Experimental study of hydrogen production via the steam reforming of hydrogen-rich biomass pyrolysis gas under the catalysis of Ni/γ-Al2O3
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摘要: 本实验对比研究了富氢生物质热解气和甲烷（CH4）蒸汽重整，探讨了富氢生物质热解气组分对CH4等低烃重整反应的影响机理，并揭示了Ni/γ-Al2O3催化剂在富氢热解气蒸汽重整反应中的作用机制。H2通过提供还原气氛使得催化剂表面高活性Ni0维持动态平衡，从而提高其催化活性；同时，生物质热解气对过渡碳向石墨碳的转化产生抑制作用，降低了积炭对Ni/γ-Al2O3催化活性的影响。其次，考察了反应温度、水碳比（S/C）、空速等操作条件对富氢热解气蒸汽重整反应的影响规律。反应温度和S/C的提高有效促进了CH4蒸汽重整反应，同时抑制了积炭的产生；随着反应空速的提高，CH4蒸汽重整反应的竞争性减弱，水煤气变换反应、CH4干重整反应的竞争性逐渐增加，使得CH4转化受到抑制。本实验为生物质热解气蒸汽重整反应机理研究及高效催化剂开发奠定了基础。
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关键词:
- 生物质热解气 /
- 蒸汽重整 /
- Ni/γ-Al2O3 /
- 氢气
Abstract: In this paper, the steam reforming reactions of the hydrogen-rich biomass pyrolysis gas and methane (CH4) were compared. The influence mechanism of hydrogen-rich biomass pyrolysis gas components on the reforming reaction of CH4 and other low hydrocarbons was discussed, and the catalytic effect of Ni/γ-Al2O3 catalyst was revealed. H2 could provide a reductive atmosphere to maintain the dynamic balance of the highly active Ni0 on the catalyst surface, so as to improve its catalytic activity. At the same time, biomass pyrolysis gas could inhibit the conversion of transition carbon to graphitic carbon, reducing the influence of carbon deposition on the catalytic activity of Ni/γ-Al2O3. In addition, the influence of operating conditions such as reaction temperature, the ratio of steam and carbon (S/C), as well as space velocity on the steam reforming reaction of hydrogen-rich pyrolysis gas was investigated. The increase of reaction temperature and S/C ratio effectively promoted the steam reforming of CH4 and inhibited the production of carbon deposition. With the increase of space velocity, the competitiveness of CH4 steam reforming reaction was weakened, whereas that of water gas shift reaction and CH4 dry reforming was increased. Hence, the transformation of CH4 was inhibited. This paper cound lay a foundation for the research on the mechanism of biomass pyrolysis gas steam reforming reaction and the development of high-efficiency catalysts.-
Key words:
- biomass pyrolysis gas /
- steam reforming /
- Ni/γ-Al2O3 /
- hydrogen
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图 1 生物质热解气蒸汽重整制氢装置示意图
Figure 1 Device diagram of biomass pyrolysis gas steam reforming for hydrogen production
图 2 不同原料气蒸汽催化重整的
$ {x}_{\text{CH}_{\text{4}}} $ 和$ {{n}}_{{\text{H}_{2}}}/{{n}}_{\text{CO}} $ 随反应时间的变化Figure 2 Variation of
$ {x}_{\text{CH}_{4}} $ and$ {{n}}_{\text{H}_{2}}/{{n}}_{\text{CO}} $ against reaction time in steam catalytic reforming of different feed gases
图 3 14Ni/γ-Al2O3催化剂的孔径分布
Figure 3 Distribution of pore size for the 14Ni/γ-Al2O3 catalysts
图 5 14Ni/γ-Al2O3催化剂的XPS谱图
Figure 5 XPS spectra of 14Ni/γ-Al2O3 catalysts (a): Ni 2p; (b): C 1s
图 6 不同Ni负载量Ni/γ-Al2O3催化剂催化生物质热解气重整对比
Figure 6 Comparative analysis of biomass pyrolysis gas reforming catalyzed by Ni/γ-Al2O3 catalyst with different Ni loading
(a): Variation of $ {x}_{\text{CH}_{4}} $ and $ {{n}}_{\text{H}_{2}}/{{n}}_{\text{CO}} $ with reaction time; (b): Components of gas product and $ {{I}}_{\text{H}_{2}} $
图 7 不同反应温度下14Ni/γ-Al2O3催化剂催化生物质热解气重整对比
Figure 7 Comparative analysis of biomass pyrolysis gas reforming catalyzed by 14Ni/γ-Al2O3 catalyst at different reaction temperature
(a): Variation of $ {x}_{\text{CH}_{4}} $ and $ {{n}}_{\text{H}_{2}}/{{n}}_{\text{CO}} $ with reaction time; (b): Components of gas product and $ {{I}}_{\text{H}_{2}} $
图 8 不同S/C比下14Ni/γ-Al2O3催化生物质热解气重整对比
Figure 8 Comparative analysis of biomass pyrolysis gas reforming catalyzed by 14Ni/γ-Al2O3 catalyst at different S/C ratios
(a): Variation of $ {x}_{\text{CH}_{4}} $ and $ {{n}}_{\text{H}_{2}}/{{n}}_{\text{CO}} $ with reaction time; (b): Components of gas product and $ {{I}}_{\text{H}_{2}} $
图 9 不同反应空速下14Ni/γ-Al2O3催化生物质热解气重整对比
Figure 9 Comparative analysis of biomass pyrolysis gas reforming catalyzed by 14Ni/γ-Al2O3 catalyst at different Reaction space velocity
(a): Variation of $ {x}_{\text{CH}_{4}} $ and $ {{n}}_{\text{H}_{2}}/{\text{n}}_{\text{CO}} $ with reaction time; (b): Components of gas product and $ {{I}}_{\text{H}_{2}} $
表 1 生物质热解气和CH4蒸汽催化重整进出口流量和积炭量对比
Table 1 Comparison of inlet and outlet flow and carbon deposition for the steam catalytic reforming of biomass pyrolysis gas and CH4
Type of gas Carbon deposition /(g·gcatal−1·h−1) CH4 H2 CO CO2 C2H4 Biomass pyrolysis gas inlet flow /(mol·min−1) 0.38 0.57 0.34 0.23 0.07 0.147 outlet flow /(mol·min−1) 0.03 2.34 0.59 0.34 − CH4 inlet flow /(mol·min−1) 1.57 − − − − 0.037 outlet flow /(mol·min−1) 0.38 2.97 0.98 0.11 − 
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表 2 催化剂的物理吸附
Table 2 Physical adsorption test results of catalysts
Sample BET surface area /
(m2·g−1)Pore volume /
(cm3·g−1)Average pore diameter /nm 14Ni/Al2O3
before reaction127.7 0.49 15.2 14Ni/Al2O3
after CH4 reforming103.5 0.47 17.7 14Ni/Al2O3
after biomass pyrolysis gas reforming103.1 0.49 18.5
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表 3 不同Ni负载量下的积炭量
Table 3 Catalyst deposition under different Ni loading
Nickel loading w/% 10 14 18 Catalyst deposition /(g·gcata−1·h−1) 0.100 0.147 0.107
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表 4 不同反应条件下的积炭量
Table 4 Deposition under different reaction conditions
Reaction conditions Deposition /(g·gcata−1·h−1) Temperature /℃ 600 700 800 900 0.147 0.080 0.060 0.040 S/C ratio 1 3 5 10 0.147 0.092 0.064 0.036 Space velocity /h−1 1200 4800 9600 12800 0.147 0.120 0.162 0.190
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