液相体系Ru-Co3O4催化CO2加氢制甲烷过程中的溶剂效应研究  

Solvent effect on the activity of Ru-Co3O4 catalyst for liquid-phase hydrogenation of CO2 into methane

作　　者：宋英健 崔晓静 邓天昇 秦张峰[1] 樊卫斌[1] SONG Ying-jian;CUI Xiao-jing;DENG Tian-sheng;QIN Zhang-feng;FAN Wei-bin(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China;Department of Chemistry and Chemical Engineering,Taiyuan Institute of Technology,Taiyuan 030008,China)

机构地区：[1]中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西太原030001 [2]中国科学院大学,北京100049 [3]太原工业学院化学与化工系,山西太原030008

出　　处：《燃料化学学报》2021年第2期178-185,共8页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(U1910203,21972159)资助。

摘　　要：采用共沉淀法制备了Ru-Co3O4催化剂,考察了其在液相体系的CO2加氢制甲烷催化性能,并与浸渍法制备的Ru基催化剂(Ru/SiO2、Ru/CeO2、Ru/ZrO2、Ru/TiO2)进行了对比,探讨了不同溶剂(水、正丁醇、1, 4-丁内酯、DMF、十氢萘、环己烷、异辛烷)对催化性能的影响规律。发现Ru-Co3O4具有较高的加氢催化活性和产物选择性,十氢萘和异辛烷作溶剂显示出良好的催化性能。在200℃及H2/CO2=3∶1(v/v, 4 MPa)条件下,CO2转化率达45.6%,CH4的选择性约97%。同位素标记实验和原位漫反射红外光谱结果表明,十氢萘和异辛烷中的叔碳离子可以起到较强的供氢作用,从而提高了催化活性。Ru-Co3O4 catalyst was prepared by the co-precipitation method. Its catalytic performance in liquid-phase hydrogenation of CO2 into methane was investigated, and compared with those of the conventional Ru-based catalysts(Ru/SiO2, Ru/CeO2, Ru/ZrO2, Ru/TiO2) prepared by impregnation method. The solvents including H2O, n-butanol,1,4-butyrolactone, DMF, n-nonane, decalin, cyclohexane and isooctane had significant solvent effects on the catalytic performance. Compared with other solvents, the catalyst showed higher activity and selectivity catalytic performance when decalin and isooctane was applied as the solvent. At 200 ℃ and H2/CO2=3:1(v/v, 4 MPa) and with decalin as the solvent, the conversion of CO2 and the selectivity of CH4 reached 45.6% and 97%, respectively. The isotope labeling experiments and in-situ diffuse reflectance infrared spectra showed that the hydrogen atoms of the tertiary carbon in decalin and isooctane were active for CO2 hydrogenation reaction, thus improving the catalytic activity.

关 键 词：二氧化碳 液相加氢 甲烷 溶剂效应 供氢作用 

分 类 号：O643.36[理学—物理化学] X773[理学—化学]