焦炉煤气甲烷重整制氢热力学分析和实验研究(英文)

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.

Hydrogen Production from Coke Oven Gas by Methane 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 CH_4/O_2 molar ratios of 1.7-2.1 and reaction temperatures of 825-900 ℃. We obtained CH_4 conversions of 91.0%-99.9%, H_2 selectivity of 87.0%-93.4%, and CO selectivity of 100%-107% at 1.01×10~5 Pa. The effect of H_2 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 CH_4/O_2 was 2 at 1.01×10~5 Pa and 825-900 ℃. A maximum conversion rate of 98.6% was achieved for CH_4 using COG, while the maximum selectivities of H_2 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 BaCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ) (BCFNO) membrane reactor was also investigated for the POM in COG. The reforming process was successfully performed. At 875 ℃, 95% CH_4 conversion, 80.5% H_2 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.