物理化学学报 >> 2010, Vol. 26 >> Issue (02): 350-358.doi: 10.3866/PKU.WHXB20100212

催化和表面结构 上一篇    下一篇

焦炉煤气甲烷重整制氢热力学分析和实验研究

杨志彬, 张玉文, 张云妍, 丁伟中, 沈培俊, 刘勇, 周宇鼎, 黄少卿   

  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
  • 收稿日期:2009-05-05 修回日期:2009-11-24 发布日期:2010-01-26
  • 通讯作者: 丁伟中 E-mail:wzhding@shu.edu.cn

Hydrogen Production fromCoke Oven Gas byMethane Reforming: Thermodynamic Analysis and Experimental Study

YANG Zhi-Bin, ZHANG Yu-Wen, ZHANG Yun-Yan, DING Wei-Zhong, SHEN Pei-Jun, LIU Yong, ZHOU Yu-Ding, HUANG Shao-Qing   

  1. Shanghai Key Laboratory of Modern Metallurgy and Materials Processing, Shanghai University, Shanghai 200072, P. R. China
  • Received:2009-05-05 Revised:2009-11-24 Published:2010-01-26
  • Contact: DING Wei-Zhong E-mail:wzhding@shu.edu.cn

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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1.01×105 Pa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2.94 J, 同时得出在CH4/O2摩尔比2, 温度825-900 ℃及1.01×105 Pa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-啄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16.3 mL·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.

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

Abstract:

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 1.01×105 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 1.01×105 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-啄(BCFNO) membrane reactor was also investigated for the POMin 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.

Key words: Coke oven gas, Hydrogen, Thermodynamic analysis, Mixed-conducting membrane reactor, NiO/MgO solid solution catalyst