焦炉煤气甲烷重整制氢热力学分析和实验研究(英文)  

Hydrogen Production from Coke Oven Gas by Methane Reforming:Thermodynamic Analysis and Experimental Study

作　　者：杨志彬[1] 张玉文[1] 张云妍[1] 丁伟中[1] 沈培俊[1] 刘勇[1] 周宇鼎[1] 黄少卿[1] 

机构地区：[1]上海大学上海市现代冶金与材料制备重点实验室,上海200072

出　　处：《物理化学学报》2010年第2期350-358,共9页Acta Physico-Chimica Sinica

基　　金：国家高技术研究发展计划(863)(2006AA11A189);上海市科委重点科研项目(06DZ12212);先进钢铁材料技术国家工程研究中心(050209);上海大学研究生创新基金资助~~

摘　　要：对焦炉煤气甲烷部分氧化重整热力学进行分析,考察反应温度、CH4/O2摩尔比及水蒸气加入量等因素对重整性能的影响,并分析焦炉煤气原始氢含量对其部分氧化重整性能的影响.分析结果表明甲烷转化率均随CH4/O2摩尔比和水蒸气加入量的增大以及反应温度的升高而增大.在CH4/O2摩尔比1.7-2.1,温度825-900℃及压力1.01×105Pa的反应条件下,可得较好重整性能;甲烷转化率,氢及一氧化碳的选择性分别为91.0%-99.9%,87.0%-93.4%和100%-107%,重整后得到的氢量增大到原始氢量的1.95-2.05倍,每摩尔焦炉煤气消耗的热量仅为2.94J,同时得出在CH4/O2摩尔比2,温度825-900℃及1.01×105Pa条件下,往焦炉煤气内添加体积分数为2%-4%的水蒸气时重整性能得到较大提高;重整后甲烷转化率、氢及一氧化碳选择性分别由92.6%、87.2%、104%增大到98.6%、96.4%、107%.并在BaCo0.7Fe0.2Nb0.1O3-δ透氧膜反应器上研究NiO/MgO固溶体催化剂焦炉煤气部分氧化重整性能.结果表明该重整反应效果较好,于875℃下获得16.3mL.cm-2.min-1透氧量,95%甲烷转化率及80.5%氢和106%一氧化碳选择性.且所得实验结果与热力学分析结果符合较好,表明NiO/MgO固溶体催化剂有较好的催化重整性能.A thermodynamic analysis of the partial oxidation of methane （POM） in coke oven gas （COG） was carried out. The optimized conditions were CH4/O2 molar ratios of 1.7-2.1 and reaction temperatures of 825-900 ℃. We obtained CH4 conversions of 91.0%-99.9%, H2 selectivity of 87.0%-93.4%, and CO selectivity of 100%-107% at 1.01×10^5 Pa. The effect of H2 in the COG on the performance of POM was also investigated between 825 and 900 ℃. The optimized volume ratio of steam addition was 2%-4% and the molar ratio of CH4/O2 was 2 at 1.01×10^5 Pa and 825-900 ℃. A maximum conversion rate of 98.6% was achieved for CH4 using COG, while the maximum selectivities of H2 and CO were 96.4% and 107%, respectively. The amount of hydrogen obtained after reforming was doubled despite a thermal consumption of only 2.94 J ·mol^-1 for the COG. The performance of a NiO/MgO solid solution catalyst packed on a BaCo0.7Fe0.2Nb0.1O3-8（BCFNO） membrane reactor was also investigated for the POM in COG. The reforming process was successfully performed. At 875 ℃, 95% CH4 conversion, 80.5% H2 selectivity, and 106% CO selectivity at an oxygen permeation flux of 16.3 mL .cm^-2.min^-1 were achieved. The results for POM reforming in COG on the membrane reactor were consistent with the thermodynamic analysis. The NiO/MgO solid solution catalyst, therefore, has good activity and is suitable for application in hydrogen production.

关 键 词：焦炉煤气 氢 热力学分析 混合导体透氧膜反应器 NiO/MgO固溶体催化剂 

分 类 号：TQ116.22[化学工程—无机化工]