铈锆固溶体及稀土改性β沸石分子筛对甲、乙硫醇催化分解的研究
发布时间：2018-08-05 16:02
【摘要】：天然气及石油产品中存在较难脱除的低碳硫醇物质,主要包括甲硫醇(CH3SH)和乙硫醇(C2H5SH)。硫醇的存在影响了天然气石油产品的加工与利用。另一方面,低碳硫醇更是一种有恶劣臭味的污染气体,严重危害人类的身心健康和生存环境。目前催化分解作为一种高效、低消耗的低碳硫醇脱除方法深受关注。甲、乙硫醇催化分解的产物可作为工业原料应用于资源再生与利用。本论文通过尿素研磨燃烧法快速制备铈锆固溶体催化剂应用于甲、乙硫醇催化分解。考察三种焙烧温度(450℃、600℃和750℃)条件下Ce0.8Zr0.2O2固溶体催化剂常压下催化分解乙硫醇的效果。采用XRD、TEM、BET、H2-TPR、XPS和Raman等表征手段对催化剂的物理化学性质、表面结构进行研究。另外,本文对H-Beta型、H-Y型沸石及其一系列稀土改性复合氧化物催化分解乙硫醇的活性进行了初步的探究。要结果归纳如下:(1)通过尿素研磨燃烧法快速制备纳米颗粒Ce0.8Zr0.2O2固溶体催化剂,该催化剂对甲硫醇分解具有较好的分解活性。与传统表面活性剂-辅助法相比,该方法具有操作简洁、耗时少的优点,并且甲硫醇催化分解的活性得到了提高。借助产物分析可推测CH3SCH3为铈锆固溶体催化剂催化分解甲硫醇的中间产物,高温条件下主要分解产物为H2S和CH4,并存在少量的H2、其他烃类。通过尿素研磨燃烧法制备铈锆固溶体催化剂有助于较多的Zr进入CeO2骨架结构中,从而形成较多的氧空位。实验结果表明,该催化剂催化分解甲硫醇的活性取决于氧空位浓度、表面化学吸附氧含量以及还原性。(2)考察不同焙烧温度下Ce0.8Zr0.2O2固溶体催化剂常压下催化分解乙硫醇的活性,发现铈锆固溶体对乙硫醇催化降解有较好活性。表征结果表明:在一定范围内升高焙烧温度有利于更多Zr4+进入CeO2晶格,从而增加氧空位浓度,但过高的温度会使催化剂颗粒团聚,并降低催化剂表面吸附氧的相对含量,并导致催化剂比表面积一定程度的降低。600℃焙烧的铈锆催化剂表现出对乙硫醇催化分解最佳活性,得益于催化剂外部Ce3+相对浓度、氧空位浓度与比表面积的协同作用。一方面,这些催化剂外部Ce3+相对浓度与催化剂氧空位浓度,有利于氧迁移,对催化分解反应有促进作用,另一方面催化剂比表面积越大,越有利于反应物吸附、暴露更多活性位点,进而有助于催化活性的提高。(3)与H-Y型沸石分子筛相比,H-Beta型沸石分子筛对于乙硫醇催化分解具有更佳的活性,且分解产物乙烯选择性很高。对不同稀土(La,Ce,Pr,Nd,Sm,Eu,Gd,Er,Y)改性的一批次H-Beta型沸石分子筛催化剂进行活性效果评价,其活性大小顺序为:9%Er/H-Beta9%Gd/H-Beta9%Nd/H-Beta9%Eu/H-beta9%Y/H-Beta9%La/H-Beta9%Sm/H-Beta9%Ce/H-BetaH-Beta9%Pr/H-Beta除了 Eu改性的H-Bate沸石分子筛,其余稀土改性的H-Beta沸石分子筛与未改性的H-Beta沸石分子筛相比,其催化分解乙硫醇的活性明显提高。Er、Gd改性的H-Beta沸石分子筛催化剂催化分解乙硫醇的活性最好。稀土改性有助于提高H-Beta型沸石分子筛催化剂的反应寿命。
[Abstract]:Low carbon mercaptan, which is difficult to remove in natural gas and petroleum products, mainly includes methinol (CH3SH) and ethinol (C2H5SH). The presence of mercaptan affects the processing and utilization of natural gas petroleum products. On the other hand, low carbon mercaptan is a kind of bad odor pollution gas, which seriously endangers the physical and mental health and living environment of human beings. Catalytic decomposition is a highly efficient and low consumption method for the removal of low carbon mercaptan. The products of catalytic decomposition of methyl and ethyl mercaptan can be used as industrial raw materials for resource regeneration and utilization. In this paper, the preparation of cerium zirconium solid solution catalyst by urea grinding combustion method was applied to the catalytic decomposition of ethyl thiol. Three kinds of calcination were investigated. The effect of catalytic decomposition of ethyl thiol on Ce0.8Zr0.2O2 solid solution catalyst under normal pressure at temperature (450, 600 and 750 C). The physical and chemical properties and surface structure of the catalyst are studied by means of XRD, TEM, BET, H2-TPR, XPS and Raman. In addition, this paper has a series of H-Beta, H-Y zeolite and a series of rare earth modified compound oxides. The activity of catalytic decomposition of ethyl mercaptan is preliminarily explored. The results are summarized as follows: (1) the rapid preparation of nano particle Ce0.8Zr0.2O2 solid solution catalyst by the urea grinding combustion method, the catalyst has good decomposition activity for the decomposition of methyl mercaptan. Compared with the traditional surfactants auxiliary method, the method has simple operation and less time consuming. The activity