Phosphotungstic acid immobilized on amino-functionalized TS-1 zeolite as a solid acid catalyst for the synthesis of tributyl citrate

The amino-functionalization of TS-1 zeolite followed by immobilization of phosphotungstic acid(HPW)was presented to prepare a strong solid acid catalyst for the synthesis of bio-based tributyl citrate from the esterification of citric acid and n-butanol.γ-Aminopropyltriethoxysilane(APTES)was first grafted on the TS-1 zeolite via the condensation reactions with surface hydroxyl groups,and subsequently the HPW was immobilized via the reaction between the amino groups and the protons from HPW-forming strong ionic bonding.The Keggin structure of HPW and MFI topology of TS-1 zeolite were well maintained after the modifications.The amino-functionalization generated abundant uniformly distributed active sites on TS-1 for HPW immobilization,which promoted the dispersity,abundance,as well as the stability of the acid sites.The tetrahedrally coordinated framework titanium and non-framework titania behaved as weak Lewis acid sites,and the protons from the immobilized HPW acted as the moderate or strong Brønsted acid sites.An optimized TBC yield of 96.2%(mol)with a conversion of-COOH of 98.1%(mol)was achieved at 150℃for 6 h over the HPW immobilized on amino-functionalized TS-1.The catalyst exhibited good stability after four consecutive reaction runs,where the activity leveled off at still a relatively high level after somewhat deactivation possibly caused by the leaching of a small portion of weakly anchored APTES or HPW.

Titanium-rich TS-1 zeolite for highly efficient oxidative desulfurization

The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.

The synthetic strategies of hierarchical TS-1 zeolites for the oxidative desulfurization reactions

With the increasingly stringent standards for limiting sulfide content in liquid fuels,oxidative desulfurization(ODS)has become a promising ultra-deep desulfurization process in fuel desulfurization.TS-1 zeolites show great potential as catalysts for ODS reactions,due to its remarkable oxidation activity at low temperatures and pressure.However,the inherent microporous structure of conventional TS-1 zeolites restricts the mass transportation and renders the active sites in the microporous space of TS-1 zeolites inaccessible for bulky aromatic organosulfur compounds.Fabrication of hierarchical TS-1 zeolites by incorporating meso-/macropores into microporous TS-1 zeolites is an effective strategy to improve mass transportability.In recent years,abundant efforts have been dedicated to developing synthetic strategies of hierarchical TS-1 zeolite,thereby improving its catalytic performance in the ODS process.This mini-review addresses the synthetic methods of hierarchical TS-1 catalysts and their catalytic performance in the ODS reactions.In addition,some current problems and prospects of synthesis routes for constructing hierarchical TS-1 catalysts have also been revised.We expect this mini-review to shed light on the more efficient preparation strategies of hierarchical TS-1 zeolites for the ODS process.

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-Al_2O_3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,H2O_2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。

氧化铝陶瓷管负载TS-1沸石膜的制备及表征

利用二次晶种生长法在α-Al2O3陶瓷管上制备TS-1沸石膜,详细研究了晶化时间对TS-1沸石膜表面形貌、沸石层厚度、沸石生长速率及气体渗透性能的影响。通过扫描电子显微镜(SEM),X-射线衍射仪(XRD),红外光谱(FTIR)、紫外光谱(UV-Vis)及N2渗透测试对TS-1沸石膜进行了全面表征。研究结果表明:随着晶化时间的延长,TS-1膜层表面沸石粒子互生性增强,且膜层厚度也随之增加。然而,随着沸石层厚度的增加,其气体传输性能下降。当晶化时间为48 h,沸石生长速率最快,为0.087μm/h,此时TS-1沸石膜厚度为4μm,表面平整,无明显缺陷。

TS-1分子筛膜制备和催化性能的研究

采用二次水热合成法在管状莫来石支撑体上制备TS-1分子筛膜,通过XRD、FT-IR、UV-Vis和SEM表征技术考察二次水热合成法中浸涂支撑体时晶种悬浮液浓度、合成液中的nH_2O_2/nSiO_2比率、合成液中晶种添加量等对TS-1分子筛膜的生长和催化性能的影响.当合成液的摩尔组分比、晶种液浓度、合成液中的nH_2O_2/nSiO_2比率、溶液中晶种添加质量分数、合成温度和合成时间分别为SiO_2∶0.03TiO_2∶0.2TPAOH∶120H_2O、5%、6、1%、150℃和24h时,连续致密的TS-1分子筛膜在H_2O_2氧化异丙醇反应中表现出良好的催化性能.其次,在渗透汽化-催化氧化耦合反应过程中,当异丙醇与H_2O_2摩尔比和反应温度分别为1∶2和70℃时,异丙醇的转化率达到81.14%,TS-1分子筛膜的通量为2.23kg/(m^2·h).

