钛硅分子筛的技术现状及国内专利分析

Research progress of titanium silicalite catalys tZhangxiaoming Zhangzhaorong Soujiquan Lishuben(Lanzhou Institute of Chemical Physics fine petrochemical intermediates National Engineering Research Center, Lanzhou 730000)The role of titanium catalyst in the oxidation reaction of organic compounds is well known [1, 2]. Introduced in the molecular sieve framework due to the molecular sieve having a regular pore structure and large specific surface area characteristics, hetero atom, having an oxidation-reduction ability to preparenovel catalytic oxidation catalyst, has been more interesting subject in 1983 ENI [3] the T ar amasso its collaborators first successful synthesis of the titanium-containing zeolite catalyst of TS-1, a subsequent study found, Tammonia oxidation [7] S-1 with H2O2 aqueous solution as oxidant and the oxidation reaction of a series of organic compounds, such as olefin epoxidation [4], the aromatic hydrocarbon ring hydroxylation [5, 6], ketone, alkane oxidation[8, 9] and the alcohol oxidation [10] and so the process has a unique shape-selective catalytic function as compared with other types of catalytic systems, the system (1) the mild reaction conditions (atmospheric pressure, 0 - 100 ° C); (2) the unique function of the shape-selective catalytic oxidation; (3) environmental friendliness.TS-1 has been very limited because the aperture is only about 0. 55 nm, and its range of applications where the aerodynamic diameter is greater than 0.60 nm substrate molecules can not enter within its pores without reactivity. Orderovercome this limitation, the type of catalyst to get a wider range of applications, the majority of scientists have successfully synthesized T S-2 [11], Ti-Beta [12] and a series of large aperture zeolite catalysts.In recent years, with the development of the petroleum refining and fine petrochemical technology requires the use of some reorganization of the oil to be effective. M41S [13, 14], HMS [15] and MSU [16] series of mesoporous molecular sieves Tiheteroatom derivatives T i-MCM-41 [17], Ti-MCM-48 [18], Ti-HMS [19, 20] and of Ti-the MSU [16] emerged, the latter in the selective oxidation of organic compoundsshowed higher catalytic activity.This paper reviews the recent years, the progress made in terms of microporous and mesoporous titanium silicalite catalyst preparation, characterization, and catalytic reaction.T S-1 is first synthesized, and also so far been studied most, and more thoroughly of a class of titanium silicalite catalyst. T S-1 is a Silicalite-1 isomorphously substituted derivatives thereof, having the MFI structure. TS- work and the results achieved many comments have been reported [10, 21 - 24] here only a brief overview of the TS-1 preparation, characterization, and their corresponding catalytic reaction.The classical method of preparing a zeolite catalyst is a hydrothermal synthesis method in the the earliest patent literature, Tar amasso [3] reported two preparation T S-1 The method of one is tetraethyl orthosilicate (T EOS) and tetraethylammonium n-titanate (TEOT) as silica source and a titanium source, and tetrapropyl ammonium hydroxide (TPA OH) as templating agent;other is a silica sol as a silicon source, and to dissolve in H2O2 the titanate as titanium source TPAOH templating agent in addition to the hydrothermal synthesis method, the TS -1 can also be obtained by the method of secondary synthesis TiCl4 and dealumination of ZSM-5 for vapor phase reaction, to give with hydrothermal synthesis method is similar to the structure [25], but this method is easy to cause anatase. Huanxin et al [26] for the titanium source, TEOS as a silicon source, and succeeded in synthesizing a T S-1 to T iCl3 The same catalytic activity, with the same reported in the literature, and the process can be effectively prevented from generation of anatase In addition, Tuel and T aarit, continuous coverage positive ions with phosphorus [27], 1, 6 - hexamethylene diammonium ion (Di -TPA) [28], tetraethyl ammonium hydroxide (TEAOH) / T PAOH and T EAOH / tetrabutyl ammonium hydroxide (T BA OH) [29] as a template to prepare T S-1 process. described using different Preparation of Template T S-1 is likely the. Preparation of Titanium Silicalite reagent over Na +, K + and other