Citation: YANG Zhi-Bin, ZHANG Yu-Wen, ZHANG Yun-Yan, DING Wei-Zhong, SHEN Pei-Jun, LIU Yong, ZHOU Yu-Ding, HUANG Shao-Qing. Hydrogen Production fromCoke Oven Gas byMethane Reforming: Thermodynamic Analysis and Experimental Study[J]. Acta Physico-Chimica Sinica, 2010, 26(02): 350-358. doi: 10.3866/PKU.WHXB20100212
焦炉煤气甲烷重整制氢热力学分析和实验研究
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/M 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/M 固溶体催化剂有较好的催化重整性能.
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关键词:
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焦炉煤气
- / 氢
- / 热力学分析
- / 混合导体透氧膜反应器
- / NiO/M 固溶体催化剂
English
Hydrogen Production fromCoke Oven Gas byMethane Reforming: Thermodynamic Analysis and Experimental Study
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/M 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/M solid solution catalyst, therefore, has od activity and is suitable for application in hydrogen production.
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