二次生长法FAU型沸石膜的合成与表征

采用二次生长成膜的方法,在合成液的配比为46Na2O∶12.8SiO2∶1Al2O3∶4 500 H2O的稀溶液中,在大孔α-Al2O3陶瓷管载体外表面,合成出致密的FAU型沸石膜,并用扫描电镜、X射线衍射以及气体渗透性能等手段对沸石膜进行了表征.用热浸渍法将与载体孔径尺寸相近的晶种引入载体表面,晶种嵌入了载体表面的孔口和次孔口,且均匀地分布在膜管表面,明显改善了载体的表面性质,促进了膜的生长.所制备的膜表面晶粒相互交织生长完好,致密,连续,规整,无裂缺,沸石膜厚约6~7μm.H2的渗透率为1.46×10-6mol/(m2.s.Pa),H2/SF6的理想分离因子为9.67,高于其努森扩散值8.54.对稀溶液中沸石膜的形成机制也进行了探讨.     

二次生长法中ZSM-5型沸石分子筛膜合成规律的研究

采用正交试验法,考察了ZSM-5沸石膜合成过程中,制膜液碱量、膜板剂的用量、晶种的引入方式等对成膜的影响;确定了采用浸涂法引入晶种,晶化液摩尔组成为n(Na2O)∶n(Al2O3)∶n(SiO2)∶n(TPABr)∶n(H2O)=15∶1∶100∶20∶10 000,在180℃,晶化48 h,可在多孔α-Al2O3陶瓷管支撑体外表面合成了ZSM-5沸石分子筛膜.用XRD,SEM和单组分气体的渗透对膜进行了表征.结果表明,所合成的沸石膜是典型的ZSM-5沸石膜,膜表面晶粒生长发育较完整,排列紧密,无较大裂缺;H2,N2在膜内的渗透率分别为4.51×10-6,1.34×10-6mol/(m2.s.Pa);膜的H2/N2理想分离因数为3.37.     

无模板剂二次生长法制备可调大孔的沸石泡沫

利用聚氨酯泡沫为模板,经纳米silicalite-1沸石晶种化后,在不含有机模板剂的凝胶体系中进行二次生长,制备了具有丰富可调大孔的ZSM-5沸石材料,该材料保持了聚氨酯泡沫模板的大孔结构.这种沸石构建的大孔材料可以在一定程度上消除扩散限制,有望使沸石在吸附、分离以及催化领域能够得到更有效的利用.     

ZSM—5沸石膜的合成与表征

叙述了沸石膜的发展与应用,综述了 Ｚ Ｓ Ｍ － ５ 沸石膜的合成、修饰与表征方法．制备膜最常用的方法为水热法在载体上直接就地合成．气相化学沉积法（ Ｃ Ｖ Ｄ） 、溶胶－ 凝胶法（ｓｏｌ － ｇｅｌ） 以及合成后积炭等方法被用来对膜的缺陷进行修饰．膜的表征手段为 Ｘ Ｒ Ｄ、 Ｓ Ｅ Ｍ、气体渗透等     

继代晶种法合成NaA分子筛膜

开发继代晶种法合成低成本、易重复的NaA分子筛膜:采用前一代分子筛膜晶化后剩余的母液为晶种液,将其涂敷于载体表面,干燥后置于合成液中,并在微波加热条件下合成NaA分子筛膜.考察了初代母液合成时间对NaA分子筛膜的性能影响,渗透汽化性能测试结果显示:初代母液的合成时间和分子筛膜的晶化时间均为12.5 min时合成的NaA分子筛膜表现出最优的渗透汽化性能,渗透汽化温度为70℃时,其渗透通量达到1.25 kg/(m~2·h),分离系数达到10 000以上.采用优化的合成条件,用继代晶种法连续合成出五代NaA分子筛膜,其渗透汽化测试得到的乙醇脱水性能基本相同,表明继代晶种法可以重复合成性能优良的NaA分子筛膜.     