TS-1分子筛膜的制备

在多孔管状莫来石支撑体外表面水热合成TS-1型分子筛膜.讨论了合成配比、合成温度、晶种引入等因素对膜合成的影响.采用X射线衍射仪(XRD)、红外光谱仪(FT-IR)、紫外可见分光光度计(UV-VIS)和扫描电子显微镜(SEM)对TS-1分子筛及分子筛膜进行了表征.通过乙醇-水混合物对膜的渗透汽化分离性能进行检测.结果表明,Ti进入了分子筛的骨架中,且最佳n(TiO2)/n(SiO2)=0.02,最佳合成温度200℃,采用原位法可以获得缺陷较少的TS-1分子筛膜.该膜对乙醇具有较好的选择性,分离因子为62,通量为0.76 kg/(m2.h).

用于回收酰胺类溶液的TS-1渗透汽化膜的制备和性能测定

采用晶种法制备了不同Ti含量的TS-1/α-Al_2O_3分子筛膜,并用于渗透汽化回收酰胺类溶液。通过X-射线衍射(XRD)、傅里叶红外光谱(FT-IR)、扫描电子显微镜(SEM)等对合成的分子筛膜进行表征,结果表明钛原子进入到分子筛骨架。渗透汽化实验结果显示,TS-1分子筛膜具有较好的分离性能且优先透过有机物,可用于酰胺类有机物的回收利用。n(Ti)/n(Si)为0.015合成的TS-1分子筛膜,在进料温度为65℃,操作压力为300 Pa的条件下,分离质量分数为5%的DMF/H_2O和DMAc/H_2O溶液,渗透通量分别为1.34 kg/(m^2·h)和1.13 kg/(m^2·h),回收后溶液的质量分数提高到19.4%和16.2%。

浸没式陶瓷膜反应器中超细TS-1催化苯羟基化一步连续合成苯酚（英文）

A new route towards phenol production by one-step selective hydroxylation of benzene with hydrogen peroxide over ultrafine titanium silicalites-1(TS-1) in a submerged ceramic membrane reactor was developed, which can maintain the in situ removal of ultrafine catalyst particles from the reaction slurry and keep the process continuous.The effects of key operating parameters on the benzene conversion and phenol selectivity, as well as the membrane filtration resistance were examined by single factor experiments. A continuous reaction process was carried out under the obtained optimum operation conditions. Results showed that the system can be continuously and stably operated over 20 h, and the benzene conversion and phenol selectivity kept at about 4% and 91%, respectively. The ceramic membrane exhibits excellent thermal and chemical stability in the continuous reaction process.

Al_2O_3中空纤维陶瓷膜上TS-1膜的制备

采用相转化纺丝/烧结技术制备Al2O3多孔中空纤维膜,并以此为载体,通过晶种法考察不同晶种诱导条件制备TS-1复合中空纤维膜,并采用扫描电子显微镜、气体渗透性能测试装置等设备对所制备的TS-1复合中空纤维膜进行微观结构及渗透性能的表征。结果表明,晶种法制备的TS-1复合中空纤维膜的N2渗透速率较小,并且表面平整无缺陷,因此该方法适合制备性能优良的TS-1复合中空纤维膜。

Aromatic compounds-mediated synthesis of anatase-free hierarchical TS-1 zeolite:Exploring design strategies via machine learning and enhanced catalytic performance

