Beta分子筛研究进展

Beta分子筛是一种结构独特的催化材料,其在石油炼制及精细化工中得到了广泛应用,本文综述了Beta沸石的多种合成工艺路线、以及结构表征方法的相关进展,这对Beta分子筛的合成发展有着积极的意义。     

Beta沸石/炭复合膜的气体分离效果研究

沸石/炭分子筛复合膜具有较优良的气体分离效果,是一种非常有发展潜力的膜材料。本研究分别用纳米Beta分子筛和Beta沸石纳米团聚体合成了Beta沸石/炭复合膜,结果表明,Beta沸石纳米团聚体所制备的复合膜的气体分离性能优于纳米Beta分子筛所制备的复合膜。     

以天然硅铝质黏土矿物为原料制备沸石分子筛及其应用

沸石分子筛是一种具有规则孔道结构的硅铝酸盐晶体,在气体吸附分离、工业催化、重金属离子污染治理等领域被广泛应用。传统沸石分子筛的水热合成常以含硅、铝的化工产品以及有机模板剂为原料,不仅价格昂贵,且污染环境。因此,开展以天然黏土为原料绿色合成沸石分子筛的相关研究,将廉价的天然黏土资源转化成高附加值的化工产品,具有重要的研究意义与经济效益。从天然黏土活化工艺、黏土基沸石合成工艺技术及相关机理等方面介绍了黏土基沸石分子筛的研究进展,重点综述了黏土基沸石分子筛作为工业固体酸催化剂、气体吸附分离反应器及重金属吸附剂的应用,并对黏土基沸石分子筛的未来发展趋势进行了展望。     

纳米Beta沸石的合成与表征及催化苯和丙烯烷基化性能

合成了纳米Beta沸石,并采用X射线衍射(XRD)、透射电镜(TEM)、比表面(BET)、程序升温脱附(NH3-TPD)以及吡啶-红外光谱(Py-IR)等方法对其结构和酸性进行了表征。比较了纳米Beta和常规大晶粒Beta沸石的催化性能,对纳米Beta沸石催化烷基化的关键参数进行了优化。结果表明:在硅铝物质的量比为25~30时,所合成的纳米Beta沸石具有较高的结晶度,晶粒尺寸在20 nm左右。同常规Beta沸石相比,纳米Beta沸石具有更大的BET比表面积和孔容,其比表面积可达600 m2/g,总孔容达0.42 cm3/g,介孔和大孔贡献超过50%。纳米Beta沸石具有较高的总酸量和B酸含量。作为苯和丙烯的烷基化催化剂,纳米Beta沸石具有更好的反应稳定性和选择性。在苯烯比3.0,反应温度150~160℃的条件下,异丙苯选择性可达89%,杂质正丙苯含量可降到极低水平。在工业试验中,纳米Beta沸石也表现出良好的综合性能,催化剂的稳定性和选择性优于同类Beta沸石催化剂。     

金刚烷的研究进展及应用现状

本文综述了金刚烷的几个主要应用领域,几种技术路线,以及目前的市场现状。通过几种主要工艺技术对比,得出Al Cl3催化异构化法和沸石催化法仍将是未来主要工艺路线。随着原料的供给富裕,金刚烷及衍生物的合成技术及应用领域将进一步拓宽。     

介微材料孔Beta-KIT-6的合成及影响因素探析

采用纳米组装法,在酸性条件下,以Beta沸石微晶为原料,P123和正丁醇为介孔导向剂,合成出Beta-KIT-6介微孔复合材料。分析了合成过程中Beta-KIT-6介孔有序度不同的原因。探索了正丁醇用量、HCl浓度、Beta沸石微晶质量分数对介微孔复合材料Beta-KIT-6介孔有序度的影响。结果表明:当正丁醇和TEOS摩尔比为1.5,正丁醇和P123质量比为100,HCl浓度为0.75 mol/L,Beta/P123质量比为88时,所合成的介微孔复合材料具有较好的介孔有序度。     

