用不含有机模板剂的晶化液在多孔α-Al2O3管上合成ZSM-5沸石膜

采用不含有机模板剂的晶化液在平均孔径为2μm的多孔α-Al2O3管上合成了ZSM-5沸石膜.纳米ZSM-5沸石晶种的摩尔组成为9TPAOH25TEOS0.25 Al2O3480H2O.多孔α-Al2O3载体管外表面用这些粒度为100nm左右的晶种悬浮液浸涂、干燥后,依据纳米ZSM-5沸石晶种的DTA/TG进行煅烧,在不含有机模板剂的摩尔组成为67Na2OAl2O3240SiO26000H2O晶化液中合成了ZSM-5膜.XRD确定膜晶体为ZSM-5沸石,SEM表明沸石膜无缺陷,膜厚度约为8μm.制备的ZSM-5沸石膜H2的渗透率为1.50×10-6mol.m2·S-1.Pa-1,理想分离因数αH2/N2为3.85左右.     

汽相转化法制备纳米晶组成的块状ZSM-5多孔沸石

在ZSM-5沸石前驱体中加入羧甲基纤维素钠并制得干胶, 然后通过蒸汽相转化制得了大块状ZSM-5沸石。由于羧甲基纤维素钠与硅铝物种之间的相互作用干扰了沸石晶体的正常生长, 这种干扰所产生的“键阻断”作用导致合成的大块状ZSM-5沸石由100~150 nm的初级ZSM-5沸石晶体组成, 在这些初级粒子之间存在2~20 nm的二次介孔结构。异丙苯催化裂化结果表明, 由于纳米沸石具有较高的外表面积和较大的介孔孔容, 比参比催化剂表现出更高的异丙苯转化率。     

气相转移法制备多孔双相沸石复合物

采用气相转移法制备了同时含有Y和ZSM-5沸石的双相沸石复合物。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、N₂吸附-脱附和骨架红外(FT-IR)等手段对合成的样品进行了表征。结果表明, 合成的样品受Y型沸石的添加量、干胶制备条件和气相转移法转化条件的影响; 水热预处理后的ZSM-5沸石前驱体中具有ZSM-5沸石的骨架特征振动峰, 归结于ZSM-5沸石晶核或微晶的形成, 这有利于在气相转移法转化过程中引导或促使体系向ZSM-5沸石相的转变, 并有利于抑制ZSM-35杂晶的形成; Y型沸石在蒸汽处理过程中的脱铝过程导致合成的沸石复合物具有介孔结构。     

用不含有机模板剂的晶化液在多孔α-Al2O3管上合成ZSM-5沸石膜

采用不含有机模板剂的晶化液在平均孔径为2μm的多孔α-Al₂O₃管上合成了ZSM-5 沸石膜.纳米ZSM-5沸石晶种的摩尔组成为9TPAOH:25TEOS:0.25 Al₂O₃:480H₂O.多孔α-Al₂O₃载体管外表面用这些粒度为100nm左右的晶种悬浮液浸涂、干燥后,依据纳米ZSM-5 沸石晶种的DTA/TG进行煅烧,在不含有机模板剂的摩尔组成为67Na₂O:Al₂O₃:240SiO₂: 6000H₂O晶化液中合成了ZSM-5膜.XRD确定膜晶体为ZSM-5沸石,SEM表明沸石膜无缺陷,膜厚度约为8μm.制备的ZSM-5沸石膜H₂的渗透率为1.50×10-6mol·m²·s^-1·Pa^-1,理想分离因数α_H/N2为3.85左右.     

天然沸石及沸石类分子筛

介绍了方沸石、斜发沸石、浊沸石、毛沸石、钙交沸石、菱沸石、丝光沸石、辉沸石、片沸石等常见天然沸石的结构、性能和开发应用情况;并对钛硅沸石、微孔-大孔双孔结构β沸石、手性沸石及ZSM-5沸石薄膜这几种典型沸石类分子筛材料的合成方法和特性作了介绍;针对目前对沸石的研究和应用现状提出了几点建议.     

ZSM-5分子筛介孔的构筑

在微孔结构的ZSM-5沸石分子筛中构筑介孔,可以有效地解决ZSM-5分子筛在催化反应过程中的扩散传质和催化剂失活问题.重点阐述了在初始的合成体系中加入炭黑、介孔碳、表面活性剂等作为模板剂来构筑含介孔结构的ZSM-5和利用碱液或酸液对已合成的微孔的ZSM-5进行后处理来构筑介孔,并对含有介孔结构的ZSM-5的性质和相关的应用做了评价和展望.     