Simultaneous achievement of constructing mesopores and eliminating anatase is a long-term pursuit for enhancing the catalytic performance of TS-1.Here,we developed an aromatic compounds-mediated synthesis method to prepare anatase-free and hierarchical TS-1 for olefin epoxidation.A series of hierarchical TS-1 zeolites were prepared by introducing aromatic compounds containing different functional groups via the crystallization process.The formation of intercrystalline mesopores and insertion of titanium into framework were facilitated at different extent.The synergistic coordination of carboxyl and hydroxyl in aromatic compounds with Ti(OH)4 realizes the uniform distribution of titanium species and eliminates the generation of anatase.Noteworthily,eight machine learning models were trained to reveal the mechanism of additive functional groups and preparation conditions on anatase formation and microstructure optimization.The prediction accuracy of most models can reach more than 80%.Benefiting from the larger mesopore volumes(0.37 cm3⋅g−1)and higher content of framework Ti species,TS-DHBDC-48h samples exhibit a higher catalytic performance than other zeolites,giving 1-hexene conversion of 49.3%and 1,2-epoxyhenane selectivity of 99.9%.The paper provides a facile aromatic compounds-mediated synthesis strategy and promotes the application of machine learning toward the design and optimization of new zeolites.

纳米晶种涂层法合成Silicalite-1沸石膜

用纳米晶种涂层二次生长成膜法在大孔旺．A1203（孔径4～6μm）陶瓷管上合成Silicalite-1沸石膜．用X射线衍射（XRD）和扫描电镜（SEM）表征分析了沸石膜的形态，并通过单组分气体渗透实验对合成膜管的渗透性能进行了测试．结果表明，合成的Silicalite-1沸石膜连续、互生，看不出晶间孔；沸石膜层厚8-10μm；常温常压下HE／N2的理想分离系数为3．9，超过其努森扩散值3．74，H2／C3H8的理想分离系数为19．1，远大于其Knudsen扩散比值4,69，且H2的渗透率达到1．43×10^-6mol／（m^2·s·Pa）．气体分离数据表明，该膜没有明显的缺陷存在．

堇青石载体表面Silicalite-1沸石膜的合成与表征

沸石分子筛膜是近十年发展起来的一种新型无机膜.它具备一般无机膜结构稳定、耐高温与化学侵蚀、机械强度高等优点.尤其是,它的结构孔径均匀、精密,具备分子筛分性能.沸石晶体中的阳离子可被其它离子交换.硅铝比可以调节,硅铝原子可被其它原子取代.这些特性,使研制孔径与分子尺寸相匹配、均匀致密的沸石分子筛膜,成为实现分子水平上分离和膜催化的关键.这是当前无机膜材料研究的前沿和热点.通常,用于分离与催化的沸石膜是在无机多孔载体上合成的.α-氧化铝是文献报道的制备方法中最常用的载体。

在玻璃上合成有取向的silicalite-1分子筛膜及其生长机理

The growth and orientation of zeolite crystals on a glass substrate was investigated by changing the roughness and setting of the substrate surface.The orientation control of crystals on the glass substrate was achieved.It was found that the setting and treatment of the glass substrate had a substantial effect on crystal orientation.When the substrate surface was upward, the preferential growth of crystal was along the a-axis.However, the preferential growth of crystal was along b-axis when the substrate surface was downward.According to experimental results, a film formation mechanism was proposed to account for the growth and orientation of crystals on the glass substrate.

高性能Silicalite-1分子筛膜的合成

Synthesis of high performance Silicalite-1 zeolite membranes on silica tubes was first reported in this paper.After two-step in-situ hydrothermal synthesis,well intergrown Silicalite-1 zeolite membranes were synthesized on silica tubes after aging at 75 ℃ for 12 h.The Silicalite-1 zeolite membranes were characterized by SEM.The separation performance towards ethanol/water mixtures was evaluated by pervaporation.With temperature increasing,the flux of S-1 membrane,increased from 0.2 kg·m-2·h-1 at 30 ℃ to ca. 1.0 kg·m-2·h-1 at 80 ℃, while the separation factor decreased from 110 to 89.These results showed that silica supports may be more suitable for preparing high performance Silicalite-1 membranes.

