State Key Laboratory of Low-carbon Smart Coal-fired Power Generation and Ultra-clean Emission Guoneng Changzhou Power Generation Co.
China Energy Science and Technology Resesrch Institute Co. Ltd.
Wuhan Institute of Technology

中国煤炼焦工业副产物煤焦粉产量大、活性低，难以被直接回收利用，常规热化学利用方式反应条件苛刻、催化剂易失活且存在动力学限制。本研究通过造纸副产物碱木质素作为可弃型催化剂，构建碱木质素强化化学链气化的方式来处理煤焦粉，实现工业副产物协同资源化利用。热转化实验和动力学分析研究表明，碱木质素可强化煤焦粉化学链气化过程，促进煤焦粉热解峰向低温方向移动。当煤焦粉与碱木质素质量比为1∶3时，反应活化能比单独煤焦粉反应降低87.56%。固定床实验证实气化温度提高、碱木质素以及载氧体赋存量增加，可以有效提高燃料碳转化率及合成气产物选择性，促进气化反应进行，但氧载体过量会导致合成气转化为终端产物，降低合成气选择性。在气化温度为950 ℃，煤焦粉与碱木质素质量比为1∶2， 氧载体与煤焦粉/碱木质素混合体系质量比为1∶1的最佳反应条件下，基于NiFe2O4的碱木质素/煤焦粉化学链气化合成气选择性高达82.85%。该研究为碱木质素与煤焦粉的资源化利用提供科学依据。

The pulverized coal char from the byproduct of China's coal coking industry has high yield and low activity, which is difficult to be directly recycled. The conventional thermochemical utilization method has harsh reaction conditions, catalyst deactivation and kinetic limitations. By using the alkali lignin from paper-making as a disposable catalyst, an alkali lignin enhanced chemical looping gasification method was constructed to treat coal coke powder, which can realize the collaborative resource utilization of industrial by-products. In this study, the reaction process of alkali lignin and coal char powder was studied by thermogravimetry and kinetic analysis. The thermal transformation experiment and kinetic analysis showed that alkali lignin could strengthen the chemical looping gasification process of pulverized coal char and promote the pyrolysis peak to move to low temperature. When the mass ratio of pulverized coal char to alkali lignin was 1∶3, the activation energy was 87.56% lower than that of coal coke powder alone, indicating that there was a synergistic effect between the two in the co pyrolysis process. The experiments in fixed bed reactor verified that the carbon conversion rate and the selectivity of syngas increased as the increasing of temperature and the content of alkali lignin and oxygen carrier, which effectively promoted the gasification reaction. However, excessive oxygen loading led to combustion reaction between syngas and lattice oxygen and reduce syngas selectivity. Under the optimal reaction conditions of 950 ℃, the mass ratio of coal char powder to alkali lignin was 1∶2, and the mass ratio of oxygen carrier to pulverized coal char/alkali lignin was 1∶1, the selectivity of syngas of alkali lignin/coal char powder in chemical looping gasification was 82.85%. This study provides a scientific basis for the resource utilization of alkali lignin and coal char powder.

国家自然科学基金 (51976226，52276191 )资助

高行龙, 安风霞, 胡耘, 陈国庆, 易群, 武小燕, 曹晋曾, 姚炜珊, 魏国强. 碱木质素强化煤焦粉化学链气化实验研究[J]. 燃料化学学报（中英文）, 2024, 52(7): 995-1005.

GAO Xinglong, AN Fengxia, HU Yun, CHEN Guoqing, YI Qun, WU Xiaoyan, CAO Jinzeng, YAO Weishan, WEI Guoqiang. Experimental study on alkali lignin enhanced chemical looping gasification of pulverized coal char[J]. Journal of Fuel Chemistry and Technology, 2024, 52(7): 995-1005.