鈰鋯固溶體及稀土改性β沸石分子篩對甲、乙硫醇催化分解的研究
發(fā)布時間：2018-08-05 16:02
【摘要】：天然氣及石油產(chǎn)品中存在較難脫除的低碳硫醇物質(zhì),主要包括甲硫醇(CH3SH)和乙硫醇(C2H5SH)。硫醇的存在影響了天然氣石油產(chǎn)品的加工與利用。另一方面,低碳硫醇更是一種有惡劣臭味的污染氣體,嚴重危害人類的身心健康和生存環(huán)境。目前催化分解作為一種高效、低消耗的低碳硫醇脫除方法深受關(guān)注。甲、乙硫醇催化分解的產(chǎn)物可作為工業(yè)原料應(yīng)用于資源再生與利用。本論文通過尿素研磨燃燒法快速制備鈰鋯固溶體催化劑應(yīng)用于甲、乙硫醇催化分解�？疾烊N焙燒溫度(450℃、600℃和750℃)條件下Ce0.8Zr0.2O2固溶體催化劑常壓下催化分解乙硫醇的效果。采用XRD、TEM、BET、H2-TPR、XPS和Raman等表征手段對催化劑的物理化學性質(zhì)、表面結(jié)構(gòu)進行研究。另外,本文對H-Beta型、H-Y型沸石及其一系列稀土改性復合氧化物催化分解乙硫醇的活性進行了初步的探究。要結(jié)果歸納如下:(1)通過尿素研磨燃燒法快速制備納米顆粒Ce0.8Zr0.2O2固溶體催化劑,該催化劑對甲硫醇分解具有較好的分解活性。與傳統(tǒng)表面活性劑-輔助法相比,該方法具有操作簡潔、耗時少的優(yōu)點,并且甲硫醇催化分解的活性得到了提高。借助產(chǎn)物分析可推測CH3SCH3為鈰鋯固溶體催化劑催化分解甲硫醇的中間產(chǎn)物,高溫條件下主要分解產(chǎn)物為H2S和CH4,并存在少量的H2、其他烴類。通過尿素研磨燃燒法制備鈰鋯固溶體催化劑有助于較多的Zr進入CeO2骨架結(jié)構(gòu)中,從而形成較多的氧空位。實驗結(jié)果表明,該催化劑催化分解甲硫醇的活性取決于氧空位濃度、表面化學吸附氧含量以及還原性。(2)考察不同焙燒溫度下Ce0.8Zr0.2O2固溶體催化劑常壓下催化分解乙硫醇的活性,發(fā)現(xiàn)鈰鋯固溶體對乙硫醇催化降解有較好活性。表征結(jié)果表明:在一定范圍內(nèi)升高焙燒溫度有利于更多Zr4+進入CeO2晶格,從而增加氧空位濃度,但過高的溫度會使催化劑顆粒團聚,并降低催化劑表面吸附氧的相對含量,并導致催化劑比表面積一定程度的降低。600℃焙燒的鈰鋯催化劑表現(xiàn)出對乙硫醇催化分解最佳活性,得益于催化劑外部Ce3+相對濃度、氧空位濃度與比表面積的協(xié)同作用。一方面,這些催化劑外部Ce3+相對濃度與催化劑氧空位濃度,有利于氧遷移,對催化分解反應(yīng)有促進作用,另一方面催化劑比表面積越大,越有利于反應(yīng)物吸附、暴露更多活性位點,進而有助于催化活性的提高。(3)與H-Y型沸石分子篩相比,H-Beta型沸石分子篩對于乙硫醇催化分解具有更佳的活性,且分解產(chǎn)物乙烯選擇性很高。對不同稀土(La,Ce,Pr,Nd,Sm,Eu,Gd,Er,Y)改性的一批次H-Beta型沸石分子篩催化劑進行活性效果評價,其活性大小順序為: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沸石分子篩,其余稀土改性的H-Beta沸石分子篩與未改性的H-Beta沸石分子篩相比,其催化分解乙硫醇的活性明顯提高。Er、Gd改性的H-Beta沸石分子篩催化劑催化分解乙硫醇的活性最好。稀土改性有助于提高H-Beta型沸石分子篩催化劑的反應(yīng)壽命。
[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.
【學位授予單位】：昆明理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36
本文編號：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.
【學位授予單位】：昆明理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36
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