用于乙醇水蒸气重整Co/CeO_2催化剂的研究
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摘要
乙醇重整制氢催化剂存在的核心问题是由于积碳等导致稳定性差,CeO_2具有储-释氧能力并可与活性组分产生相互作用,因此可以调节活性组分的化学状态和有利于积炭的氧化消除,从而提高催化剂的稳定性。本文研究新催化剂—Co/CeO_2催化剂,主要研究内容包括催化剂结构和催化性能以及制备方法—结构性能的关系,并对乙醇水蒸气重整制氢反应(SRE)积碳和载体效应进行了初步探讨。
采用共沉淀法制备了Co/CeO_2催化剂,研究发现该系列催化剂中钴的主要存在形式包括小晶粒钴的氧化物、大晶粒Co3O4和进入CeO_2晶格的钴;制备条件中Co3O4含量、焙烧温度和老化时间影响钴在催化剂中的存在形式。结合催化剂性能测试结果可得,催化剂中高分散小晶粒钴的氧化物(还原所得的钴)是关键的活性组分。其中10%Co/CeO_2-C-650催化剂对SRE反应具有高活性、高选择性和较好的稳定性。
采用浸渍法分别制备了Co/CeO_2和Co/CeXTi1-XO_2催化剂,与共沉淀法制备的催化剂相比,该系列催化剂产物中甲烷含量较高。载体中Ti的加入并不能改善催化剂性能,Ti可能和Ce或Co发生相互作用,从而削弱了Co和Ce的相互作用,导致催化剂性能下降。XRD结果显示浸渍法制备的Co/CeO_2催化剂主要物相是Co3O4和CeO_2,比较发现制备方法对催化剂中钴的化学状态有显著的影响。该系列催化剂中20%Co/CeO_2-I-650催化剂对SRE反应具有高活性和高选择性和较好的稳定性。
考察了制备方法对Co /CeO_2催化剂结构、还原性能和催化性能的影响,证实了钴和CeO_2之间存在协同效应,CeO_2对CoOx的还原产生影响,被还原出的Co0是SRE反应的主要活性组分;制备方法的不同使得Co与载体间的相互作用不同,其中共沉淀制备的催化剂进入氧化铈晶格的钴较多,其表面的钴铈作用较弱,钴更容易被还原,因此具有较多的活性组分,使得该催化剂的活性和选择性较好,积碳程度较小,同时,二者结构上的差异导致沉积碳种类不同。
利用共沉淀法制备的10%Co/CeO_2-C-650催化剂,考察了反应温度和反应时间对积碳的影响,结合DTA-TG热分析技术和SEM,初步探讨了SRE反应中积碳量和积碳种类的规律。
探讨氧化铝作为SRE反应制氢催化剂载体的可行性,考察了载体Al2O3对催化剂性能及结构的影响。
Catalyst stability is a crucial problem for hydrogen production in steam reforming of ethanol (SRE), which can be caused by carbon deposition, metal sintering, and so on. CeO_2 has a good oxygen-storage capacity and tends to interact with active component. The presence of CeO_2 is benefit for carbon oxidation and adjusting chemical nature of active component. These would improve catalyst stability. In our work, new Co/CeO_2 catalysts for SRE were studied. The study included catalyst structure, catalytic performance and the relation of preparation method with structure and catalyst performance. Besides, the carbon deposition and the effect of support were also investigated on the Co/CeO_2 catalysts for SRE.
The Co/CeO_2 catalysts were prepared by co-precipitation. The research indicates that cobalt exists in three forms including cobalt oxide with small crystal size, bulk Co3O4, and cobalt in CeO_2 lattice in these catalysts. Both the content of cobalt and calcination temperature affects the form of cobalt. Combining with activity test, metal cobalt reduced from high dispersion oxides of cobalt with small crystal size is crucial active component. The 10%Co/CeO_2-650 catalyst prepared by co-precipitation method shows high activity, selectivity and good stability.
The Co/CeO_2 and Co/CeXTi1-XO_2 catalysts were prepared by impregnation method. They show higher selectivity towards methane than Co/CeO_2 prepared by co-precipitation method. It shows that the addition of Ti does not improve catalyst performance. Ti may interact with Ce or Co, and weaken the interaction between Co and Ce, so it results in the decrease of catalytic performance. In addition, XRD results show that only Co3O4 and CeO_2 phases can be observed in the Co/CeO_2 catalysts prepared by impregnation method. So the chemical nature of cobalt in the catalysts is affected obviously by preparation method. The 20%Co/CeO_2-I-650 catalyst prepared by impregnation method also shows good catalytic performance for SRE.
The effect of preparation method on catalyst structure, reduction capability and catalytic performance was investigated. The results indicate that the synergistic effect exists between cobalt and CeO_2, which influences the reduction of CoOx. Co0 reduced from CoOx is key active component. The preparation method influences the interaction between cobalt and CeO_2. In comparison with catalysts prepared by impregnation, more Co ions enters into CeO_2 lattice, and results in weaker interaction between active phase and ceria on surface of Co3O4/CeO_2 prepared by co-precipitation. Thus, it is easier to reduce Co species to metal cobalt that is active for SRE. Meanwhile, the incorporation of Co ions into CeO_2 crystal lattice is beneficial for resistance to carbon deposition.
