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生物油模型化合物水相重整制氫熱力學(xué)分析
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國(guó)家自然科學(xué)基金資助項(xiàng)目(50906091);廣東省自然科學(xué)基金資助項(xiàng)目(9151007006000003、10251007006000000)


Thermodynamic Analysis of Hydrogen Production by Aqueous Phase Reforming of Three Model Compounds in Bio-oils
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    摘要:

    利用Gibbs自由能最小化原理對(duì)生物油模型化合物水相重整制氫過(guò)程進(jìn)行了熱力學(xué)平衡計(jì)算,考察了反應(yīng)溫度為340~660K、壓力比psys/pH2O為0.1~2.0時(shí)兩個(gè)變量對(duì)H2選擇性、CH4選擇性、積碳以及原料轉(zhuǎn)化率的影響。計(jì)算結(jié)果表明,當(dāng)體系存在甲烷化與積碳反應(yīng)時(shí),原料轉(zhuǎn)化率大于99.99%且無(wú)固態(tài)碳生成,但甲烷化較制氫反應(yīng)熱力學(xué)更有利。限制甲烷化反應(yīng)后可提高H2選擇性,其產(chǎn)氫機(jī)理主要為原料的直接裂解反應(yīng),且1mol甲醇、乙酸與乙二醇可分別生成約0.999、1.940、1.999mol的固態(tài)碳。同時(shí)限制甲烷化反應(yīng)和積碳反應(yīng),在反應(yīng)溫度500K、壓力比psys/pH2O為1.1時(shí),水相重整甲醇、乙酸、乙二醇可得到H2選擇性為74.98%、66.64%、71.38%,且3種原料轉(zhuǎn)化率均大于99%。

    Abstract:

    Thermodynamic analysis employing Gibbs free energy minimization for aqueous phase reforming of three model compounds in bio-oils for hydrogen production was presented. Effect of temperature (340~660K) and pressure ratio psys/pH2O(0.1~2.0) on H2 and CH4 selectivity, carbon formation and conversion of model compounds were calculated. The results showed that when considering both methanation and carbon formation reactions, the conversion of the model compounds were over 9999% and no carbon formation was found, but mathanation was far more thermodynamically favorable than hydrogen production reaction. H2 selectivity were greatly improved without mathanation. Further analysis showed that the H2 production mechanism was mainly related to directly cracking of model compounds other than to aqueous reforming reaction, however, it was found that about 0.999, 1.940, 1.999 mole solid carbon formed when feeding per mole of methanol, acetic acid and ethylene glycol in the inlet streams. After restricting both mathanation and carbon formation reaction in the system, aqueous phase reforming of methanol, acetic acid and ethylene glycol at temperature of 500K and psys/pH2O of 1.1 could achieve H2 selectivity of 74.98%, 66.64%, 71.38%, and the conversion of the feedstocks were over 99%.

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謝建軍,陰秀麗,蘇德仁,吳創(chuàng)之,祝京旭.生物油模型化合物水相重整制氫熱力學(xué)分析[J].農(nóng)業(yè)機(jī)械學(xué)報(bào),2011,42(8):104-110. Xie Jianjun, Yin Xiuli, Su Deren, Wu Chuangzhi, Zhu Jingxu. Thermodynamic Analysis of Hydrogen Production by Aqueous Phase Reforming of Three Model Compounds in Bio-oils[J]. Transactions of the Chinese Society for Agricultural Machinery,2011,42(8):104-110.

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