甲烷与二氧化碳催化氧化重整制合成气的研究
伊尔夏提·地里夏提
学位类型硕士
导师吾满江·艾力、侯振山
2015-05-22
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料工程
关键词甲烷 二氧化碳重整 Ni 催化剂 蛭石 柱撑
摘要

甲烷二氧化碳重整制取合成气反应,不仅为天然气资源的合理利用及缓解温室气体排放量提供了有效的解决途径,还因其为一可逆的强吸热过程,可作为能量传输系统,用来贮存太阳能、核能等。因而,近年来引起全世界学术界及工业界的广泛关注。该过程工业化的一个关键性问题,就是高活性、高稳定性实用型催化剂的研制开发。目前大量的研究集中于贵金属及镍基催化剂。前者价格昂贵,后者因积炭严重稳定性差。本论文重点对Ni 催化剂体系进行研究,经过合理设计,得到了一系列既具有优良的催化活性,又有独特的抗积炭性能的Ni 催化剂。本论文以柱撑蛭石为载体制备了一系列Ni 质量含量在4%-12%之间的催化剂。通过添加不同的金属助剂改性来制备镍基催化剂,结合XRD、BET、TPR、TG、SEM、XPS 等表征手段,对镍基催化剂上甲烷同时氧化和二氧化碳重整制合成气反应的催化性能及反应失活机理进行了系统的研究。采用新疆尉犁蛭石矿,依次经过HNO3 酸化,600℃灼烧,NaCl 交换,再用Keggin 离子插层,得到了羟基铝柱撑蛭石。实验结果表明,最佳的柱撑条件是硝酸浓度3mol/L,[OH-]:Al3+=2.4。镍负载量为12wt%时,Ni/CPVMT 催化剂活性最高。随焙烧温度的增加,金属- 载体相互作用增强, Ni/CPVMT 催化剂的活性和稳定性提高。往12Ni/CPVMT 催化剂中添加Mg、Ca、La 和Ba 改性能有效提高催化活性和稳定性。碱土金属改性的镍基催化剂活性和稳定性优于碱金属改性的催化剂。添加不同金属助剂对金属镍与载体间的相互作用都有不同程度的促进。Ca 的添加促进了Ni 的分散,阻止了金属Ni 颗粒在反应过程中烧结。在目前氧化重整反应过程中,积碳能被O2 消除。

其他摘要
The catalytic reforming of CH4 with CO2 has received extensive attention of industrial and academic circles all over the world. This reaction has also important environmental implications because both CH4 and CO2 are regarded as the main factors leading to the green-house effect. Thus, this process exhibits certain poten- tial to be used as thermochemical heat-pipe for recovery, storage and transmission of solar and other renewable energy sources. At present, one of the key problems for the application of this process is the development of practical catalysts with high activity and high stability. But the catalyst for the reaction at home and abroad studies have been largely focused on precious metals and nickel-based catalysts, precious metal catalyst is expensive , carbon deposition of nickel-based catalysts at the same time is serious and has low stability. The work is focused on the study of Ni-based catalysts, which has aeries of excellent catalytic activity and unique resistance of Ni catalysts by rational design. In this paper, the modified Ni-based catalysts have been prepared with piallared vermiculite as supports, which Ni contents weer between 4-12swt% and different metals as promoter, and characterized by XRD, BET, TGA, TPR, SEM, XPS and TEM. The catalytic performance and deactivation mechanism of catalysts have been investigated in the simultaneous oxidative conversion and CO2 reforming of methane to syngas. The natural vermiculite supplied from Weilim iner of Xinjiangwas submitted to an nitric acid treatment followed by calcinations, oxalic acid treatment, and sodium form by ion exchange, which results in the increase of the framework Al ratio, the reduction of the layer charge density, and the conversion of the vermiculite into a form of sodium- vermiculite. The results showed that the nitric acid concentrations 3mol/L and [OH-]:Al3+=2.4。 The Ni/CPVMT catalyst with Ni loading of 12wt% exhibited the highest catalytic activity. The catalytic activity and stability of Ni/CPVMT catalyst increased with calcined temperature increasing due to the stronger interaction between nickel particles and the support. The addition of Mg, Ca, La and Ba into Ni/CPVMT effectively enhanced the catalytic activity and stability of catalysts. The alkaline earth metal-modified Ni catalysts exhibited better catalytic activity and stability than alkali metal-modified ones. The addition of different metals as promoter improved metal-support interaction to some degree. The addition of Ca into Ni/CPVMT promoted the dispersion of Ni and prevented the sintering .
文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4274
专题新疆维吾尔自治区精细化工工程技术研究中心
作者单位中国科学院新疆理化技术研究所
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GB/T 7714
伊尔夏提·地里夏提. 甲烷与二氧化碳催化氧化重整制合成气的研究[D]. 北京. 中国科学院大学,2015.
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