alkali metal ions of the concentration should be sufficiently low, because the alkali metal ions will hinder the titanium atom in the molecular sieve framework embedded; another the one hand, to prevent the preparation process difficult to dissolve the anatase anatase formation will lead to subsequent reaction of H2O2 decomposition and reduce the catalytic activity in order to prevent the generation of anatase, the preparation process should be vigorously stirred, so that titanium source in the silicon source is highly fragmented., Thangaraj, [7] the slower rate of hydrolysis the of tetrabutylammonium positive titanate (TBOT) Alternate TEOT, with anhydrous isopropyl alcohol as a co-solvent, and achieved good effect.TS-1 zeolite catalyst unique shape-selective catalytic oxidation function, undoubtedly has a direct relationship with the skeleton of T i (Ⅳ) Therefore, the focus of such zeolite characterization is to determine the existence of T i (Ⅳ) in the molecular sieveits ligand environment. characterization of TS-1, except for routine characterization of X-ray diffraction (XRD), N2 adsorption / desorption method, Fourier transform infrared spectroscopy (FT-IR) 29Si magic anglespinning nuclear magnetic resonance spectroscopy(29Si-MAS-NMR), diffuse reflectance UV - visible spectrum (DR UVVis), X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure analysis (XANES) and other technologies exist in the form of tetrahedral coordination T i (Ⅳ) provided the basis forAccording to the naming of IUPAC [40], the aperture between 2 - 50 nm molecular sieves for mesoporous molecular sieves. 1990s, class zeolite inorganic materials separation, ion exchange and catalytic disciplines one of the hot to longchain surfactants as templating agent, have been successfully synthesized M41S [13, 14], HMS [15] and MSU [16] and a series of mesoporous molecular sieves. formation mechanism of the pore structure of mesoporous molecular sieve research has been reported[41 - 46] At the sametime, Ti [17 - 20], V [47], Zr [48], Mn [49] and Cr [50] with the redox ability of transition metal atoms into mesoporous molecular sieveskeleton structure, get a lot of new catalysts for the preparation of fine chemicals which T i atom isomorphous substitution in the hole titanium silicalite has important significance of theoretical research and industrial application value.The Gont ier and T uel [20] also Press T anev to method prepared Ti-HMS, and preparation process of various factors such as the proportion of T iO2 / SiO2, isopropanol, surface active agent chain length, characteristic of the titanium source and of Surf / SiO2 system. found that in the preparation process, when the two reagents is mixed for 15 min, the resulting product had with Hex ago nal various characteristics of most of Surf / SiO2 the best ratio of 0.3 increase this proportion of the aperture increases, but the specific surface area and adsorption capacity is greatly reduced.Reviewed above on the synthesis, characterization and catalytic oxidation properties of titanium silicalite and mesoporous molecular sieves prepared its heteroatom derivatives can be seen, the titanium silicalite as a new type of selective oxidation catalyst demandis very important to the increasing volume of the preparation of fine chemicals. especially in recent years, the success of a series of mesoporous molecular sieves synthesis and application, making the range of applications greatly broaden the field has attracted more and more attention of researchersbut we should also see that there are still many problems in the field, such as the titanium silicalite catalytic reaction mechanism, the formation mechanism of mesoporous molecular sieves and skeleton in the presence of T i (Ⅳ) way for further exploration of these issuesand research will become a research focus in the coming period.钛硅分子筛催化剂的研究进展张小明张兆荣索继栓李树本( 中国科学院兰州化学物理研究所精细石油化工中间体国家工程研究中心兰州730000) 含钛催化剂在有机化合物氧化反应中的作用是众所周知的[ 1, 2] . 由于分子筛具有规整的孔道结构和较大的比表面积等特点, 在分子筛骨架中引入具有氧化还原能力的杂原子, 以制备新型的催化氧化催化剂, 一直是人们比较感兴趣的课题. 1983 年ENI[ 3] 的T ar amasso 及其合作者首次成功地合成了含钛的分子筛催化剂TS-1. 随后的研究发现, T S-1 在以H2O2 水溶液为氧化剂的一系列有机化合物的氧化反应, 如烯烃的环氧化[ 4]、芳烃环的羟基化[ 5, 6] 、酮的氨氧化[ 7] 、烷烃的氧化[ 8, 9] 及醇的氧化[ 10] 等过程中有独特的择形催化功能. 同其他类型的催化体系相比较,该体系有( 1)反应条件温和( 常压, 0- 100℃);( 2) 独特的择形催化氧化功能;( 3)环境友好等优点。

