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.     

高性能NaA分子筛-聚酰亚胺复合分离膜的制备及表征

采用微波加热法在a-Al2O3载体表面合成了NaA分子筛膜,通过对其浸渍镀膜及亚胺化处理制备出致密NaA分子筛-聚酰亚胺(PI)复合分离膜.采用XRD、FT-IR、SEM分析手段和气体渗透实验对NaA分子筛-Pl复合膜进行了表征.考察了NaA分子筛膜与NaA分子筛-PI复合膜的形貌、结构和渗透性能差异.XRD结果表明,...     

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.     

渗透汽化脱水分子筛膜的制备与应用研究

开发了擦涂-浸渍涂晶法和亚微米晶种诱导制备NaA分子筛膜技术,有效地提高了膜的成品率、缩短了合成时间,获得了适合规模化生产的制膜工艺。通过分子模拟的方法,对有机溶剂和水在分子筛膜中的传质机理进行了探讨。对NaA分子筛膜在体系中的水热、酸碱和盐稳定性进行了系统地研究,提出了相应的预处理工艺,并设计建造出渗透汽化工业应用装置,实现了长时间稳定运行。     

四通道中空纤维NaA分子筛内膜的制备与表征

采用错流真空抽吸涂晶与动态水热合成的方法在四通道陶瓷中空纤维载体的内表面制备出高性能的NaA分子筛膜, 并用于75℃下90wt%乙醇/水混合物渗透汽化脱水分离, 系统考察了晶种液流速、涂晶时间与合成温度对NaA分子筛膜形貌与分离性能的影响。结果表明, 当晶种液流速为100 mL/h、涂晶时间为5 s时制备的NaA分子筛膜致密均匀; 晶种液流速过慢或者涂晶时间过长会导致膜厚增加同时也会在膜表面产生缺陷。当膜在100℃下水热合成两次, 制备的NaA分子筛膜分离性能最佳, 此时膜的分离因子为1585, 通量高达8.8 kg/(m²•h)。当合成温度过低时, 膜的晶化程度较低, 膜表面出现缺陷; 当合成温度过高时, 膜晶体生长速率过快, 交互生长程度较差, 膜的断面产生缺陷, 导致膜分离性能较低。     

沸石分子筛膜研究进展

沸石分子筛膜材料由于其独特均一的孔道结构及可调变的表面等性质,在分子级别的分离表现了高度的分离选择性及优越性,成为膜科学与研究的前沿和热点领域之一.文章介绍了面向不同分离体系沸石分子筛膜材料设计、制备与应用,重点探讨了沸石分子筛膜材料结构与性能调控的策略,分析了其产业化生产和工业应用进程,提出了采用新策略调控沸石分子筛膜的结构与性能是沸石膜发展的关键,并指出了沸石分子筛膜的研究发展方向.     

壁厚对支撑体及所制备NaA膜脱水性能的影响

利用挤出成型法制备了不同壁厚的管式莫来石陶瓷支撑体,随后采用二次生长法在这些支撑体表面制备出了NaA分子筛渗透汽化膜,考察了壁厚对支撑体及所制备分子筛膜性能的影响.结果表明,降低壁厚有利于提高支撑体纯水通量和分子筛膜的渗透通量.壁厚为1.8 mm的支撑体较壁厚为2.4 mm的支撑体纯水通量提高了24%,所制备的分子筛膜用于实际乙醇脱水过程平均通量提高了27%.进一步降低壁厚导致支撑体强度及截面圆度降低,无法满足实际工业应用需求.     

