二次晶化法修饰改性钛硅分子筛及催化环己酮氨氧化反应

采用无机钛硅原料合成了钛硅分子筛TS-1,经酸处理后对合成的钛硅分子筛TS-1进行二次晶化修饰改性.用X射线衍射仪(XRD)、傅立叶红外光谱(FT-IR)和扫描电子显微镜(SEM)对二次晶化后的钛硅分子筛进行表征,发现晶粒变小,钛进入了分子筛的骨架中.考察了二次晶化后的催化剂对环己酮氨氧化反应的催化性能.结果表明,二次晶化法可提高TS-1分子筛的催化性能,在氨、环己酮和过氧化氢的物质的量之比为2.0∶1.0∶1.5、催化剂用量为18 g/mol和75 ℃的条件下,反应4 h后,过氧化氢的转化率、环己酮的转化率和环己酮肟的收率分别为98.12%,97.07%和93.33%.     

碱用量对TPABr-乙胺体系合成TS-1分子筛结晶和催化性能的影响

以无机钛硅为原料、四丙基溴化铵(TPABr)为模板剂、乙胺水溶液为碱源的TPABr-乙胺体系合成钛硅分子筛TS-1,研究了碱用量对TS-1分子筛结晶和催化性能的影响。利用FT-IR、XRD、UV-Vis和SEM等对TS-1分子筛的结晶情况进行了表征。以催化烯丙醇环氧化为探针反应,研究碱用量对TS-1分子筛催化性能的影响。在硅源、碱源摩尔比1∶1.9与1∶0.25之间调节碱加入量,结果表明,TPABr-乙胺体系法合成的样品,具有典型的MFI特征结构。合成出的TS-1分子筛晶体呈长方体形,长度约为4.4~8.8μm。碱用量减少得到的TS-1催化剂样品的相对结晶度低;当碱用量降低至0.25时,得到无定形态粉末;碱用量增多合成的TS-1分子筛样品相对结晶度高,非骨架钛物种和锐钛矿含量减少,晶粒的尺寸缩小,催化丙烯醇氧化产物的选择性显著提高,达到98%。     

钛硅分子筛的改性:文献综述

钛硅分子筛(TS-1)是由钛原子取代纯硅分子筛中的部分硅原子的一类具有MFI型结构的微孔沸石分子筛,它与H2O2溶液组成的体系在有机催化氧化反应中得到了广泛应用。本文对TS-1在工业应用中存在的问题作了分析,在此基础上,对近年来国内外科研工作者通过改性处理来提高TS-1的催化性能作了文献综述,并对其今后的研究方向作了展望。     

钛硅分子筛TS-1合成及催化环己酮氨氧化的研究进展

钛硅分子筛TS- 1催化的环己酮氨氧化反应是一个绿色过程。介绍了TS- 1分子筛的合成、TS- 1分子筛催化的环己酮氨氧化及环己酮氨氧化与过氧化氢生产的集成。指出提高催化剂的性能、降低其生产成本是今后研究的重点 ,绿色氧化剂过氧化氢的生产与氨氧化过程的集成是今后环己酮肟生产的发展方向     

无机原料制备TS-1分子筛及其催化环己酮氨氧化

分别以硅溶胶和白炭黑为硅源、三氯化钛为钛源合成了TS-1分子筛。采用XRD、FT-IR、SEM、TEM和低温N2吸附-脱附等方法表征,表明两种无机硅源均可制备结晶度较好和晶体结构完整的TS-1分子筛。将制备的TS-1分子筛用于催化环己酮氨氧化,结果表明,在优化反应条件下,硅溶胶制备的TS-1分子筛具有比白炭黑制备的TS-1更好的催化性能。     