亲水性沸石膜在异丙醇脱水中的应用及其耐酸性研究

采用二次生长法,在α-Al2O3陶瓷管上制备亲水性NaA、T型、ZSM-5沸石膜,采用SEM对其进行表征.比较3种亲水性膜在异丙醇/水体系的渗透汽化性能,考察其在不同的料液温度下对异丙醇的分离效果.通过优化膜合成液中Si/Al和F-/Si的摩尔比、合成时间等条件,提高ZSM-5沸石膜的渗透汽化性能.分析考察膜的耐酸性能,结果显示ZSM-5沸石膜具有良好的耐酸性;将ZSM-5沸石膜在pH为5.8的酸性溶液浸泡10天后,用于97%的乙酸乙酯/水体系中渗透汽化脱水,渗透液水含量可达99.59%,渗透通量可达0.12kg/(m2·h),分离因数高达7 894.     

二维沸石纳米片的合成及其分离膜研究现状

二维(2D)纳米片堆叠构建的层状分离膜的出现为下一代高效膜分离技术开辟了新途径.2D沸石纳米片具有纳米级别的厚度及较大的横纵比，其面内规整孔道为分子传质提供了丰富的路径，并可有效缩短传统无孔纳米片堆叠构筑的二维膜内分子绕行的传质路径，有望用于制备具有优异分离性能的二维材料膜.本文综述了2D沸石纳米片的合成方法及沸石纳米片膜的研究进展，重点介绍了2D沸石纳米片合成方法，包括表面活性剂辅助合成、沸石层状前驱体剥离和Assembly-disassembly-organization-reassembly(ADOR)法，以及2D沸石纳米片膜的制备方法及其在膜分离中的应用，最后对该领域当前的技术局限性和未来的研究方向进行展望.     

沸石降解法合成孔壁含有沸石结构单元的介孔结构材料

提出了一种合成孔壁含有沸石结构单元的介孔结构材料的新方法一降解法,即利用不同硅铝比的β沸石和ZSM-5沸石为原料在碱溶液中处理得到降解液,然后以此降解液为硅铝源在表面活性剂P123的模板作用下组装了孔结构类型为SBA-15的介孔结构材料,分别简称为MSB(β沸石降解合成)和MSZ(ZSM-5沸石降解合成).产物的IR光谱、N₂吸附、29Si MAS NMR图谱和对重芳烃的加氢脱烷基反应催化活性均说明降解法合成的介孔结构材料MSB和MSZ的孔壁中含有了沸石的结构单元.     

以聚乙二醇为模板凝胶转化制备介孔ZSM-5沸石及其催化性能

以聚乙二醇为介孔导向剂, 通过凝胶转化制备了介孔ZSM-5沸石。研究表明, 在TPA⁺/SiO₂=0.1时经过9~15 h溶剂挥发制得的凝胶, 在160℃处理24 h可得到介孔ZSM-5沸石; 挥发时间太短或太长会得到纯的ZSM-5沸石或介孔材料, 说明在凝胶的制备过程中, 通过控制溶剂的挥发程度, 既可为沸石生长过程提供所需的水分, 又能避免沸石晶体形成过程中无定型相的产生, 从而在较低的TPA⁺浓度下获得介孔ZSM-5沸石。与传统的ZSM-5沸石相比, 利用该方法制备的介孔ZSM-5沸石不仅具有微孔/介孔多级孔结构, 同时具有沸石材料较强的酸性、较高的水热稳定性和择形催化性能, 使其在苯甲醛与正丁醇的大分子醇醛缩聚反应中能有效地克服传统沸石孔径限制的缺点, 收率高达42.4%。     

A novel method for the growth of ZSM-5 zeolite membrane on the surface of stainless steel

Thin ordered micropore ZSM-5 zeolite membrane has formed on the stainless steel surface. The influence of three different pre-treatment methods for the growth of ZSM-5 zeolite membrane on the stainless steel was studied, including mechanical polishing, soaking in a 20 wt.% sulfuric acid aqueous solution and anodic oxidation treatment. It was found that the anodic oxidation technique was more favorable for the growth of ZSM-5 zeolite membrane on the stainless steel surface compared with the other two methods. By this appropriate pre-treatment process, ordered ZSM-5 zeolite membrane was immobilized on the stainless steel surface and it showed good interaction with the stainless steel. Energy-dispersive X-ray (EDX) spectroscopy result indicates that the ZSM-5 zeolite membrane has a Si/Al ratio of 37. X-ray diffraction (XRD), N₂ adsorption and scanning electron microscopy (SEM) were used to study the crystal structure, specific surface area and morphologies of the ZSM-5 zeolite membrane.     