钯复合膜表面缺陷修饰材料的研究

利用钯膜分离氢是高纯或超纯氢气生产的主要方式,然而,钯膜表面缺陷是影响氢分离纯度的主要因素.本文选择NaA分子筛和γ-Al2O3两种缺陷填充材料对初镀后的钯膜表面缺陷进行修饰,发现两种材料修饰后钯膜透氮量分别下降了57和2倍,NaA分子筛材料修饰后钯膜的透氮量为未修饰钯膜的1/2 500.经过补镀和活化后,在相同钯膜厚度(2.5μm)条件下,3种钯膜透氮量分别为1.91×10-3、6.12×10-4和4.89×10-3m3/(h·m2·MPa).不同修饰材料修饰的钯膜的氢氮分离因子顺序为NaA分子筛＞γ-Al2O3＞无修饰,说明通过修饰钯膜缺陷的方法可提高钯膜的氢分离选择性,且用NaA分子筛材料要优于γ-Al2 O3材料,因为NaA分子筛在缺陷中可根据缺陷形状原位生长,更能有效填补缺陷.NaA分子筛材料修饰后的钯膜经过20次300～400℃以及0.1～1.0 MPa的温度和压力循环仍保持性能不变,具有较高的稳定性.     

NaA型分子筛掺杂PAN/PES复合纳米纤维膜制备及性能研究

通过水热法合成NaA型分子筛颗粒,采用静电纺丝技术成功制备了NaA型分子筛掺杂聚丙烯腈(PAN)/聚醚砜(PES)复合纳米纤维膜。以扫描电子显微镜、X射线衍射、傅里叶变换红外光谱分析等手段对制备的NaA型分子筛以及PAN/PES/NaA复合纳米纤维膜进行表征及测试,同时探索了NaA型分子筛的掺杂量、纤维膜的面密度以及测试粒径、时间、气溶胶流速对空气过滤性能的影响。空气过滤测试结果表明:在NaA型分子筛掺杂量为1.5%(质量分数),纤维膜面密度为0.72g/m~2条件下,对粒径为0.33μm的邻苯二甲酸二辛酯气溶胶颗粒的过滤效率高达96.525%,空气过滤压降仅为65.337Pa,品质因数为0.096Pa~(-1)。     

不同预植晶种法制备NaA分子筛膜及其表征

采用多种预植晶种法在管状ɑ-Al2O3外表面水热晶化制备NaA分子筛膜.使用XRD、SEM对合成的膜层进行形貌表征,并用渗透气化技术考察膜的醇水分离性能.结果表明,采取搽涂-浸渍法在支撑体表面预植晶种,并进行2次4h水热晶化成膜制备的膜性能最好,在343K进料液中乙醇质量分数为90%时分离因子与渗透通量分别为6824和1.40kg/(m2·h).并考察操作温度以及料液水含量对膜渗透汽化分离性能的影响.随料液中水含量的增加,分离因子先升高后下降,渗透通量呈增大趋势;随着操作温度升高,分离因子逐渐降低而渗透通量随之增加.     

微波场中NaA分子筛膜合成规律的研究

采用微波加热技术,常压回流条件下,在多孔氧化铝载体上制备出连续NaA分子筛膜,详细考察了放置方式、碱度、钠离子浓度以及合成次数对膜形成的影响.XRD和SEM表征结果显示,竖立放置和平置在顶部有利于提高膜的连续程度;高的碱度和高的钠离子浓度都不利于形成连续膜,反而溶解膜层;凝胶体系更易抑制转晶;在较短的合成时间里,多次合成有利于形成连续致密膜.     

沸石分子筛膜苛刻环境有机物脱水的研究进展

苛刻环境酸性条件下有机物的脱水在工业上有重大需求.尽管NaA沸石分子筛膜渗透蒸发在中性温和条件下乙醇等有机物脱水已经实现了工业化,但沸石分子筛膜有机酸的脱水或强酸性条件下(pH<3)的有机物的脱水在国际上刚刚起步,面临的关键技术问题是沸分子筛膜的耐酸性和膜的通量极低.对国际上酸性条件下有机物脱水沸石膜的研究现状进行了简要的概述和分析,介绍了功能化修补法高性能MOR沸石膜的研制等,及我们在这领域所做的各种尝试和取得的成果,指出沸石膜微结构的调控是高性能乙酸脱水分离膜制备的关键,对未来发展予以展望.     