用廉价原料合成钛硅分子筛（TS-1）的研究的开题报告一、研究背景和意义分子筛是一种具有高度有序微孔结构的材料，其孔道大小和形状能够限制分子大小和形状，从而起到分子筛选、催化和吸附的作用。

其中，钛硅分子筛是一种重要的催化剂材料，具有广泛的应用前景。

但是，现有的工业生产钛硅分子筛的方法主要采用高成本的原料，制备过程中也存在一定的环境问题，如产生大量废气、废液等，不仅造成资源浪费，还会带来环境污染。

因此，研究用廉价原料合成钛硅分子筛具有重要的现实意义和应用价值。

二、研究内容和方法本研究的主要内容是探索用廉价原料制备钛硅分子筛的方法，并对其性能进行测试和评价。

具体步骤如下：1. 确定原料：本研究选取的原料为钛酸四丁酯、异丙醇、硅酸乙酯和氢氧化钠等廉价原料。

2. 制备方法：采用溶胶-凝胶法合成钛硅分子筛（TS-1）。

3. 性能测试：对合成的钛硅分子筛进行催化性能、晶体结构和形貌等方面的测试和评价，包括X射线衍射、傅里叶变换红外光谱、扫描电子显微镜等方法。

三、研究预期目标和意义1. 实现用廉价原料制备高质量的钛硅分子筛（TS-1）；2. 探索制备过程中的关键影响因素和优化方法；3. 分析合成的钛硅分子筛的结构和催化性能，评估其应用价值和环境友好程度；4. 对推广和应用该方法具有重要的现实意义和资源保护意义。

四、可行性分析本研究选取的原料为常见的工业化学品，成本低廉，易于获取。

采用的制备方法也是一种成熟的合成方法。

目前关于用廉价原料合成钛硅分子筛的研究尚处于初步阶段，但已经有部分研究证明了其可行性和应用价值。

因此，本研究具有一定的可行性。

五、研究进展和计划目前，已确定本研究的研究内容、方法和预期目标，并初步探讨了可行性。

下一步计划进一步深入研究制备过程中的关键影响因素和优化方法，并进行性能测试和分析。

预计在完成实验数据的收集、分析和整理后，可得到具有一定参考意义的研究成果。

钛硅分子筛的合成研究1钛硅分子筛TS-1合成及应用研究****学院***0902 ***摘要:本文重点综述了近年来钛硅分子筛催化材料的合成、改性及其催化应用的研究进展，包括钛硅分子筛( T S-1) 的水热合成方法和同晶取代合成法、钛硅分子筛双氧水体系的应用研究及近年中孔钛硅分子筛的进展.关键词：钛硅分子筛TS-1；催化氧化；双氧水；合成The Syntheses and Applications of TitaniumSilicalite TS Molecular SievesAbstract：Recent developments in the synthesis，modification andcatalyticproperties of titanium silicalite molecular sieve are reviewed，including thedevelopments in the synthesis of TS-1 with hydrothermal，applicat ions of titanium silicalite cataly tic ox idation system using hydr ogen pero xide, andresearch of mesopo rous titanium silicalite mo lecular sieves.自1983年有专利报道了以TS-1类钛硅分子筛为催化剂、稀双氧水(H2O2质量分数为30%)为氧化剂催化氧化苯酚同时生产邻、对苯二酚以来,有关分子筛类催化剂的羟基化反应报道甚多,研究得也最为充分。

TS-1分子筛的诞生掀起了有机物非均相选择性催化氧化的一场革命,特别是对于在温和条件下,用稀双氧水溶液为氧化剂的选择性氧化具有独特的性能。

TS-1分子筛催化剂使反应具有如下显著优点:①反应条件温和,可在常压、低温(20~100℃)下进行;②氧化目的产物收率高,选择性好;③工艺过程简单;④由于使用低浓度过氧化氢作为氧化剂,氧化源安全易得;⑤还原产物为H2O,反应体系没有引入杂质,不会造成环境污染。

催化新材料——钛硅分子筛合成及应用研究材料化学1001班郑胜男10150123摘要评述了钛硅分子筛新催化材料的合成及其催化应用的研究进展, 包括钛硅分子筛(TS-1) 的水热合成方法、原料、模板剂、影响因素、TS-1 同晶取代法合成、表征、活性中心、钛硅分子筛双氧水体系的应用研究及近年中孔钛硅分子筛的进展。

对未来的研究提出了建议。

关键词钛硅苯酚羟基化环氧化催化氧化双氧水分子筛Abstract Recent developments in the applicat ions and syntheses of titanium silicalite molecular sieves as a new kind of catalytic materials were reviewed, including developments of TS-1 hydrothermal synthesis methods, raw materials, templating agents, affecting factors, TS-1 synthesis by isomorphous replacement , charaterization, active sites, applications of titanium silicalite cataly ticox idation system using hydrogen peroxide, and research of mesoporous titanium silicalite molecular sieves. Suggest ions for further research were proposed.一、钛硅分子筛TS-1的水热法合成1.钛硅分子筛合成原料及TS-1水热合成方法钛硅沸石分子筛是指在沸石分子筛骨架中含有钛原子的一类杂原子分子筛, 现有TS-1、TS-2、TiB、TS-48、ETS-10 等。

