM‐35 zeolite catalysts

This study was performed for the development of a green and promising approach for the synthesis of methyl acrylate and acrylic acid by a one‐step aldol condensation reaction of dimethoxymethane and methyl acetate over cesium oxide‐supported on ZSM‐35 zeolite catalysts; the effect of base sites as well as acid sites on the aldol condensation reaction was studied in detail. It was found that base sites were harmful for aldol condensation due to their failure in catalyzing the decomposition of dimethoxymethane precursor into formaldehyde, whereas the acid site was indispensable for the reaction to proceed. This reaction cannot take place without an acid site. Although acid sites in H‐form of the zeolite（HZSM‐35） are indispensable for the aldol condensation reaction, not all of them tend to favor this reaction. A strong acid catalyzes methanol‐to‐olefin‐like reactions resulting in hydrocarbon byproducts, which are finally transferred to hard coke. Medium strong acids and weak acids are great candidates for the target aldol condensation reaction with high activity and selectivity. A γ‐Al2O3 sample with abundant weak‐strength Lewis acid sites, together with a few medium‐strong‐strength acid sites, performs well with a high activity and considerable stability during the synthesis of methyl acrylate and acrylic acid.

Effects of Colloidal Silica Binder on Catalytic Activity and Adhesion of HZSM-5 Coatings for Structured Reactors

HZSM-5 coating using three colloidal silica binders, acidic colloidal silica （ACS）, neutral colloidal silica （NCS） and basic colloidal silica （BCS）, was prepared to study the effect of hinders on their adhesion and catalytic activity. Scanning electron microscopy characterization indicated that the zeolite coating using BCS shows the smoothest surface with higher homogeneity and adherence strength. The specific surface area, relative crystallization and acid site strength of zeolites are also dependent on the binder used. Catalytic cracking of supercritical n- dodecane over the series of zeolite coating with various binders indicated that HZSM-5 coating with BCS exhibits the highest and the most stable catalytic activity compared with other kinds of binders, and also exhibits a stable catalytic activity ascribed to its proper acid property and microstructure.

External surface modification of as-made ZSM-5 and their catalytic performance in the methanol to propylene reaction

Post-synthetic treatment of high-silica as-made ZSM-5 with organic template in the micropores was explored to reduce/remove the external surface acid density of ZSM-5. It is found that Na_2H_2 EDTA treatment can selectively remove the surface Al atoms, but generates new acid sites（likely silanol nests） on the external surface. H_3PO_4 treatment is unable to remove surface Al atoms, while small amount of P is left on the external surface, which effectively decreases the acid density. The catalytic performance of the resultant materials is evaluated in the methanol conversion reaction. H_3PO_4 treatment can effectively improve both the catalytic lifetime and the stability of propene selectivity.This occurs due to a combination of the increased tolerance to the external coke deposition and the depressed coking rate（reduced side reactions）. Na_2H_2 EDTA treatment only prolongs the catalytic lifetime, resulting from the improved tolerance to the external coke deposition. Under the optimized H_3PO_4 treatment condition, the resultant ZSM-5 gives a catalytic lifetime of about 1.5 times longer than the precursor. Moreover, the propene selectivity is improved, showing a slight increasing trend until the deactivation.

Synthesis of ZSM-5 monoliths with hierarchical porosity through a steam-assisted crystallization method using sponges as scaffolds

Self‐supporting ZSM‐5crystals with hierarchical porosity were prepared through a steam‐assisted crystallization method using sponges as rigid scaffolds.The synthesized materials were characterized by X‐ray diffraction,nitrogen sorption,scanning electron microscopy,transmission electron microscopy,solid‐state nuclear magnetic resonance spectroscopy and ammonia temperature‐programmed desorption.The ZSM‐5monoliths exhibited high crystallinities,hierarchical porous structures and strong acidities.They showed superior catalytic performance in the liquid‐phase esterification reaction between benzyl alcohol and hexanoic acid.

Physicochemical Properties and Catalytic Performance of a Novel Aluminosilicate Composite Zeolite for Hydrocarbon Cracking Reaction

A novel micro-micro/mesoporous aluminosilicate ZSM-5-Y/MCM-41 composite molecular sieve with a MCM-41 type structure was synthesized through a novel process of the self-assembly of CTAB surfactant micellae with silica-alumina source originated from alkaline treatment of ZSM-5 zeolite. The physical properties of the ZSM-5- Y/MCM-41 composite molecular sieve were characterized by XRD, Py-FTIR and N2 adsorption-desorption techniques. Different kinds of molecular sieves including ZSM-5, Y zeolite, AI-MCM-41, ZSM-5/MCM-41 and ZSM-5-Y/MCM- 41 as cracking catalysts were investigated, using 1,3,5-triisopropylbenzene （1,3,5-TIPB） as the probe molecule. Catalytic tests showed that the ZSM-5-Y/MCM-41 composite molecular sieve exhibited higher catalytic activity compared with the microporous ZSM-5 zeolite, Y zeolite, mesoporous A1-MCM-41 molecular sieve and ZSM-5/MCM-41 composite molecular sieve under the same conditions. The remarkable catalytic activity was mainly attributed to the presence of the hierarchical pore structure and proper acidity in the ZSM-5-Y/MCM-41 composite catalyst. Meanwhile, a carbcnium ion mechanism was put forward for the cracking of 1,3,5-TIPB.

Synthesis of Mesoporous Chromium Silicates Molecular Sieves in Strong Acidic Media by Assembly of Preformed CrS1 Precursors with Triblock Copolymer

Chromium-incorporated mesoporous silica materials （MCrS） have been successfully prepared in strong acidic media by assembly of preformed CrSI precursors with triblock copolymer of the Pluronic type （P123） by a two steps procedure. Various techniques including XRD, N2 adsorption, FT-IR spectroscopy, diffuse reflectance UV-vis （DRUV-vis） and EPR were employed for the materials characterization. MCrS materials have a hexagonal structure with uniform mesopores and contain Cr（V） and Cr（VI） under low and high Cr content and that the mesoporous walls contain the MFI structure building units.

An integrated approach to the key parameters in methanol‐to‐olefins reaction catalyzed by MFI/MEL zeolite materials

Identification of the catalyst characteristics correlating with the key performance parameters including selectivity and stability is key to the rational catalyst design. Herein we focused on the identification of property-performance relationships in the methanol-to-olefin(MTO) process by studying in detail the catalytic behaviour of MFI, MEL and their respective intergrowth zeolites. The detailed material characterization reveals that both the high production of propylene and butylenes and the large Me OH conversion capacity correlate with the enrichment of lattice Al sites in the channels of the pentasil structure as identified by 27 Al MAS NMR and 3-methylpentane cracking results. The lack of correlation between MTO performance and other catalyst characteristics, such as crystal size, presence of external Brønsted acid sites and Al pairing suggests their less pronounced role in defining the propylene selectivity. Our analysis reveals that catalyst deactivation is rather complex and is strongly affected by the enrichment of lattice Al in the intersections, the overall Al-content, and crystal size. The intergrowth of MFI and MEL phases accelerates the catalyst deactivation rate.

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH_(3)-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.