二次晶化法合成高钛含量TS-1分子筛及其催化性能评价

以正硅酸乙酯为硅源、钛酸丁酯为钛源、四丙基氢氧化铵(TPAOH)为模板剂,采用二次晶化法在TPAOH/SiO_2=0.1时合成不同硅钛比的TS-1分子筛,通过XRD、FTIR、UV-Vis、SEM等对TS-1分子筛的结构和形貌进行表征,并以苯酚羟基化反应为探针反应考察其催化性能。结果表明,胶液中硅钛比相同时,二次晶化法合成的TS-1分子筛骨架钛含量高于传统方法,且随着胶液中钛含量的增加,骨架钛含量呈增加趋势;当硅钛比为20时,骨架钛含量达到饱和,多余钛原子以锐钛矿形式聚集;TS-1分子筛粒径较小,为200~300nm。由于骨架钛含量高、粒径小,TS-1分子筛在苯酚羟基化反应中表现出较好的催化性能,当硅钛比为20时,苯酚转化率达到最高,为27.30%。     

多级结构钛硅分子筛及其催化氧化应用研究进展

近年来,多级结构钛硅分子筛(TS-1)引起了越来越多的关注.本文综述了多级结构钛硅分子筛制备研究的最新进展,介绍了不同的制备方法和先进表征技术,并比较了各制备方法的优劣势,讨论了合成材料的孔结构、活性钛物种对烯烃环氧化催化反应和燃油催化氧化脱硫性能的影响.最后,对多级结构钛硅分子筛面临的挑战和未来的发展前景进行了展望.     

超声波辅助合成钛硅分子筛及其脱硫性能的研究

分别以四丙基溴化铵(TPABr)和四丙基氢氧化铵(TPAOH)为模板剂,氢氧化钠(Na OH)和四丙基氢氧化铵为碱源,在超声波辅助下合成了钛硅分子筛TS-1,考查了超声对不同条件合成TS-1的影响,同时与传统方法合成的钛硅分子筛进行了比较。通过X射线衍射(XRD)、傅里叶红外(FT-IR)、紫外可见(UV-vis)、扫描电镜(SEM)等表征了合成的样品。以模型油中噻吩的脱除为探针反应,采用双氧水(H_2O_2)为氧化剂,合成的TS-1为催化剂对其进行氧化脱硫性能研究。结果表明,当TPAOH为模板剂和碱源时,超声对钛硅分子筛合成影响较小;当TPABr为模板剂,Na OH为碱源时,超声对钛硅分子筛合成影响较大;与传统方法合成的钛硅分子筛相比,超声波辅助方法合成的钛硅分子筛晶粒较小,骨架钛含量较多,氧化脱除噻吩的活性较高。     

钛硅分子筛TS-1的放大合成研究

采用四丙基氢氧化铵为模板剂,对水热合成法制备钛硅分子筛TS-1工艺进行中试放大研究,通过XRD、SEM、UV-Vis等手段对TS-1的结构及形貌进行表征,并以苯酚羟基化反应为探针反应考察其催化性能。结果表明,10L反应釜合成的TS-1分子筛具有更高的结晶度和更小的晶粒尺寸,其催化性能也优于小试合成的TS-1。进一步研究了放大合成过程中模板剂用量和晶化条件对合成分子筛性能的影响,确定了其最佳工艺条件,为TS-1分子筛的工业化生产提供依据。     

含钛分子筛合成研究的新进展

本文综述了具有独特氧化性能的含钛分子筛合成研究新进展,探讨了在合成TS-1和TS-2沸石中不同硅源、钛源、模板剂及合成路线对其结构性能的影响,评述了Ti-MCM-4、Ti-TMS、Ti-β型等含钛沸石的合成技术。     

钛硅分子筛TS-1合成及应用的研究进展

综述了钛硅分子筛TS－1合成，表征以及催化性能方面的研究进展，着重讨论了合成过程中影响钛进入分析筛骨架的因素，详细介绍了XRD，FT－IR，UV－Vis,XPS,^29SiMAS,NMR等表征技术对TS－1分子筛的分析结果。TS－1双氧水体系的应用研究进展。     

