摘要
SO_4~(2-)／M_XO_Y超强酸作为一类新型的催化剂，具有酸强度高、催化活性高、易分离、无腐蚀及对环境友好等优势，因而广泛用于酯化、烷基异构化、聚合及酰化等有机反应。但由于SO_4~(2-)／M_XO_Y超强酸存在比表面小、酸量少、成本较高及使用寿命较短等不足之处，因而在一定程度上制约了其推广应用。本论文利用储量丰富、价格低廉的广西宁明膨润土为原料，经提纯钠化后，采用微波辐射法制备出具有高比表面及热稳定性好的铝交联膨润土(Al-PILC)，再将活性组分SO_4~(2-)／TiO_2(ST)超强酸负载于其上，制备了负载型超强酸ST／Al-PILC催化剂。采用粉末X射线衍射(XRD)、吡啶吸附红外光谱(Py-IR)、傅立叶变换红外光谱(FT-IR)，X-射线光电子能谱(XPS)及N_2等温吸附-脱附等多种现代测试手段，对催化剂的晶体结构及表面性能进行了表征，并以苯甲酸与正戊醇酯化反应为探针反应考察了催化剂的活性及活性稳定性。为进一步提高负载催化剂的活性稳定性，还采用稀土元素镧和铈对ST／Al-PILC催化剂进行了改性，并探讨稀土元素对催化剂的结构及表面性能的影响。根据表征分析及实验结果得出以下结论：
在微波辐射时间为10min，OH~-／Al~(3+)(摩尔比)为2：1，投料比Al~(3+)／土为5mmol／g的条件下，可制备出性能较好的铝交联膨润土载体。所得交联产物的层面距(d 001)为19.8 (?)，比表面积为239 m~2／g，
孔体积为0.34 ml/g。与传统水热法相比，微波辐射法制备的铝交联膨
润土比表面积较大，孔径分布较为集中，热稳定性较高，经650“C
焙烧后，层柱结构完好无损。而传统水热法制备的铝交联膨润土比表
面积较小(仅为198 mZ/g)，孔径分布较为弥散，经650“c焙烧后层
柱结构完全塌陷。
Hammett指示剂法测定结果表明，负载型超强酸ST/AI一PILC催
化剂的酸强度可通过控制TIO:的负载量加以调节。TIO:负载量越小，
ST/AI一PILC催化剂的酸强度越低，当TIO:负载量达到29.5%时，样
品才具有超强酸性。与ST相比，ST/Al一PILC催化剂酸强度减小，但
与载体Al一PILC相比，ST/A1一PILC的酸强度大幅度提高。毗陡吸附
红外光谱分析结果表明，ST/Al一PILC催化剂表面同时具有Lewis酸
及Br6nsted酸，且表面酸中心数量远远大于载体Al一PILC的酸中心
数量。低温N:吸附一脱附实验结果显示，载体Al一PILC的引入，有效
地增大了催化剂的比表面。XRD测试结果表明，ST负载于载体
Al一PILc后，使TIO:锐钦矿晶相的形成及其向金红石晶相的转变被迟
滞。FT一11毛光谱分析结果表明，sT/AI一PILc中5042一离子与Tio:形
成了桥式双配位的酸中心结构。
通过考察催化剂对苯甲酸与正戊醇醋化反应的催化活性，表明载
体Al一PILC催化活性很低，ST/AI一PILC催化剂使反应物苯甲酸的转
化率显著提高，而ST催化剂的活性低于ST/AI一PILC催化剂。对催
化剂活性稳定性及失活原因的考察结果表明，载体Al一PILC的引入，
减缓了催化剂的失活速率，使ST/AI一PILC的活性稳定性比ST有所
提高。ST/AI一PILC催化剂的失活，不是由于活性组分中硫的价态变
化或催化剂中TIO:晶型的变化，而是有机物覆盖了催化剂的部分活
I陛中心以及催化剂上活性物种硫元素的流失所致。对失活催化剂的再
生实验结果表明，高温焙烧及补充活性组分法能使失活催化剂的活性
得到有效的恢复。
稀土元素斓和钵对ST/AI一PILC催化剂的改性研究表明，斓和饰
的引入对TIO:锐钦矿晶相形成温度无影响，但斓对TIO:的转晶有迟
滞作用，而饰对TIO:的转晶有促进作用，稀土斓和饰的引入对
ST/Al一PILC催化剂的酸强度及酸中心数量有不同的调变作用，斓的
引入使得ST/AI一PILC的超强酸中心的强度有所增强，酸中心数量增
加，而饰的引入则导致催化剂的酸强度及酸中心的数量下降。稀土元
素斓及钵改性对ST/Al一PILC催化剂的活性没有显著的影响，但使催
化剂的活性稳定性大为提高，稀土斓及钵提高ST/AI一PILC催化剂活
性稳定性的原因是有效地减少了催化剂表面5042一的流失。
广西宁明膨润土矿为国内特大型矿床之一，该矿虽然储量丰富，
但目前只开发了一些初级产品，资源的利用率不高，产品的附加值较
低，因此探索膨润土新的应用功能，有利于进一步拓宽我区膨润土矿
产资源的应用领域和促进地方经济的发展。
SO42-/MxOY type superacid, as a new type of catalyst, has some advantages such as its high acid strength and high activities in many organic reactions, it is easy to seperated from the reaction mixture, no corrosive to reactor and friendly to the environment. So it has been extensively used in many organic catalytic reactions of esterification, isomerization of n-alkanes, polymerization, acylation and so on. However, SO42-/MxOY also has some disadvantages such as small in surface area, hard to adjust its acidity and easy to deactivate, which limited its utilization in some extent. In this thesis, a naturally abundant bentonite from Ningmin County, Guangxi Zhuang Autonomous Region was used as raw material to prepare A1-pillared clay by using microwave irradiation method. The A1-pillared clay is of large surface area and good thermal stability. ST/A1-PILC (SO42-/TiO2/Al-pillared clay) solid superacid was prepared by loading active component SO42/TiO2 on Al-pillared clay. The texture structure and surface prope