利用煤矸石制备4A沸石的方法

煤矸石是采煤和洗煤过程产生的废弃物。主要矿物学成分为高岭土的煤矸石,由于硅铝成分与4A沸石相近适用于制备4A沸石。以煤矸石为原料制备4A沸石的主要3种方法：水热法、熔融法和碱溶法。比较了水热法、熔融法和碱溶法等各自工艺路线的优点及产品质量;选择价格低廉、较短工艺路线成为未来研究的重点。     

水热晶化法合成Beta沸石分子筛的研究

Beta沸石分子筛是一种具有三维十二元环孔结构的高硅沸石分子筛,具有独特的催化性能,在石油炼制及精细化工中有着广泛的应用。本文以四乙基溴化铵(TEABr)和四乙基氢氧化铵(TEAOH)为模板剂,以硅溶胶或硅胶粉末为硅源,以铝酸钠为铝源通过水热晶化法合成了Beta分子筛,并通过XRD等手段对合成样品进行表征。同时详细考察了模板剂浓度、晶化温度、晶化时间等因素对Beta分子筛晶化过程的影响,得到了合成Beta分子筛的最佳合成条件。     

廉价矿物合成沸石分子筛的研究进展

介绍了由廉价矿物合成沸石分子筛的矿物原料种类、原料的预处理方法和合成沸石分子筛的类型,并对廉价矿物合成沸石分子筛的未来发展进行了展望。     

4A沸石的生产和应用

介绍了目前世界上生产4A沸石的各种工艺概况和工艺路线的优缺点。重点介绍了采用铝矾土或高岭土为原料，经烧结成熟料，再用碱溶解形成铝酸钠，不用补加吕源，或直接用氢氧化铝做铝源，在适宜的合成条件下，与硅酸钠直接合成4A沸石，产品质量达到洗涤剂用4A沸石的国家标准。并简单介绍了生产4A沸石的不同合成条件、不同晶化条件对产品质量的影响和4A沸石的化学组成、性能特点以及应用。     

粉煤灰基沸石的制备及应用研究进展

粉煤灰是燃煤电厂产生的固体废弃物,其主要成分中包含大比例的SiO₂、Al₂O₃,是合成沸石的理想原料。粉煤灰合成沸石的方法随着研究的深入而逐渐成熟,从起初的一步水热法到现在的复合水热法,从以未经处理的粉煤灰为原料到现在使用预处理过的粉煤灰为原料,粉煤灰合成沸石的工艺一直在进步。从粉煤灰的预处理、合成沸石方法、产物应用领域三方面综述了研究进展,并对其整体发展趋势进行了展望。     

Practical Application of Hierarchical Beta Zeolite in a Vacuum Gas Oil Hydrocracking Catalyst

A hierarchical Beta zeolite has been successfully mass-prepared hydrothermally and dynamically in a pilot-scale autoclave by an economical and simple process with low-cost raw materials. The characterization results indicated that the pilot-scale hierarchical Beta zeolite has the same textural, structural, and acidic properties like the bench-scale sample. Moreover, the catalyst composed of the pilot-scale hierarchical H-Beta zeolite showed higher activity and selectivity to the middle distillate than that containing microporous Beta zeolite in catalytic hydrocracking of vacuum gas oil (VGO) evaluated by an industrial pilot installation in running of 3000 h, due to the increased accessibility and the reduction of diffusion constraint of large molecules to acid sites in the Beta zeolite framework.     

Synthesis of NaA zeolite from kaolin source

In this work, zeolite NaA was successfully synthesized by a hydrothermal method using kaolin as a combined source for silica and alumina. Zeolite NaA with high static water adsorption was synthesized from the low-cost raw material, kaolin, and the reaction parameters were optimized. Metakaolin was obtained by calcining kaolin at temperatures ranged from 953 K to 1173 K. The synthesis mixture was pre-crystallized at 343 K and crystallized at 373 K successively. Zeolite NaA was obtained, which was confirmed by SEM, XRD and the water adsorption analysis. The optimized metakaolinization temperature was found at 973 K. The influence of Na₂O/SiO₂ molar ratio, pre-crystallization time and seed on the crystallization of NaA zeolite was investigated. A thorough mixing of metakaolin and NaOH solution was favourable for the nucleation/crystallization rate. The obtained NaA zeolite under the optimized conditions shows excellent crystallinity and static water adsorption of 28.0 wt-%, which was higher than 25.9 wt-% of the commercial NaA zeolite. Kaolin was suggested to be a feasible and economical raw material for the practical industrial applications for NaA zeolite.     