Attempts to Synthesize Zeolitic Composites from Stellerite

A feasible method to synthesize NaA and NaY zeolite from stellerite, the very cheap raw material found in China, was reported in this article to reduce the cost of zeolite synthesis for the first time. After stellerite is calcined above 973 K with sodium carbonate, this natural zeolite can be slowly dissolved in alkali solution and partly forms the gels, then transforms to zeolite NaA or NaY by structural rearrangement. The effect of synthetic conditions such as the ratio of different cation used in the reactive mixture on the resulting zeolite is examined. Furthermore, a new NaA/MCM-41 composite possessing both micropore and mesopore is synthesized by adding the NaA zeolite into the synthetic system, and the impact of zeolite additive on the pore structure of final porous composite is also explored.     

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.     

Synthesis of zeolites NaA and analcime using rice husk ash as silica source without using organic template

Silica was extracted from Fajr rice husk ash (RHA) with approximately 97% purity, converted to sodium and potassium silicate solutions and used as silica source for the synthesis of NaA and analcime zeolites. NaOH and KOH without organic templates were used in the synthesis of NaA and analcime zeolite, respectively. Conventional heating and microwave-assisted hydrothermal were used in zeolite synthesis. Zeolites were characterized with XRD, SEM and IR spectroscopy. Heating time and Si/Al ratio were optimized for the synthesis of zeolites.     

陶瓷中空纤维内表面动态水热合成NaA分子筛膜及其表征

采用动态水热法在氧化铝陶瓷中空纤维内表面原位合成了NaA分子筛膜。利用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)表征了分子筛膜的物相及微观形貌,通过渗透汽化测试考察了膜的乙醇/水分离性能,研究了合成工艺参数对成膜过程及膜质量的影响。结果表明,动态下合成的分子筛膜,晶体交联紧致,膜层薄且连续性好,厚度约4μm;提高动态速度有利于降低载体内外合成液的温差和浓度差,缩短晶化时间。在温度343K下,分离质量分数90%的乙醇/水体系,膜的渗透通量和分离因子可达1.03kg/(m2·h)和3 781,对乙醇/水表现出良好的分离效果和可重复性。     

Electrophoretic technique for hydrothermal synthesis of NaA zeolite membranes on porous α-Al2O3 supports

Uniform and dense NaA zeolite membranes were prepared on the α-Al₂O₃ support by electrophoretic technique. The membrane morphology and membrane thickness were investigated by XRD, SEM and pervaporation properties for dehydration of 95 wt.% isopropanol/water mixture at 343 K, respectively. Under the action of the applied electric field, the negatively charged zeolite particles could migrate to the support surface homogenously and rapidly, forming uniform and dense membranes in a short time. High quality NaA zeolite membrane, with a separation factor (water/isopropanol) of 3281 and a flux of 1.24 kg/m² h, could be prepared by electrophoretic technique with the electrical potential of 1 V. The formation mechanism of zeolite membrane in the electric field is discussed.     

Investigations on the relative effectiveness of some tertiary alkanolamines in the synthesis of large-crystal zeolite NaA

The relative efficiency of four different tertiary alkanolamines as nucleation suppressors in the synthesis of large-crystal zeolite NaA has been investigated by systematically varying the amount of each in synthesis solutions and following the phase and particle size of zeolites obtained. One additive, 2,2-bis (hydroxymethyl)-2,2′,2″-nitrilotriethanol, was found to be considerably more effective than the best previously known nucleation suppressor, 2,2′,2″-nitrilotriethanol (triethanolamine), yielding large zeolite NaA crystals at appreciably lower solution additive concentrations. In addition, a spherical phase that was formed in competition to large-crystal zeolite NaA was identified as LOSOD, rather than as the previously suggested NaP. The crystallization of LOSOD was found to be suppressed by increased solution NaOH concentration, allowing the synthesis of larger zeolite NaA crystals.     

以高岭土为原料合成NaA沸石的实验研究

以天然黏土矿物高岭土为原料采用水热晶化法合成NaA沸石。通过XRD、静态饱和水吸附量等测试手段详细考察了初始反应混合物的Na2O／SiO2比和氢氧化钠溶液浓度对NaA沸石结晶度的影响。通过实验研究得到NaA沸石的二元结晶相图及结晶变化规律，并优化工艺参数得到NaA沸石最佳合成条件。