钛硅分子筛的结构与物化特性研究进展于晓东 曹　钢(北京燕化石油化工股份公司化学品事业部,102501) 对钛硅分子筛的结构和物化特性的研究进行了综述,讨论了金属离子、非骨架TiO 2和表面酸性等对该分子筛的物化特性的影响。

关键词:　钛硅分子筛　特性　表面酸性 收稿日期:　2001-12-17。

作者简介:于晓东,工程师。

1992年毕业于华东化工学院,曾从事异丙苯、乙基苯酚等的工艺开发工作,后就读于母校,获硕士学位,现从事化工工艺开发工作。

钛硅分子筛(TS )由于其良好的催化性能,近年来,一直是分子筛催化剂领域的研究热点。

对于该分子筛的合成、应用已有大量文献报道[1～5],但有关它的表面性质方面的报道较少。

作者对TS -1的合成、表征及其在苯羟基化中的应用进行了详细的研究[6]。

本文从金属离子、非骨架TiO 2和表面酸性等三个方面对该分子筛的结构与物化特性的研究进展进行了综述。

1　钛硅分子筛的结构TS -1是具有MFI 结构的晶体,自首次成功合成以来,研究者通过F T -IR 、XRD 、XPS 、EX 2AFS 、Raman 等测试手段(见表1),对其结构特征进行了大量研究。

一般认为,TS -1和其它含钛分子筛中的钛离子均为四价。

XAN ES 和EXAFS 研究表明,骨架钛为完美的四面体结构[TiO 4],它随机地分布在分子筛骨架中,Ti —O 键长为0.180～0.181nm 。

Ti (IV )进入分子筛骨架改变了单元晶胞参数,如由XRD 获得的TS -1(1.1%Ti )的晶格常数为a =2.011nm 、b =1.992nm 、c =1.339nm ,而单斜晶系Sili 2calite -1和铝的类似物ZSM -5的晶胞常数分别为a =2.010nm 、b =1.987nm 、c =1.336nm 和a =2.007nm 、b =1.992nm 、c =1.342nm 。

lini 等[7]研究发现,晶胞常数与骨架钛(而不是非骨架钛)的含量呈线形关系。

钛硅分子筛全球专利申请现状及其发展趋势随着科学技术的不断发展，硅钛分子筛不断吸引着人们的关注。

硅钛分子筛的优越的物理性质使其成为高性能材料的理想候选材料之一。

作为一种以分子筛结构为基础的半导体材料，硅钛分子筛具有良好的电子传输性能、高的变形温度、极低的水吸收性和高的压缩强度，可以作为电子、光学、热控、储能和纳米催化反应等领域的关键材料。

由于具有独特的特性，硅钛分子筛应用范围更加广泛，因此，全球范围内的用户对其发展兴趣非常浓厚。

本文针对硅钛分子筛的专利申请，通过研究民用类和工业类的硅钛分子筛全球专利申请情况，分析全球专利申请现状及其发展趋势。

一、民用类硅钛分子筛全球专利申请现状根据专利数据库信息，2000年到2020年期间，全球范围内民用类硅钛分子筛申请了231项专利，其中以中国、美国、日本、德国和英国五国申请最多，专利领域以半导体、传感器、电子器件、催化剂和太阳能电池等前沿技术领域为主。

二、民用类硅钛分子筛全球专利申请发展趋势从2000年至2020年期间，全球民用类硅钛分子筛全球专利申请数量发展趋势主要分为三个阶段。

在2000年至2011年期间，申请数量缓慢上升，平均每年申请数量为20件；2011至2015年，全球专利申请数量急剧增长，平均每年申请数量达到65件；2016至2020年，申请数量整体维持在150件上下，其中2016年专利申请数量达到顶峰，之后稳定下降。

综上所述，近几年来，随着新技术的不断发展，全球范围内硅钛分子筛的专利申请量呈上升趋势。

民用类和工业类专利申请量呈双曲线状强势上涨，但是在2016年之后逐渐稳定下降。

通过研究可以发现，硅钛分子筛的研发及投入十分重视，主要用于高端实用领域，其成为更具竞争力的材料。

在未来，将会出现更多申请技术领域和更多申请专利国家，硅钛分子筛优越的性能将使其在更多领域应用得到更广泛的推广。