Titanhaltige Molekularsiebe als Katalysatoren für selektive Oxidationsreaktionen mit Wasserstoffperoxid

Titanium Containing Molecular Sieves as Catalysts for Selective Oxidation Reactions with Hydrogen Peroxide Titanium silicalite (TS-1) is known to be a highly-efficient and selective redox molecular sieve that has been found to catalyze a range of synthetically useful oxidation reactions with hydrogen peroxide under mild conditions. Among these reactions which are often influenced also by the shape-selective properties of the Ti-containing molecular sieve are olefin epoxidation, the oxidation of alcohols to carbonyl compounds, aromatic hydroxylations and ammoximation of cyclohexanone to cyclohexanone oxime. A critical review on the present literature on TS-1 catalysts and further Ti-containing molecular sieves is given mainly focused on the questions connected with the identification of the catalytic active titanium species and the mechanism of some of the reactions. Therefore, the procedure of the synthesis of TS-1 as well as the results obtained from the most of the physico-chemical investigations are analyzed. There are no final correlations to realize between the parameters of the synthesis, the results of characterization and the catalytic properties of TS-1.     

丙烯直接气相氧化过程中Ag/TS-1催化剂上活性银物种的分布

在常压固定床、石英反应器中,以丙烯直接气相氧化反应为探针,考察了硅烷化处理及TS-1中模板剂对Ag/TS-1催化性能的影响.同时,采用UV-Vis、ICP和TEM等手段对其进行了表征.结果表明：在丙烯直接气相氧化过程中,载体TS-1硅烷化后所制备的Ag/TS-1的催化性能增强.通过硅烷化处理负载2%SiO₂,制备的Ag/TS-1的丙烯转化率可达2.1%,环氧丙烷选择性98.4%.用TS-1原粉（含有模板剂）所制备的Ag/TS-1不具有环氧化性能.分子筛内外表面的银物种均具有环氧化性能,但内表面的银物种在丙烯气相氧化过程中起决定性的作用.     

A test reaction for titanium silicalite catalysts

The catalytic hydroxylation of phenol to hydroquinone and catechol can be used for checking the quality of titanium silicate catalysts since the selectivity of these catalysts is strongly affected by the presence of small amounts of non-framework titania. Titanium silicates prepared by modification of [Al]ZSM-5 exhibits the same catalytic properties as hydrothermally synthesized TS-1 of high purity.     

含钛高硅沸石TS－1、TS－2的合成及表征之进展

近年来，人们成功地制备了分别具有ＭＦＩ和ＭＥＬ拓扑结构的含钛高硅沸石ＴＳ－１和ＴＳ－２。这些新型沸石对温和条件下用双氧水氧化许多有机化合物有独特的催化效果，因而引起了人们的极大关注。本文较详细地介绍了ＴＳ－１和ＴＳ－２的合成方法、表征方法及催化性能，并综述了不同条件对合成和表征的影响。     

Preparation of titanium silicalite-1 catalytic films and application as catalytic membrane reactors

Titanium silicalite-1 (TS-1) films were prepared on porous α-Al₂O₃ tubes using nanosized silicalite-1 (Sil-1) particles as seeds by hydrothermal treatment and a TS-1 catalytic membrane reactors (CMR) was reasonably designed and evaluated by phenol hydroxylation with hydrogen peroxide as oxidant. Some factors on influencing TS-1 film formation and catalytic properties were investigated and the TS-1 films were characterized by scanning electron microscope (SEM), transmission electron micrograph (TEM), X-ray diffractometer (XRD), FTIR, UV–vis and X-ray fluorescence (XRF). It was indicated that TS-1 films prepared from Sil-1 and TS-1 seeds were comparable in structure, morphology and reaction behavior. The crystallization time and times of TS-1 film had a strong effect on its morphology, thickness and orientation. However, the film thickness could be easily controlled by crystallization time and times. The Ti/Si ratio in synthesis solution intensely influenced the content of the titanium atoms incorporated as framework Ti that was correlated well with the activity. The maximum Ti (IV) incorporated corresponds to a Ti/Si ratio of approximately 0.02–0.03. A constant conversion for phenol hydroxylation was obtained with the film thickness of over 7.5 μm. It is demonstrated that most of the reaction occurred in a shallow layer near the film due to the mass transfer effects in the TS-1 films.     