MIL-53/4A沸石复合材料的制备及吸附水性能的研究

通过水热合成法制备4A沸石分子筛,在4A沸石分子筛上制备了金属有机骨架(MIL-53)/4A沸石复合材料,研究了原材料配比、晶化时间和晶化温度对复合材料结构的影响,得到了制备复合材料结构的最佳实验条件:4A与对苯二甲酸摩尔比例为0.8:1,晶化时间为10 h,晶化温度为443 K.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)、氮气吸附对该复合材料进行表征,并对该材料吸附水蒸气性能进行了测试.结果表明该复合材料具有微孔的孔道结构,并具有较好的亲水性.     

Modification of carbon membranes and preparation of carbon-zeolite composite membranes with zeolite growth

A novel method for the modification of carbon membranes was developed by zeolite growth on the surface of porous carbon tubes using a hydrothermal synthesis method and carbon-zeolite composite membranes were successfully obtained. Zeolite seeds for the zeolite growth were introduced to the inner surface of the tubes by using a slip-casting technique in 1 wt.% seed ethanol solution and continuous and highly intergrown zeolite layers on the seeded tubes were formed by subsequent hydrothermal synthesis. Different types of zeolite layers can be grown on porous carbon tubes by using different types of zeolite seeds. Without zeolite seeds, a zeolite layer could not be formed on the carbon surface. SEM, XRD and pure gas permeation characterization indicates that the carbon-zeolite membranes are continuous and defect-free.     

BETA zeolite nanowire synthesis under non-hydrothermal conditions using carbon nanotubes as template

The properties of carbon nanotubes, used as a nanometric template and as a reactor for the synthesis of BETA zeolite, have been investigated. The confinement effect of the carbon nanotubes, induced by the high aspect ratio of the tubes could be effectively used for the synthesis of one-dimensional nanowire zeolitic materials under non-hydrothermal macroscopic conditions. Zeolite material is easily recovered by combustion of the nanotubes. The average sizes of the zeolite particles are about 20 nm. The BETA zeolite was successfully used as a catalyst for benzoylation of anisol. The zeolite catalyst exhibits a high activity compared to a commercial BETA, essentially due to its high external surface area.     

哌嗪合成新工艺

以乙二胺为原料气固相催化合成哌嗪和三乙烯二胺,对实验用催化剂进行制备与考察,筛选出用CaC l2改性的HZSM-5型分子筛为催化剂,确定了最佳工艺条件为:反应温度为340℃,乙二胺的质量分数为40%,进料流率为0.40 mL/m in。结果表明:合成采用CaC l2改性的HZSM-5型分子筛,以乙二胺为原料合成哌嗪的工艺路线是可行的,在最佳工艺条件下,乙二胺的转化率为95%,哌嗪的收率为65%,三乙烯二胺的收率为25%。     

磁性Fe_3O_4/Beta沸石复合材料制备及其水体磷污染物吸附行为研究

自制得到磁性Fe3O4/Beta沸石复合材料,并通过SEM、XRD、FT IR,磁滞回线表征鉴定,相应最佳吸附除磷实验条件为:0.05g磁性Fe3O4/Beta沸石复合材料对5mL,50mg/L PO34-溶液(pH值为3.0)吸附率近100%,吸附平衡时间为6h,吸附行为符合Freundlich方程,可在碱性介质溶液中脱附再生。磁性Fe3O4/Beta沸石复合材料基于磁基质易于水体分离操作,过程简便可控,实际应用前景广阔。