沸石分子筛膜合成的新方法

沸石分子筛膜在气体分离、渗透汽化、蒸汽渗透、水处理及膜反应器等领域均有广阔的应用前景.由于沸石膜的性能受到晶间缺陷、薄膜厚度及晶体取向性等诸多因素的影响,因此其研究焦点主要集中于沸石膜制备工艺的改进.本文分类介绍了近十年沸石膜合成的新方法,并对其特点进行了总结,主要包括:(1)载体预处理方法中的预堵孔技术新操作方法、载体表面改性新操作方法;(2)晶种层制备方法中的分级晶种浸涂法、湿摩擦涂种法、蒸汽辅助转化涂种法;(3)晶化过程操作方法中的油浴晶化法、无凝胶蒸汽辅助晶化法、水热晶化法+干凝胶转化法、超声波辅助法;(4)模板剂去除方法中的O-RTP法、臭氧氧化法、等离子体辅助焙烧法;(5)膜层后处理方法中的化合物沉积改性法和室温离子液体改性法等.此外对沸石膜合成方法的发展方向也进行了展望.     

负载型TS-1沸石膜催化剂的制备、表征及其催化性能研究

利用水热合成法在α-Al₂O₃陶瓷管表面制备了连续完整的钛硅(TS-1)沸石膜, 并且利用该膜催化剂催化丙烯直接环氧化合成环氧丙烷(PO)。采用SEM、XRD、FT-IR和UV-Vis等表征手段及丙烯环氧化反应测试, 详细研究了合成液中Ti/Si比对TS-1沸石膜形貌、结构及催化性能的影响。结果表明, 合成液中Ti/Si比在0.01~0.04范围内, 所合成的TS-1沸石膜均具备典型MFI型拓扑结构。但当Ti/Si比>0.02时, 随着Ti/Si比升高, TS-1沸石膜表面沸石颗粒排列变得杂乱, 且TS-1沸石沉积量逐渐减少, 沸石晶间缺陷增多, 丙烯渗透速率增大。而且, 当Ti/Si比= 0.03、0.04时, 由于所合成的TS-1沸石膜中存在大量非骨架钛, 导致在丙烯环氧化反应中PO选择性和PO生成速率明显降低。当Ti/Si比为0.02时, 合成的TS-1沸石膜骨架钛含量最高, 其催化性能最佳, H₂O₂转化率、PO选择性和生成速率分别为12.43%、95.80%和15.78 mmol/(h·g)。TS-1沸石膜在丙烯环氧化反应中重复使用8次, 其催化性能保持相对稳定。     

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.     

抽空涂晶法合成A型分子筛膜及渗透汽化性能研究

采用抽空涂晶二次生长法在管状α-Al2O3基膜上合成了具有高选择性、高渗透量的A型分子筛膜.XRD结果表明,分子筛膜晶相中只有A型分子筛存在;SEM表明,基膜表面覆盖了一层致密连续的分子筛膜.考察了A型分子筛膜的渗透汽化性能,结果表明,在温度为323K和343K下,当原料液中异丙醇的质量分数为95%时,其水/异丙醇分离系数都大于10000,渗透量分别为1.27kg/(m2·h)和1.74kg/(m2·h).     

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.     

ZSM—5型沸石膜的合成及应用于乙苯脱氢反应研究进展

重点介绍了国内外关于ZSM－5沸石膜的合成及应用于乙苯脱氢反应应用现状,分析和阐述了当今ZSM－5沸石膜合成的方法和特点及今后面临的挑战。     

Toward the rational design of zeolite synthesis: The synthesis of zeolite ZSM-18

ZSM-18 has, until now, only been made using one trisquaternary ammonium ion, 2,3,4,5,6,7,8,9-octahydro-2,2,5,5,8,8-hexamethyl-1H-benzo[1,2-c:3,4-c′:5,6-c″]tripyrrolium, 1. This trisquaternary is difficult to make and destabilizes the zeolite during calcination. We used modeling to aid the design and selection of new templates for ZSM-18. The geometry and charge distribution of these templates were chosen to best fit our estimate of “templating.” Template 2, tris-(2-trimethylamonioethyl)amine, is easy to synthesize in high yield and can be routinely calcined to produce highly sorptive ZSM-18. Template 3, tris-(2-trimethylamonioethyl)methane, produces ZSM-18 only when seeded. Si n.m.r. and Al n.m.r, indicate that aluminum is not located exclusively in the three rings as has been predicted theoretically. [H]-ZSM-18 can be steam-dealuminated. The Si n.m.r, of the dealuminated material agrees with the number of sites and relative occupancies expected.     

