Hydrogen production from wood vinegar reforming over cobalt modified nickel-based catalyst
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摘要: 为了实现木醋液的高值化利用,在固定床反应器中,进行木醋液催化重整制氢实验,采用浸渍法制备一系列不同Co添加量的Ni基催化剂,以产氢率、碳转化率、H2选择性和积炭量为主要评价指标,探究液时空速、反应温度、镍钴比等工况对木醋液催化重整制氢的影响,同时采用 XRF、H2-TPR、SEM及元素分析等方法对催化剂进行了表征。结果表明,液时空速增加,产气量增大,但液时空速过高会加速催化剂失活。高温有利于木醋液的催化重整制氢反应,温度到达900 ℃时,氢气产率最高。随着钴添加量的增加,反应产生的积炭降低,但氢气产率也会有所下降。因此,当液时空速为60 h−1,温度为800 ℃时,采用Ni-0.5Co/Al2O3催化剂,最适于木醋液的催化重整制氢实验。Abstract: In order to realize high value utilization of wood vinegar, a series of Ni based catalysts with different Co contents prepared by impregnation method were tested in a fixed bed reactor. The effects of liquid space-time velocity, reaction temperature and Ni/Co ratio on hydrogen production, carbon conversion, H2 selectivity and carbon deposition were investigated. The catalysts were characterized by XRF, H2-TPR, SEM and elemental analysis. The results show that the gas production increases with the increase of space-time velocity of liquid, but the catalyst deactivation is accelerated when the space-time velocity of liquid is too high. High temperature is conducive to the catalytic reforming of wood vinegar to produce hydrogen. When the temperature reaches 900 °C, the hydrogen yield is the highest. With the increase of cobalt content, the carbon deposition and hydrogen yield decrease. Therefore, when the liquid space velocity is 60 h−1 and the temperature is 800 °C, the Ni-0.5Co/Al2O3 catalyst is most conducive to the hydrogen production experiment of wood vinegar.
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Key words:
- wood vinegar /
- hydrogen from reforming /
- nickel-based catalyst /
- carbon deposition
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表 1 木醋液的主要成分统计
Table 1 Statistical result on the main components of wood vinegar
No RT Name Mol.formula Area/% 1 4.297 water H2O 23.95 2 4.958 acetic acid, methyl ester C3H6O2 1.73 3 7.474 acetic acid C2H4O2 16.63 4 8.496 2-propanone, 1-hydroxy- C3H6O2 6.71 5 10.026 propanoic acid C3H6O2 1.81 6 11.152 1-hydroxy-2-butanone C4H8O2 1.41 7 12.591 butanoic acid C4H8O2 0.54 8 13.05 3-cyclopentene-1-acetaldehyde, 2-oxo- C7H8O2 1.17 9 14.788 2-cyclopenten-1-one, 2-methyl- C6H8O 0.68 10 17.849 2-cyclopenten-1-one, 3-methyl- C6H8O 0.68 11 17.989 butyrolactone C4H6O2 0.98 12 19.532 2-cyclopenten-1-one, 2-hydroxy-3-methyl- C6H8O2 2.49 13 20.377 phenol C6H6O 4.99 14 20.983 phenol, 2-methoxy- C7H8O2 1.54 15 21.797 phenol, 2-methyl- C7H8O 0.94 16 22.28 nonane, 5-butyl- C13H28 0.95 17 22.819 phenol, 4-methyl- C7H8O 0.58 18 22.874 phenol, 3-methyl- C7H8O 0.84 19 23.143 propanoic acid, 2-methyl-, anhydride C8H14O3 2.23 20 23.939 phenol, 2-methoxy-4-methyl- C8H10O2 0.84 21 24.196 cyclopropyl carbinol C4H8O 5.77 22 26.393 3(2H)-furanone, dihydro-5-isopropyl- C7H12O2 0.95 23 27.214 1,4:3,6-dianhydro-α-D-glucopyranose C6H8O4 1.16 24 29.142 phenol, 2,6-dimethoxy- C8H10O3 2.07 25 31.419 phenol, 4-methoxy-3-(methoxymethyl)- C9H12O3 0.65 26 31.713 hydroquinone C6H6O2 0.71 27 37.087 1,6-anhydro-α-D-glucopyranose (levoglucosan) C6H10O5 4.04 note: only the components with relative peak area percentage greater than 0.5% were counted in the table 表 2 催化剂的组成
Table 2 Component content of catalysts
Components a b c d e Ni/% 3.95 2.78 3.12 1.87 0.00 Co/ % 0.00 1.75 2.47 3.24 3.31 表 3 木醋液催化重整制氢反应的实验方案
Table 3 Experimental scheme of hydrogen production by catalytic reforming of wood vinegar
Factors Levels LHSV/h−1 10 20 30 40 50 60 70 80 Temperature/°C 500 600 700 800 900 Ni/Co ratio 1:0 1:0.5 1:1 0.5:1 0:1 -
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