用于分离DMF/H_2O体系的Me-silicalite-1渗透汽化分子筛膜的制备

采用二次生长法制备了用于渗透汽化分离DMF/H2O体系的杂原子取代Me-silicalite-1/α-Al2O3(Me=Co、Fe)分子筛复合膜,通过X射线衍射(XRD)、扫描电镜(SEM)、傅里叶红外光谱(FT-IR)和紫外漫反射(UV-Vis)等方法对分子筛膜进行表征,结果表明金属离子进入分子筛骨架。渗透汽化实验显示,金属离子掺杂的silicalite-1/α-Al2O3分子筛复合膜,具有较好的分离性能且优先透过有机胺,有利于工业中DMF溶剂的回收和利用。随着操作温度升高,分离因子减小,渗透通量增加。40℃分离质量分数为5%的DMF/H2O混合液时,Co-silicalite-1/α-Al2O3分子筛膜和Fe-silicalite-1/α-Al2O3分子筛膜的分离因子分别为4.4和2.9,渗透通量分别为0.66和0.84 kg·m-2·h-1。

纳米级晶种预涂层法Silicalite-1型沸石膜合成及其结构分析

在大孔-αA l2O3陶瓷管载体上采用晶种预涂层法在澄清溶液体系中水热合成了S ilica lite-1型沸石膜,用SEM和XRD表征了晶种、晶种涂层后载体和成膜后沸石膜的结构、晶形变化、晶相结构等成膜情况,并初步考查了两种不同温度(130℃和160℃)下生长成膜的结构变化.结果表明:制备的晶种呈椭球形、晶粒小(约100 nm)而均匀、纯度高,适合作晶种涂层成膜;所用载体孔径大而不均匀、表面粗糙而不平整,但经晶种涂层后表面可形成一层厚度均匀、光滑的晶种层,再水热晶化时有利于成膜,所得膜连续、清晰无裂缺,载体、晶种层和沸石膜层之间相互结合紧密;连续晶种层改善了载体表面的性能,有利于连续S ilica lite-1沸石膜的形成;合成温度不同,沸石晶粒在载体表面生长的方向不同,所形成的膜微观结构也不同.该合成方法能适合其他不同类型沸石膜的制备.

一种气相合成Silicalite-1沸石膜的新方法

A silicalite 1 zeolite membrane was in situ crystallized from a layer of silica species prepared by a novel method of low temperature chemical vapor deposition (LTCVD) on a porous cordierite substrate. XRD patterns show that the membrane consists of MFI type zeolite crystals. The investigation with SEM indicats that the membrane is about 50 μm thick, and covered with well intergrowth MFI zeolite crystals of about 10 μm in size. The EDX analysis confirms that the membrane is composed of silica in the absence of Al, indicating high silica MFI(Silicalite 1) zeolite grown on the support. The ratio of pure gas permeation is 296 for H 2/ iso butane and 13.7 for n / iso butane at room temperature respectively, confirming that the membrane synthesized on the support of cordierite is high quality without pinhole.

高渗透率高选择性Silicalite-1沸石膜的合成与表征

利用重复水热合成法在α-Al2O3陶瓷管上合成Silicalite-1沸石膜,并对合成的沸石膜进行了X射线衍射(XRD)和扫描电镜(SEM)表征,通过单组分气体渗透对膜的渗透性能进行检测。通过测试发现,H2／N2在常温常压下的理想分离因素为4.00,略大于H2／N2的Knudsen扩散比值3.74,而H2／C3H8的理想分离因素为25.96,远大于其Knudsen扩散比值4.69,H2的渗透率为4.44×10-6mol／(m2·s·Pa)。

一种简单修饰法合成的Silicalite-1沸石膜及其气体渗透性能

采用原位水热法在粗糙大孔α-Al2O3载体管上预先合成Silicalite-1沸石,程序升温焙烧该管后,用砂纸打磨管表面,再用原位水热法在打磨后的管上二次合成Silicalite-1沸石膜。利用XRD、SEM及单组分气体渗透实验对制备的沸石膜进行表征,并初步考察了影响打磨修饰法制备Silicalite-1沸石膜性能的主要因素。结果表明,合成的沸石膜是典型的Silicalite-1;其晶粒排列紧密,呈互锁生长,表面平整,无晶间孔或针孔存在。打磨前水热预处理载体管的时间和砂纸型号对合成沸石膜的质量影响较大。室温下,打磨修饰法制备的Silicalite-1沸石膜的H2渗透率达到1.2×10-6mol/(m2.s.Pa),且H2/N2、H2/C3H8和H2/SF6的理想分离系数分别达到3.9、20.6和84.8。