TS-1的制备及其催化性能研究
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摘要
钛硅分子筛TS-1由于其优异的催化氧化性能而受到极大关注,TS-1的制备及基础研究一直是催化领域的一个热点。对于TS-1的合成和催化性能研究报道较多,目前采用较多的是Thangaraj经过改进的水热合成法。但是传统的水热晶化合成法耗时、耗能,相对于传统水热合成方法,微波辐射加热法制备的分子筛晶体大小均一,纯度高,可以在其他条件相同的情况下大大缩短晶化时间。
为了考察传统水热合成法和微波辐射加热法对TS-1分子筛物化性能的影响,本次实验以TEOS为硅源,以TBOT钛源,以TPAOH为模板剂,采用传统水热合成法和微波辐射加热法两种方式分别制备了不同钛含量的几种TS-1样品,研究了微波辐射加热合成中,模板剂用量及晶化时间对合成TS-1分子筛的影响,确定了微波晶化合成TS-1需要的模板剂TPAOH用量(摩尔配比1Si:x Ti:0.36TPAOH:50H2O)及晶化时间(3.5小时),并借助FI-IR、XRD、SEM、UV-Vis、ICP等测试手段对合成的TS-1样品的表面形貌、晶体结构、晶粒大小、钛物种的存在形式进行了表征,测定了不同样品的钛含量。结果得出:在钛含量低时,两种方法制得样品的钛元素完全以骨架钛的形式存在,但微波辐射法合成样品有更高的钛含量,结晶更完善,晶粒之间出现少量粘连现象。随着钛含量增大,两种方法制得分子筛的钛含量逐渐接近,超过骨架钛含量上限(2.5%)的部分钛以非骨架形式(TiO2)存在,晶粒粒径增大,且均出现粘连堆积现象,但微波辐射制得的样品晶粒之间堆积成纤维状,说明微波辐射更有利于形成晶粒之间的堆积结构。
为了进一步研究两种方法对TS-1分子筛催化性能的影响,将两种方法制得的不同钛含量的TS-1分子筛用于正己烷部分氧化反应,结果表明:随着钛含量增大,两种方法制得分子筛的催化活性增加,且其氧化产物分布趋势相同,都有利于生成2-己酮。钛含量低时,微波辐射晶化合成的样品比常规水热合成样品的催化活性更高,但随着钛含量的增加,微波辐射法制备的样品受其晶体结构的影响,虽然反应速度增加,但是选择性下降。
Titanosilicalite-1 (TS-1) has attracted great attention due to its excellent catalytic properties. The synthesis of titanosilicalite-1 has become a hot spot in the zeolite catalytic fields.The most widely-used synthetic method of TS-1 is the hydrothermal synthesis improved by Thangaraj et al. Microwave irradiation (TS1-MI) is employed to synthesize zeolites and the advantage is utilized to get homogeneous nucleation and substantial reduction in crystallization time periods compared with the conventional hydrothermal method (TS1-CM) which is time-consuming and energy-consuming.
To investigate the influence of the above two synthetic methods on the catalytic performance TS-1, in this paper, TS-1 zeolite samples with different Ti content were synthesized with TPAOH as the template, TEOS as the silicon source and tetrabutyl orthotitanate as the titanium source using the two methods respectively, and the effect of the amount of tetrapropyl ammonium hydroxide (TPAOH) and crystallization time on the properties of TS-1 zeolite prepared under microwave irradiation was studied.
The amount of TPAOH (1Si:xTi:0.36TPAOH:50H2O) and the crystallization time (3.5hours) were established. The TS-1 samples were characterized by IR、XRD、SEM、UV-vis, and the results showed that the titanium element was incorporated into the framework of zeolites with low Ti content prepared by the two methods. The samples fabricated under microwave irradiation had higher Ti content and crystallinity, and the crystal particles of TS-1 samples from microwave irradiation were found to exhibit an adhered morphology. But with the Ti content increased, the Ti content in the samples synthesized by the two methods approached gradually, and the extra amount of Ti resulted in extra-framework anatase; grain size increased, but the crystals of the sample from TS1-MI stacked on top of one another to form a fibrous morphology, which showed that microwave irradiation facilitated the form of stacked morphology.
To further study of the two methods, the TS-1 samples with various Ti content were applied in partial oxidation of n-hexane using aqueous hydrogen peroxide as the oxidant. The results indicated: with the Ti content increased, the catalytic activities of the TS-1 samples from the two synthesis methods both increased, the reaction products were both of the same trend, and both methods benefited the produce of 2-hexanone. However, the TS-1 samples from TS1-MI have higher catalytic activities than those from TS1-CM when the Ti content of the zeolites was low, and with the Ti content increased, the n-hexane reaction rate catalyzed by the TS1-MI sample increased but the selectivity decreased due to the stacked morphology.
