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煤焦表面官能团对甲烷裂解的影响

魏玲 武应全 赵建涛 谭猗生

魏玲, 武应全, 赵建涛, 谭猗生. 煤焦表面官能团对甲烷裂解的影响[J]. 燃料化学学报, 2016, 44(6): 661-667.
引用本文: 魏玲, 武应全, 赵建涛, 谭猗生. 煤焦表面官能团对甲烷裂解的影响[J]. 燃料化学学报, 2016, 44(6): 661-667.
WEI Ling, WU Ying-quan, ZHAO Jian-tao, TAN Yi-sheng. Role of coal surface functional groups in methane cracking over different chars[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 661-667.
Citation: WEI Ling, WU Ying-quan, ZHAO Jian-tao, TAN Yi-sheng. Role of coal surface functional groups in methane cracking over different chars[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 661-667.

煤焦表面官能团对甲烷裂解的影响

基金项目: 

国家自然科学基金 50628404

详细信息
  • 中图分类号: TQ544

Role of coal surface functional groups in methane cracking over different chars

More Information
  • 摘要: 采用石英管固定床反应器, 考察了1123K, CH4/N2=1:4的状态下, 煤焦表面官能团对甲烷裂解的影响。煤焦表面主要含有羟基、羰基和醚键等官能团, 分别通过氢氧化钡、苯肼和碘化氢溶液对煤焦表面进行化学处理, 除去煤焦表面相应的官能团, 研究处理后煤焦的催化活性, 得出煤焦中官能团对甲烷裂解的影响。氢氧化钡处理煤焦后, 煤焦中部分羟基被氢氧化钡消耗, 甲烷初始转化率和氢气初始收率分别为90.5%和65.2%, 说明煤焦中的羟基不利于甲烷的裂解。通过苯肼处理煤焦中羰基并使之转化, 甲烷初始转化率和氢气初始收率分别为55.4%和42.9%, 说明煤焦中的羰基对甲烷裂解有利。碘化氢处理煤焦后, 煤焦中的醚键转化成羟基, 甲烷的转化率和氢气收率都明显下降, 说明醚键的存在对甲烷裂解同样有利。随着反应时间的延长, 甲烷的转化率和氢气的收率降低, 催化剂逐渐失活。反应前后煤焦电镜扫描照片表明, 甲烷裂解生成的积炭沉积在煤焦表面, 堵塞煤焦的孔道, 煤焦的比表面积减小, 催化活性降低。
  • 图  1  实验装置示意图

    Figure  1  Schematic diagram of the experimental system

    ①: gas; ②: pressure relief valve; ③: mass flow controllers; ④: mixing chamber; ⑤: temperature controller; ⑥: quartz tube reactor; ⑦: electrically heated furnace

    图  2  1123K甲烷在不同煤焦上裂解的氢平衡

    Figure  2  Hydrogen balance over different coal chars

    ◇: Xiaolongtan liginite char; ○: char washed by barium hydroxide of equivatent-volume impregnation; ●: char washed by barium hydroxide of exceeding volume dipping; □: char washed by phenyl hydrazine of equivatent-volume impregnation; ■: char washed by phenyl hydrazine of exceeding volume dipping; △: char washed by hydrogen iodide of equivatent-volume impregnation; ▲: char washed by hydrogen iodide of exceeding volume dipping

    图  3  小龙潭煤焦以及处理煤焦的红外光谱谱图

    Figure  3  Infrared spectra of Xiaolongtan coal char and the treated chars

    a: Xiaolongtan liginite char; b: char washed by barium hydroxide; c: char washed by phenyl hydrazine; d: char washed by hydrogen iodide

    图  4  甲烷在氢氧化钡处理煤焦上裂解的转化率和氢气收率

    Figure  4  Methane conversions and hydrogen yields over different chars

    (a): conversions of methane cracking; (b): hydrogen yields of methane cracking ◇: Xiaolongtan liginite char; ○: char washed by barium hydroxide of equivatent-volume impregnation; ●: char washed by barium hydroxide of exceeding volume dipping

    图  5  甲烷在苯肼处理煤焦上裂解的转化率和氢气收率

    Figure  5  Methane conversions and hydrogen yields over different chars

    (a): conversions of methane cracking; (b): hydrogen yields of methane cracking ◇: Xiaolongtan liginite char; □: char washed by phenyl hydrazine of equivatent-volume impregnation; ■: char washed by phenyl hydrazine of exceeding volume dipping

    图  6  甲烷在碘化氢处理煤焦上裂解的转化率和氢气收率

    Figure  6  Methane conversions and hydrogen yields over different chars

    (a): conversions of methane cracking; (b): hydrogen yields of methane cracking ◇: Xiaolongtan liginite char; △: char washed by hydrogen iodide of equivatent-volume impregnation; ▲: char washed by hydrogen iodide of exceeding volume dipping

    图  7  不同煤焦反应前后的SEM照片

    Figure  7  SEM images of chars washed by different solution before (a, b, c, d) and after (a', b', c', d') being subjected to methane cracking

    (a and a': Xiaolongtan coal char, b and b': coal char washed by Ba (OH)2, c and c': coal char washed by phenyl hydrazine, d and d': coal char washed by HI)

    表  1  原煤和煤焦的工业分析和元素分析

    Table  1  Proximate and ultimate analyses of the parent coal and its char

    SampleProximate analysis wad/% > Ultimate analysis wad/%
    M A V SCHON
    Coal24.816.338.8 1.339.71.815.21.0
    Char0.723.53.0 2.068.61.43.10.8
    下载: 导出CSV
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  • 收稿日期:  2015-12-15
  • 修回日期:  2016-01-21
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-06-10

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