煤系高岭土微波合成NaA分子筛膜及其性能与表征

主要对高岭土微波合成NaA分子筛膜及其性能进行了研究.从铝源和晶化时间等方面研究了对煤系高岭土微波合成NaA分子筛膜的影响,并比较了水热合成NaA分子筛膜和微波合成NaA分子筛膜性能.通过实验发现,以高岭土为原料制备的NaA分子筛膜经微波合成,其乙醇脱水渗透汽化中分离因数超过10 000;NaA分子筛膜的微波合成在晶化时间分别为15、20和25min时,其渗透汽化通量由2.44kg/(m2.h)降低为0.92kg/(m2.h),分离因数由2 945增大为11 846,其中NaA分子筛膜在晶化时间为20min时,其分离因数和渗透通量分别为10 359和1.13kg/(m2.h);同时在相同配方条件下,水热合成的NaA分子筛膜和微波加热合成的NaA分子筛膜相比,反应时间由4h降低为20min,而分离因数由5 231增加到10 360.     

Hydrothermal synthesis of NaA zeolite membrane together with microwave heating and conventional heating

Uniform and dense NaA zeolite membrane was prepared by hydrothermal synthesis method together with microwave heating and conventional heating. The properties of the as-synthesized zeolite membrane were investigated by XRD, SEM and pervaporation evaluation for dehydration of 95 wt.% isopropanol/water mixture at 343 K, respectively. After microwave heating, the α-Al₂O₃ support surface was covered with homogeneous zeolite nuclei, which facilitated to form uniform, pure and dense NaA zeolite membrane in the following conventional heating process. High quality NaA zeolite membrane, i.e., with a separation factor (water/isopropanol) of 10,000 and a flux of 1.44 Kg/(m² h), could be hydrothermal synthesized together with microwave heating and conventional heating.     

A new growth method for the synthesis of 3C-SiC nanowires

A new method has been developed to grow nickel-catalysed SiC nanowires on silicon, by a chemical reaction involving carbon tetrachloride as a single precursor. This produces long crystalline 3C-SiC nanowires with <111> axis, as verified by transmission electron microscopy. A broad optical emission centred at about 2 eV is detected by cathodoluminescence spectroscopy. The Gaussian component at about 2.2 eV corresponds to the indirect 3C-SiC band gap emission, while the dominant red emission is related to oxygen incorporation.     

Multistep synthesis of metal sulfide clusters: A novel zeolite modification method

A general approach has been proposed for incorporating high concentrations of modifier metals into high-silica zeolites. MFI zeolites have been modified with mono- and polymetallic sulfide clusters of copper, manganese, zinc, cobalt, and nickel. The metal incorporation sequence and the nature of the anion have been shown to influence both the total content and the ratio of the modifiers in the zeolite. Using multistep syntheses, we have prepared zeolites containing superstoichiometric amounts of modifier metals. Using a variety of physicochemical characterization techniques, the zinc-containing sample has been shown to have a uniform modifier distribution. The Cu-MFI-50 and Mn-MFI-50 zeolites have been characterized by electron paramagnetic resonance and shown to contain isolated Cu²⁺ and Mn²⁺ ions stabilized on the aluminum lattice site.     

支撑β分子筛膜的制备

以四乙基溴化铵(TEABr)为模板剂合成了支撑β分子筛膜，研究了不同载体类型、预处理条件、合成次数等因素对β分子筛成膜状况的影响．实验发现大孔载体有利于分子筛前驱态凝胶在孔内成核，促进了分子筛晶体与载体的结合强度，使表面晶体能更好地交联生长，成膜效果好；对于不同的预处理过程，采用碱处理(浓度为7mol／L)时制得的分子筛膜最佳；膜厚度随合成次数的增多而增厚，经二次水热合成，即可得到完全覆盖的β分子筛膜。     

Preparation of zeolite T membranes by microwave-assisted in situ nucleation and secondary growth

Zeolite T membranes were firstly prepared on the α-Al₂O₃ tubes by microwave-assisted in situ nucleation and secondary growth. The obtained membranes were characterized by XRD, SEM, single gas permeation, and pervaporation (PV). In the PV dehydration of ethanol and 2-propanol, the as-synthesized membranes displayed high separation performance. For the 90 wt.% alcohol/water mixtures at 338 K, the water flux reached 1.23 kg m^− 2 h^− 1 for the dehydration of ethanol and 1.52 kg m^− 2 h^− 1 for the dehydration of 2-propanol; both separation factors were higher than 10, 000.