Synthesis of b-axis oriented ZSM-5 zeolite by mechanochemical-assisted quasi-solvent-free method and its MTO catalytic performance

In this paper, b-axis oriented ZSM-5 zeolite was synthesized by solvent-free method with ammonia as growth regulator. Zeolites were characterized by modern detection techniques such as XRD, SEM, BET and NH₃-TPD. The results showed that ammonia could not only promote the crystallization of ZSM-5 zeolite, but also direct the synthesis of ZSM-5 zeolite with b-axis oriented morphology, which was beneficial to enhance the selectivity of light olefins. B-axis oriented ZSM-5 zeolite did not need to be mixed and aged in aqueous solution, which could reduce the discharge of sewage, and avoided the generation of autogenic pressure in the crystallization process. Furthermore, it is consistent with the concept of environmental friendliness, which could guide the green preparation of industrial ZSM-5 zeolites.     

PBAT/ZSM-5分子筛共混薄膜的制备与性能

目的 以聚己二酸-对苯二甲酸丁二酯(PBAT)为基材,制备PBAT/ZSM-5分子筛共混薄膜,研究分子筛含量对薄膜性能的影响.方法 通过共混熔融挤出流延法制得含不同质量分数ZSM-5分子筛(0％,1％,3％,5％,7％)的PBAT薄膜,测定分析不同分子筛质量分数对薄膜的颜色、透明性、结构、气体阻隔性、力学性能等性能的影响.结果 随着分子筛质量分数的增加,透明性和断裂伸长率显著降低,抗拉强度先增加后降低,质量分数为1％分子筛的薄膜抗拉强度相对较大,较纯PBAT薄膜增加了12.34％;薄膜氧气透过性能整体上呈上升趋势,二氧化碳透过性和CO2/O2透过比均逐渐增加,水蒸气透过性显著降低,与纯PBAT薄膜相比,质量分数为7％分子筛PBAT薄膜的氧气和二氧化碳透过系数分别增加了18.48％,33.51％,水蒸气透过系数下降了43.28％,CO2/O2透过比由原来的8.84增加到9.96;薄膜表面和横截断面均变得粗糙,局部区域有团聚现象,且随分子筛含量的增加而变得明显.结论 ZSM-5分子筛的少量加入,可以影响PBAT薄膜力学性能,降低其水蒸气透过性,调节薄膜的气体选择透过性,为其应用于生鲜果蔬包装提供基础.     

酸碱复合处理制备多级孔ZSM-5分子筛及其甲醇制汽油反应性能

以商业ZSM-5分子筛为原料, 分别采用碱处理和酸碱复合处理法制备了多级孔ZSM-5分子筛。利用XRD、FT-IR、SEM、TEM以及氮气吸-脱附等手段对样品进行了表征, 并评价了样品的MTG反应性能。结果表明: 利用单纯碱处理或酸碱复合处理商业ZSM-5分子筛均可制备晶体内富含介孔和大孔的多级孔ZSM-5分子筛。与商业ZSM-5原料相比, 多级孔ZSM-5分子筛催化剂的介孔比表面积、介孔孔容以及酸性位“可接近性指数”等显著增加, 酸量明显减少, 酸强度降低。催化评价结果显示, 多级孔ZSM-5分子筛催化剂在大幅提高汽油产品收率、延长使用寿命的同时降低了芳烃收率。与碱处理样品相比, 酸处理能够进一步调节样品的酸性质和孔结构, 因此酸碱复合处理所得多级孔ZSM-5分子筛催化剂的物化性质和催化性能得以进一步提升。     

Enhanced activity of hierarchical zeolitic material with ZSM-5 structure for the tert-butylation of phenol

Nanocrytsalline phase of hierarchical zeolite structure with ZSM-5 was successfully synthesised via a facile and new method using NR latex as a polymer macrotemplate for the liquid phase alkylation of phenol with tert-butanol. X-ray diffraction pattern, FT-IR spectrum and TEM observations confirm the formation of pure and nanocrystalline zeolite ZSM-5 phase. Catalysis measurements show that the prepared zeolite ZSM-5 phase leads to high phenol conversion and 2,4-di-TBP selectivity which is mainly due to the presence of the hierarchical porosity within the zeolite ZSM-5 phase as confirmed by FESEM and pore size analyses.     