of catalytic decomposition of methyl mercaptan has been improved. With the aid of product analysis, it is speculated that CH3SCH3 is the intermediate product of methyl mercaptan catalyzed by cerium zirconium solid solution catalyst. The main decomposition products are H2S and CH4 at high temperature, and there are a small amount of H2 and other hydrocarbons. The catalyst for cerium zirconium solid solution is prepared by the urea grinding and combustion method. The results show that the catalytic activity of the catalyst for the decomposition of methyl mercaptan depends on the oxygen vacancy concentration, the surface chemical adsorption oxygen content and the reducibility. (2) the catalytic decomposition of ethyl mercaptan under the atmospheric pressure of Ce0.8Zr0.2O2 solid solution catalyst at different calcination temperatures is investigated at different calcination temperatures. (2) the catalytic decomposition of thiol in the Ce0.8Zr0.2O2 solid solution catalyst at different calcination temperatures It is found that cerium zirconium solid solution has good activity for the catalytic degradation of ethyl thiol. The results show that the increase of calcination temperature in a certain range is beneficial to more Zr4+ into the CeO2 lattice, thus increasing the oxygen vacancy concentration, but the high temperature will lead to the agglomeration of the catalyst particles, and reduce the relative content of the oxygen adsorption on the surface of the catalyst, and lead to the catalysis. The catalyst of cerium zirconium calcined at a certain degree of reduction of the specific surface area at.600 C shows the best catalytic activity for catalytic decomposition of ethyl thiol, benefiting from the relative concentration of the external Ce3+ of the catalyst, the oxygen vacancy concentration and the specific surface area. On the one hand, the relative concentration of the external Ce3+ and the oxygen vacancy concentration of the catalyst is beneficial to the migration of oxygen. Catalytic decomposition reaction has a promoting effect, on the other hand, the greater the surface area of the catalyst, the more beneficial to the adsorption of reactants, the exposure of more active sites, and the improvement of catalytic activity. (3) compared with the H-Y zeolite molecular sieve, the H-Beta zeolite molecular sieve has a better activity for ethin catalytic decomposition, and the decomposition product of ethylene selection The activity of a batch of H-Beta zeolite catalysts modified by different rare earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Y) was evaluated. The order of activity was as follows: 9%Er/H-Beta9%Gd/H-Beta9%Nd/H-Beta9%Eu/H-beta9%Y/H-Beta9%La/H-Beta9%Sm/H-Beta9% Ce/H-BetaH-Beta9%Pr/H-Beta except for the modified zeolite molecular sieve, Compared with the unmodified H-Beta zeolite molecular sieves, the remainder of the remainder modified H-Beta zeolite improved the activity of ethesol catalyzed by.Er, and the Gd modified H-Beta zeolite catalyst has the best catalytic activity to catalyze the decomposition of ethesol. The rare-earth modification helps to improve the reaction life of the H-Beta zeolite catalyst.
