CAS OpenIR  > 研究所(批量导入)
钙钛矿负载镍催化剂的开发及其用于合成气甲烷化性能的研究
Alternative TitleDevelopment of Ni catalysts Supported on Oxides and their Application for Enhanced CO Methanation
贾春苗
Subtype硕士
Thesis Advisor苏发兵
2013-05-01
Degree Grantor中国科学院研究生院
Degree Discipline化学工程
Keyword钙钛矿氧化物   ni基催化剂   co甲烷化   氧化铝   积碳
Abstract我国的能源特点是“富煤,缺油,少气”,因此提出了煤制天然气路线。一方面可以缓解我国天然气供需的矛盾,另一方面又能实现褐煤等低品质煤的高效清洁利用。因此,煤制天然气具有十分重要的意义。在这个过程中,CO甲烷化反应是一个关键的步骤。该反应是一个强放热且体积缩小的反应,工业上常采用高温高压的反应条件,这给甲烷化催化剂带来了巨大挑战。目前工业上常用的是氧化铝负载Ni基催化剂,但较高的反应温度会造成氧化铝发生相变,孔结构坍塌等,最终导致催化活性的下降。钙钛矿氧化物因其具有优异的高温热稳定性、活泼的晶格氧、成本较低及储量丰富等特点,在许多高温反应中得到了广泛的应用。但将其用于甲烷化过程的研究却未见报道。 本课题的主要研究内容为:(1)采用过量浸渍法制备低镍含量的Ni/CaTiO3和Ni/Al2O3催化剂以及Ni/XTiO3 (X=Ca, Ba, Mg, Sr)催化剂。(2)采用物理吸附,化学吸附,TG/DTA,XRD,SEM,TEM,XPS及C-S分析仪对催化剂的物理化学性质进行表征。(3)通过在常压不同空速,以及加压条件下对催化剂进行性能评价,得到催化剂在不同温度、不同压力及不同空速下的CO甲烷化活性;又在高温高压下对催化剂进行长时间寿命实验,考察催化剂的稳定性;并将催化剂水热老化之后进行评价,考察催化剂的水热稳定性;另外,将催化剂应用于CO2甲烷化反应体系,考察催化剂对CO2甲烷化反应的活性。 实验结果表明:在低镍含量条件下,CaTiO3负载的Ni基催化剂具有比传统型Ni/Al2O3催化剂更高的CO及CO2甲烷化活性。主要影响因素为:①载体CaTiO3具有强的热稳定性;②Ni与载体CTO的相互作用力较弱,有利于NiO在较低的温度下完全还原;③载体CaTiO3表面非酸性,有利于抑制积碳;④Ni/CTO催化剂中Ni颗粒具有合适的粒径大小。在Ni/XTiO3 (X=Ca, Ba, Mg, Sr)催化剂中,Ni/BaTiO3的催化活性和稳定性都较高,具体原因目前还尚不明确,还有待探究。 关键词:钙钛矿氧化物,Ni基催化剂,CO甲烷化,氧化铝,积碳
Other AbstractChina is a country with abundant coal meanwhile poor oil and a little natural gas, and facing challenges in meeting the ever-growing demand of natural gas. Thus, the direction of producing substitute natural gas (SNG) from coal was proposed. It can meet the demand of natural gas, and also can achieve the efficient and clean use of lignite and other low-quality coal. Therefore, producing SNG from coal has great significance. In this process, CO methanation reaction is a key reaction that is highly exothermic and volume reduced, which bring about a big challenge for the development of methanation catalysts. As we know, Ni/Al2O3 catalysts are highly favorable for CO methanation in industry. However, high reaction temperature often causes remarkable changes to the Al2O3 support, e.g., variation in pore structure and crystal phase transformation, which may cause the quick decline in catalytic activity. The perovskite oxides possess the peculiarities of high thermal stability, and good reactivity of lattice oxygen, low cost, and rich resource. As supports or catalysts, they have been widely used in a number of high temperature reactions. However, the perovskite oxide-supported Ni catalysts have not been explored for the CO methanation reaction. In this work, Ni/CaTiO3, Ni/Al2O3 and Ni/XTiO3 (X=Ca, Ba, Mg, Sr) were prepared by impregnation method for methanation of CO to produce SNG. A series of characterization were carried out on these catalysts. We also performed the catalytic test under the condition of different WHSV, pressure and temperature. The results revealed that the Ni/CaTiO3 catalysts showed better performance than Ni/Al2O3 for CO methanation under different reaction conditions. This is because of the relatively weak interaction between Ni and CaTiO3 support, high stability of CaTiO3 support, the absence of acidic sites on the surface of CaTiO3, and the proper Ni particle size. Ni/BaTiO3 exhibited better than Ni/CaTiO3, and the structure-performance relationship of the catalysts is still to be explored. Overall, the work is important to the development of effective CO methanation catalysts for SNG production. Key words: perovskite oxide, Ni catalyst, CO methanation, Al2O3, carbon deposition
Pages58
Language中文
Document Type学位论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/8263
Collection研究所(批量导入)
Recommended Citation
GB/T 7714
贾春苗. 钙钛矿负载镍催化剂的开发及其用于合成气甲烷化性能的研究[D]. 中国科学院研究生院,2013.
Files in This Item:
File Name/Size DocType Version Access License
钙钛矿负载镍催化剂的开发及其用于合成气甲(4108KB) 限制开放CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[贾春苗]'s Articles
Baidu academic
Similar articles in Baidu academic
[贾春苗]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[贾春苗]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.