Optimization of crystal growth of hierarchical porosity ZSM-5 zeolite based on coal fly ash “waste utilization”

In this study, ZSM-5 zeolite with hierarchical porosity structure was synthesized by hydrothermal method using Al(OH)₃, SiO₂ extracted from coal fly ash as aluminum source and silicon source. The optimal synthesis parameters of ZSM-5 zeolite were determined via an orthogonal analysis table. The optimum synthesis conditions were: SiO₂/Al₂O₃/Na₂O/hexadecyltrimethylammonium bromide/tetrapropyl ammonium bromide/H₂O = 1/0.08/0.25/0.05/0.17/50, and the optimum crystallization temperature and crystallization time were 160 °C and 48 h, respectively. Scanning electron microscopy showed that the synthesized ZSM-5 zeolite exhibited a spherical shape. Nitrogen adsorption-desorption and Brunauer-Emmett-Teller measurement analysis displayed that the best sample ZSM-5 molecular sieve showed a typical type IV isotherm, and the micropores and mesopores coexisted in the sample, indicating the successful preparation of ZSM-5 zeolite with hierarchical porosity structure. The crystal growth of ZSM-5 under different hydrothermal conditions follows the “S” adjustment.     

Cu/Zn/Ce/ZSM-5分子筛的碱改性及催化性能研究

采用NaOH溶液和金属离子(Cu~(2+)、Zn~(2+)、Ce~(4+))改性ZSM-5分子筛。通过SEM、XRD等表征手段,探讨NaOH溶液浓度、Cu/Zn/Ce物质的量比以及不同制备方法对ZSM-5分子筛形貌及性能的影响。以光催化辅助降解酸性大红GR模拟废水,考察改性后的ZSM-5分子筛的催化活性。结果表明,当NaOH溶液的浓度为0.2mol/L、Cu负载量为8%、Cu/Zn/Ce物质的量比为8∶4∶1、制备方法为溶胶-凝胶法时,分子筛的催化性能最佳,离子溶出量较小。     

Synthesis of mesoporous ZSM-5 from rice husk ash with ultrasound assisted alkali-treatment method used in catalytic cracking of light naphtha

A series of mesoporous ZSM-5 zeolite was synthesized with ultrasonic assisted alkali-treatment technique and their catalytic activity was investigated in catalytic cracking of light naphtha. ZSM-5 zeolite was synthesized from rice husk ash without using any organic template. Effect of alkali-treatment conditions on physicochemical properties of synthesized zeolite was investigated with XRD, FESEM, TEM, N2 adsorption-desorption isotherm, NH3-TPD and TGA technique. It was found that ultrasound energy facilitates the creation of hierarchical structure of ZSM-5 during alkali-treatment. According to XRD analysis, zeolite structure was preserved after 20 min ultrasonic assisted alkaline treatment. However, prolonged dessilication time led to the destruction of MFI zeolite structure. The synthesized ZSM-5 represented highly ordered hexagonal-shape morphology. With increasing alkali-treatment time, the plough land roughness appeared on the surface of zeolite. Comparison of the textural properties samples revealed that the mesopore surface area of alkali-treated samples increased considerably with the increase of ultrasonic assisted alkali-treatment time. Results from catalytic activity tests showed that ultrasound energy has great influence on the activity of ZSM-5. The sample had the highest activity after alkali-treated for 20 min in presence of ultrasound energy which was due to their appropriate hierarchical structure.     

一步合成核壳结构ZSM-5/EU-1复合分子筛及其表征

在添加适量柠檬酸的条件下采用双模板剂一步法, 一次晶化合成ZSM-5/EU-1核壳共生复合分子筛, 对其物理化学性质进行表征, 结果显示: 核壳分子筛中存在ZSM-5和EU-1两种分子筛晶相, 且EU-1分子筛在ZSM-5分子筛表面缺陷处外延生长; 复合以后核壳分子筛为微孔-介孔多级孔道结构, 且其微孔孔径达到0.94 nm; 相比于单一分子筛, 核壳分子筛的强酸量相对提高, 酸性质有所改善。通过对柠檬酸加入量、晶化时间影响因素的分析, 得到合成核壳共生结构的最佳条件为: n(citrate)/n(Al₂O₃)=0.8~1.2, 晶化时间为72~96 h, 并推测核壳分子筛可能的生长过程。