rties of ST/A1-PILC were characterized by means of modern physical and chemical techniques such a X-ray powder diffraction (XRD), nitrogen adsorption-desorption isotherms, pyridine-adsorption infra-red spectra (Py-IR), Hammett indicator method, X-ray photoelectron spectroscopy (XPS) and Fourier transformation infra-red spectra (FT-IR) technique. Catalytic activity of the catalyst was evaluated using esterification of pentanol with benzoic acid as probe reaction. In order to enhance catalytic stability of the catalyst, ST/A1-PILC was modified with rare-earth elements (La and Ce), and the effect of rare-earth elements on texture structure and surface properties of ST/A1-PILC catalyst was investigated. Several conclusions can be drawn as follows.
A1-pillared clay with good properties can be prepared when microwave irradiation time is 10 min, a molar ratio OH7Al3+=2, ratio of Al/clay is 5mmol of aluminum per gram of clay. The basal spacing, specific surface area and pore volume of the Al-pillared clay are 19.8 A, 239 m2/g and 0.34 ml/g respectively. Comparing that obtained from conventional heating method, the Al-pillared clay prepared by
microwave irradiation method has larger specific surface area, better thermal stability and its pore distribution is quite narrow. The pillared structure is still preserved well after calcination at 650C. While the conventional A1-pillared clay has lower specific surface area (only 198 m2/g) and broadening pore distribution, its pillared structure collapsed after calcination at 650C.
The testing results of Hammett indicator method show that the acid strength of ST/A1-PILC catalyst can be adjusted by the loading of TiO2. The acid strength decreases with the decrease in the loading of TiO22. When the loading of TiO2 is less than 29.5 wt%, the samples have no superacidity. Py-IR spectra show that ST/A1-PILC catalyst possesses both Lewis and Bronsted acid sites, and the number of acid sites on ST/ Al-PILC is much larger than that on Al-PILC carrier. The adsorption and desorption of N2 experiment indicates that the introduction of Al-PILC carrier into ST can enhance the specific surface area of ST/A1-PILC catalyst effectively. The X-ray patterns indicate that Al-PILC carrier can inhibit the formation of anatase TiO2 and the transformation of anatase TiO2 into rutile TiO2. FT-IR spectra show that a bridged bidentate complex acid site was formed.
The ability of various catalysts to promoted benzoic acid esterification shows that the Al-PILC carrier exhibits very low catalytic activity, and the conversion of benzoic acid increases significantly over the ST/A1-PILC catalyst, the catalytic activity of ST/A1-PILC is higher than that of ST. By studying the stability and deactivation of catalyst, it turns out that the introduction of Al-PILC carrier into ST can reduce the rate of catalyst deactivation, acid sites partly blockage by organics and the loss of sulfur are the main contributors for deactivation, but not the change valence state of sulfur and transition of TiO2 crystal form. The
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