为了考察传统水热合成法和微波辐射加热法对TS-1分子筛物化性能的影响,本次实验以TEOS为硅源,以TBOT钛源,以TPAOH为模板剂,采用传统水热合成法和微波辐射加热法两种方式分别制备了不同钛含量的几种TS-1样品,研究了微波辐射加热合成中,模板剂用量及晶化时间对合成TS-1分子筛的影响,确定了微波晶化合成TS-1需要的模板剂TPAOH用量(摩尔配比1Si:x Ti:0.36TPAOH:50H2O)及晶化时间(3.5小时),并借助FI-IR、XRD、SEM、UV-Vis、ICP等测试手段对合成的TS-1样品的表面形貌、晶体结构、晶粒大小、钛物种的存在形式进行了表征,测定了不同样品的钛含量。结果得出:在钛含量低时,两种方法制得样品的钛元素完全以骨架钛的形式存在,但微波辐射法合成样品有更高的钛含量,结晶更完善,晶粒之间出现少量粘连现象。随着钛含量增大,两种方法制得分子筛的钛含量逐渐接近,超过骨架钛含量上限(2.5%)的部分钛以非骨架形式(TiO2)存在,晶粒粒径增大,且均出现粘连堆积现象,但微波辐射制得的样品晶粒之间堆积成纤维状,说明微波辐射更有利于形成晶粒之间的堆积结构。
为了进一步研究两种方法对TS-1分子筛催化性能的影响,将两种方法制得的不同钛含量的TS-1分子筛用于正己烷部分氧化反应,结果表明:随着钛含量增大,两种方法制得分子筛的催化活性增加,且其氧化产物分布趋势相同,都有利于生成2-己酮。钛含量低时,微波辐射晶化合成的样品比常规水热合成样品的催化活性更高,但随着钛含量的增加,微波辐射法制备的样品受其晶体结构的影响,虽然反应速度增加,但是选择性下降。
Titanosilicalite-1 (TS-1) has attracted great attention due to its excellent catalytic properties. The synthesis of titanosilicalite-1 has become a hot spot in the zeolite catalytic fields.The most widely-used synthetic method of TS-1 is the hydrothermal synthesis improved by Thangaraj et al. Microwave irradiation (TS1-MI) is employed to synthesize zeolites and the advantage is utilized to get homogeneous nucleation and substantial reduction in crystallization time periods compared with the conventional hydrothermal method (TS1-CM) which is time-consuming and energy-consuming.
To investigate the influence of the above two synthetic methods on the catalytic performance TS-1, in this paper, TS-1 zeolite samples with different Ti content were synthesized with TPAOH as the template, TEOS as the silicon source and tetrabutyl orthotitanate as the titanium source using the two methods respectively, and the effect of the amount of tetrapropyl ammonium hydroxide (TPAOH) and crystallization time on the properties of TS-1 zeolite prepared under microwave irradiation was studied.
The amount of TPAOH (1Si:xTi:0.36TPAOH:50H2O) and the crystallization time (3.5hours) were established. The TS-1 samples were characterized by IR、XRD、SEM、UV-vis, and the results showed that the titanium element was incorporated into the framework of zeolites with low Ti content prepared by the two methods. The samples fabricated under microwave irradiation had higher Ti content and crystallinity, and the crystal particles of TS-1 samples from microwave irradiation were found to exhibit an adhered morphology. But with the Ti content increased, the Ti content in the samples synthesized by the two methods approached gradually, and the extra amount of Ti resulted in extra-framework anatase; grain size increased, but the crystals of the sample from TS1-MI stacked on top of one another to form a fibrous morphology, which showed that microwave irradiation facilitated the form of stacked morphology.
To further study of the two methods, the TS-1 samples with various Ti content were applied in partial oxidation of n-hexane using aqueous hydrogen peroxide as the oxidant. The results indicated: with the Ti content increased, the catalytic activities of the TS-1 samples from the two synthesis methods both increased, the reaction products were both of the same trend, and both methods benefited the produce of 2-hexanone. However, the TS-1 samples from TS1-MI have higher catalytic activities than those from TS1-CM when the Ti content of the zeolites was low, and with the Ti content increased, the n-hexane reaction rate catalyzed by the TS1-MI sample increased but the selectivity decreased due to the stacked morphology.
引文
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