化学链耦合催化重整热解生物油制备合成气

doi:10.11949/0438-1157.20210762

摘要/Abstract

摘要：

生物油重整制合成气不仅能充分利用生物油中的成分，同时也展现了生物油转化为化学品的高值利用潜能。将载氧体NiFe₂O₄和Ni基催化剂耦合得到催化耦合化学链反应体系，为了比较催化剂的影响机制，分别构建了Ni/Si-NiFe和Ni/VR-NiFe催化耦合化学链反应体系，并以愈创木酚、乙酸和乙醇的纯物质及其混合液作为生物质热解液的模拟物，通过水蒸气重整实验考察了催化剂配比、反应温度、水碳比和反应时间对重整产物分布的影响。基于反应条件的筛选进一步通过寿命试验和BET、SEM表征，验证了反应体系的稳定性。最后，通过单组分及混合液体重整反应系统分析了化学链耦合催化反应体系的重整机制，为生物质热转化制备化学品提供了重要的理论支撑。

关键词: 化学链重整, 耦合, 催化重整, 热解生物油, 合成气

Abstract:

The reforming of bio-oil to syngas can not only make full use of the components in bio-oil, but also demonstrate the high-value utilization potential of bio-oil into chemicals. NiFe₂O₄ and Ni based catalysts were coupled to form a catalytic coupling chemical looping reaction system. In order to compare the influence mechanism of catalysts, Ni/Si-NiFe and Ni/VR-NiFe catalytic coupling chemical looping systems were constructed respectively. The pure substances and mixtures of guaiacol, acetic acid and ethanol were used as the models of biomass pyrolysis liquid. The effects of catalyst ratio, reaction temperature, water carbon ratio and reaction time on the product distribution were investigated by steam reforming experiment. Based on the screen of reaction conditions, the stability of the reaction system was further verified by life test, bet and SEM characterization. Finally, the reforming mechanism of the chemical looping coupling catalytic system was analysed through the single component and mixed liquid reforming reaction. The article provided an important theoretical support for biomass thermal conversion to produce chemicals.

Key words: chemical looping reforming, coupling, catalytic reforming, pyrolysis bio-oil, syngas

中图分类号:

TQ 028.8

孙焱, 沈晓文, 许细薇, 蒋恩臣, 刘雪聪. 化学链耦合催化重整热解生物油制备合成气[J]. 化工学报, 2021, 72(11): 5607-5619.

Yan SUN, Xiaowen SHEN, Xiwei XU, Enchen JIANG, Xuecong LIU. Coupled chemical looping and catalytic reforming to produce syngas from pyrolysis bio-oil[J]. CIESC Journal, 2021, 72(11): 5607-5619.

图/表 11

图1 重整实验平台示意图

Fig.1 Schematic diagram of reforming experimental platform

图2 不同配比的耦合体系重整后气体成分和H2/CO随时间变化趋势

Fig.2 Effect of different ratios of catalyst/carriers on the performance of reforming simulants

图3 不同耦合体系重整混合液的产物气体成分C和H元素的转化率随温度变化趋势

Fig.3 Effect of different temperatures on the coupled systems reforming

图4 不同耦合体系在不同水碳比条件下重整产物分布及元素的转化变化情况

Fig.4 Effect of different water carbon ratio on reforming performance of mixed liquid with different reaction system

图5 两种耦合体系在相同条件下重整产物分布及木质素的转化随时间变化情况

Fig.5 The distribution of reforming products and the transformation of lignin with time in the two coupling systems under the same conditions

图6 反应前后耦合体系的BET图

Fig.6 BET patterns of the spend and fresh OCs

表1 反应前后载氧体的孔隙结构参数

Table 1 Pore structure parameters of the spend and fresh OCs

样品名称	比表面积/(m2/g)	平均孔径/nm	孔容/(cm3/g)
VR-NiFe原样	1.8554	19.6952	0. 132 ×10^-3
VR-NiFe反应后	1.7037	21.5902	0.032 ×10^-3
Si-NiFe原样	23.5204	26.1521	0. 846 ×10^-3
Si-NiFe反应后	17.2746	26.5620	0. 260 ×10^-3

图7 反应前后混合体系的SEM图

Fig.7 The SEM patterns of spent and fresh mixed system

图8 模型化物的重整产物分布及转化率随时间的变化

Fig.8 The distribution of reforming products and the conversion rate variety of different single model compounds with time

图9 复合模型化物的重整产物分布及转化率随时间的变化

Fig.9 The distribution of reforming products and the conversion rate variety of different mixed model compounds with time

图10 单一模拟物的反应路径演化图

Fig.10 Reaction path evolution of single model compound

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