纳米TS-1分子筛的合成及环己酮肟化反应性能

采用预晶化后补充硅源的合成方法,在模硅物质的量比0.15条件下,合成晶粒尺寸300 nm的TS-1分子筛。考察模板剂用量和预晶化时间对分子筛合成的影响,并采用XRD、SEM、TEM、UV-vis和N2吸附-脱附对分子筛进行表征,通过环己酮肟化反应考察分子筛催化性能。结果表明,相对于传统法合成的TS-1分子筛,采用预晶化补硅法合成的TS-1分子筛具有较大的比表面积和介孔体积,而且其非骨架钛含量减少,能够有效地提高环己酮肟化反应的转化率、选择性和催化剂寿命。     

Hydrothermal synthesis of mesoporous titanosilicate with the aid of amphiphilic organosilane

Mesoporous MFI-type titanosilicates (TS-1) were hydrothermally synthesized with the aid of amphiphilic organosilane and the effects of the amphiphilic organosilane on the structural and textural properties of the resultant materials were investigated. The physicochemical properties of the samples were characterized by various techniques and their catalytic performance was investigated by the epoxidation of cyclohexene with hydrogen peroxide. The content of organosilane added was essential for the formation of uniform mesopore in TS-1, and greatly influenced the crystallinity. Highly crystallined TS-1 with uniform mesopores of 3.7 nm diameter was successfully synthesized. The mesoporous TS-1 preserved tetrahedrally coordinated Ti ions in the framework, but it was featured with more hydrophobic surface and less defect sites in comparison to conventional TS-1. Mesoporous TS-1 showed a higher conversion for the epoxidation of cyclohexene owing to an easier access of bulky molecules to the catalytic active sites. Mesoporous TS-1’s higher hydrophobicity made its epoxide selectivity two times as much as that of conventional TS-1.     

Characterization and catalytic properties of titanium silicalite-1 catalyst

Titanium silicalite 1 (TS-1) catalyst was prepared by three different hydrothermal synthesis methods. XRD, elemental analysis, SEM, IR,²⁹Si MAS NMR, UV-vis DRS, physical adsorption of nitrogen, and EXAFS analysis were then performed to evaluate its physical properties. For a test of catalytic activity, liquid phase 2-butanol oxidation and 1-hexene epoxidation using hydrogen peroxide as an oxidant were conducted. The crystal size of the TS-1 catalyst was shown to have a considerable effect on the 1-hexene epoxidation, and smaller crystals resulted in higher activity.     

Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation

Titanium silicalite-1 (TS-1) has been hydrothermally synthesized with tetrapropylammonium hydroxide (TPAOH) as the template in the presence of various amounts of Na⁺, characterized by inductively coupled plasma, X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and ultro-violet-visible spectroscopy and studied in cyclohexanone ammoximation. The characterization results show that with the increase of Na⁺ concentration in the synthesis, both the crystal sizes of TS-1and extra framework Ti increase but framework Ti decreases. The addition of Na⁺ below 3 mol-% of TPAOH in the synthesis does not influence the catalytic properties with above 98% conversion of cyclohexanone and 99.5% selectivity to cyclohexanone oxime. However, at the concentrations of Na⁺≥3 mol-% of TPAOH in the synthesis, the catalysts are deactivated faster with the increase of Na⁺ addition, which can be attributed to more high molecular weight byproducts deposited in the large TS-1 particles and the loss of the frame-work titanium. The results of this work are of great importance for the industry.