【学位授予单位】：昆明理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
本文编号：2166285
[Abstract]:Low carbon mercaptan, which is difficult to remove in natural gas and petroleum products, mainly includes methinol (CH3SH) and ethinol (C2H5SH). The presence of mercaptan affects the processing and utilization of natural gas petroleum products. On the other hand, low carbon mercaptan is a kind of bad odor pollution gas, which seriously endangers the physical and mental health and living environment of human beings. Catalytic decomposition is a highly efficient and low consumption method for the removal of low carbon mercaptan. The products of catalytic decomposition of methyl and ethyl mercaptan can be used as industrial raw materials for resource regeneration and utilization. In this paper, the preparation of cerium zirconium solid solution catalyst by urea grinding combustion method was applied to the catalytic decomposition of ethyl thiol. Three kinds of calcination were investigated. The effect of catalytic decomposition of ethyl thiol on Ce0.8Zr0.2O2 solid solution catalyst under normal pressure at temperature (450, 600 and 750 C). The physical and chemical properties and surface structure of the catalyst are studied by means of XRD, TEM, BET, H2-TPR, XPS and Raman. In addition, this paper has a series of H-Beta, H-Y zeolite and a series of rare earth modified compound oxides. The activity of catalytic decomposition of ethyl mercaptan is preliminarily explored. The results are summarized as follows: (1) the rapid preparation of nano particle Ce0.8Zr0.2O2 solid solution catalyst by the urea grinding combustion method, the catalyst has good decomposition activity for the decomposition of methyl mercaptan. Compared with the traditional surfactants auxiliary method, the method has simple operation and less time consuming. The activity of catalytic decomposition of methyl mercaptan has been improved. With the aid of product analysis, it is speculated that CH3SCH3 is the intermediate product of methyl mercaptan catalyzed by cerium zirconium solid solution catalyst. The main decomposition products are H2S and CH4 at high temperature, and there are a small amount of H2 and other hydrocarbons. The catalyst for cerium zirconium solid solution is prepared by the urea grinding and combustion method. The results show that the catalytic activity of the catalyst for the decomposition of methyl mercaptan depends on the oxygen vacancy concentration, the surface chemical adsorption oxygen content and the reducibility. (2) the catalytic decomposition of ethyl mercaptan under the atmospheric pressure of Ce0.8Zr0.2O2 solid solution catalyst at different calcination temperatures is investigated at different calcination temperatures. (2) the catalytic decomposition of thiol in the Ce0.8Zr0.2O2 solid solution catalyst at different calcination temperatures It is found that cerium zirconium solid solution has good activity for the catalytic degradation of ethyl thiol. The results show that the increase of calcination temperature in a certain range is beneficial to more Zr4+ into the CeO2 lattice, thus increasing the oxygen vacancy concentration, but the high temperature will lead to the agglomeration of the catalyst particles, and reduce the relative content of the oxygen adsorption on the surface of the catalyst, and lead to the catalysis. The catalyst of cerium zirconium calcined at a certain degree of reduction of the specific surface area at.600 C shows the best catalytic activity for catalytic decomposition of ethyl thiol, benefiting from the relative concentration of the external Ce3+ of the catalyst, the oxygen vacancy concentration and the specific surface area. On the one hand, the relative concentration of the external Ce3+ and the oxygen vacancy concentration of the catalyst is beneficial to the migration of oxygen. Catalytic decomposition reaction has a promoting effect, on the other hand, the greater the surface area of the catalyst, the more beneficial to the adsorption of reactants, the exposure of more active sites, and the improvement of catalytic activity. (3) compared with the H-Y zeolite molecular sieve, the H-Beta zeolite molecular sieve has a better activity for ethin catalytic decomposition, and the decomposition product of ethylene selection The activity of a batch of H-Beta zeolite catalysts modified by different rare earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Y) was evaluated. The order of activity was as follows: 9%Er/H-Beta9%Gd/H-Beta9%Nd/H-Beta9%Eu/H-beta9%Y/H-Beta9%La/H-Beta9%Sm/H-Beta9% Ce/H-BetaH-Beta9%Pr/H-Beta except for the modified zeolite molecular sieve, Compared with the unmodified H-Beta zeolite molecular sieves, the remainder of the remainder modified H-Beta zeolite improved the activity of ethesol catalyzed by.Er, and the Gd modified H-Beta zeolite catalyst has the best catalytic activity to catalyze the decomposition of ethesol. The rare-earth modification helps to improve the reaction life of the H-Beta zeolite catalyst.
【学位授予单位】：昆明理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
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