The impact of reaction temperature and reaction time on carbon deposition was researched on 10%Co/CeO_2-650 catalyst with co-precipitation method. Combining with DTA-TG and SEM study, the discipline between the quantities of carbon deposition and carbon species was analyzed.
The feasibility of Al2O3 as carrier for hydrogen production was investigated in SRE. Further, the effect of Al2O3 on catalyst structure and performance was studied.
采用共沉淀法制备了Co/CeO_2催化剂,研究发现该系列催化剂中钴的主要存在形式包括小晶粒钴的氧化物、大晶粒Co3O4和进入CeO_2晶格的钴;制备条件中Co3O4含量、焙烧温度和老化时间影响钴在催化剂中的存在形式。结合催化剂性能测试结果可得,催化剂中高分散小晶粒钴的氧化物(还原所得的钴)是关键的活性组分。其中10%Co/CeO_2-C-650催化剂对SRE反应具有高活性、高选择性和较好的稳定性。
采用浸渍法分别制备了Co/CeO_2和Co/CeXTi1-XO_2催化剂,与共沉淀法制备的催化剂相比,该系列催化剂产物中甲烷含量较高。载体中Ti的加入并不能改善催化剂性能,Ti可能和Ce或Co发生相互作用,从而削弱了Co和Ce的相互作用,导致催化剂性能下降。XRD结果显示浸渍法制备的Co/CeO_2催化剂主要物相是Co3O4和CeO_2,比较发现制备方法对催化剂中钴的化学状态有显著的影响。该系列催化剂中20%Co/CeO_2-I-650催化剂对SRE反应具有高活性和高选择性和较好的稳定性。
考察了制备方法对Co /CeO_2催化剂结构、还原性能和催化性能的影响,证实了钴和CeO_2之间存在协同效应,CeO_2对CoOx的还原产生影响,被还原出的Co0是SRE反应的主要活性组分;制备方法的不同使得Co与载体间的相互作用不同,其中共沉淀制备的催化剂进入氧化铈晶格的钴较多,其表面的钴铈作用较弱,钴更容易被还原,因此具有较多的活性组分,使得该催化剂的活性和选择性较好,积碳程度较小,同时,二者结构上的差异导致沉积碳种类不同。
利用共沉淀法制备的10%Co/CeO_2-C-650催化剂,考察了反应温度和反应时间对积碳的影响,结合DTA-TG热分析技术和SEM,初步探讨了SRE反应中积碳量和积碳种类的规律。
探讨氧化铝作为SRE反应制氢催化剂载体的可行性,考察了载体Al2O3对催化剂性能及结构的影响。
Catalyst stability is a crucial problem for hydrogen production in steam reforming of ethanol (SRE), which can be caused by carbon deposition, metal sintering, and so on. CeO_2 has a good oxygen-storage capacity and tends to interact with active component. The presence of CeO_2 is benefit for carbon oxidation and adjusting chemical nature of active component. These would improve catalyst stability. In our work, new Co/CeO_2 catalysts for SRE were studied. The study included catalyst structure, catalytic performance and the relation of preparation method with structure and catalyst performance. Besides, the carbon deposition and the effect of support were also investigated on the Co/CeO_2 catalysts for SRE.
The Co/CeO_2 catalysts were prepared by co-precipitation. The research indicates that cobalt exists in three forms including cobalt oxide with small crystal size, bulk Co3O4, and cobalt in CeO_2 lattice in these catalysts. Both the content of cobalt and calcination temperature affects the form of cobalt. Combining with activity test, metal cobalt reduced from high dispersion oxides of cobalt with small crystal size is crucial active component. The 10%Co/CeO_2-650 catalyst prepared by co-precipitation method shows high activity, selectivity and good stability.
The Co/CeO_2 and Co/CeXTi1-XO_2 catalysts were prepared by impregnation method. They show higher selectivity towards methane than Co/CeO_2 prepared by co-precipitation method. It shows that the addition of Ti does not improve catalyst performance. Ti may interact with Ce or Co, and weaken the interaction between Co and Ce, so it results in the decrease of catalytic performance. In addition, XRD results show that only Co3O4 and CeO_2 phases can be observed in the Co/CeO_2 catalysts prepared by impregnation method. So the chemical nature of cobalt in the catalysts is affected obviously by preparation method. The 20%Co/CeO_2-I-650 catalyst prepared by impregnation method also shows good catalytic performance for SRE.
The effect of preparation method on catalyst structure, reduction capability and catalytic performance was investigated. The results indicate that the synergistic effect exists between cobalt and CeO_2, which influences the reduction of CoOx. Co0 reduced from CoOx is key active component. The preparation method influences the interaction between cobalt and CeO_2. In comparison with catalysts prepared by impregnation, more Co ions enters into CeO_2 lattice, and results in weaker interaction between active phase and ceria on surface of Co3O4/CeO_2 prepared by co-precipitation. Thus, it is easier to reduce Co species to metal cobalt that is active for SRE. Meanwhile, the incorporation of Co ions into CeO_2 crystal lattice is beneficial for resistance to carbon deposition.
The impact of reaction temperature and reaction time on carbon deposition was researched on 10%Co/CeO_2-650 catalyst with co-precipitation method. Combining with DTA-TG and SEM study, the discipline between the quantities of carbon deposition and carbon species was analyzed.
The feasibility of Al2O3 as carrier for hydrogen production was investigated in SRE. Further, the effect of Al2O3 on catalyst structure and performance was studied.
引文
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