Catalytic pyrolysis of biomass with thermal treatment products of spent lithium-ion batteries for the upgrading of bio-oil and syngas
Catalytic pyrolysis of biomass with thermal treatment products of spent lithium-ion batteries for the upgrading of bio-oil and syngas
复制标题
利用废旧锂离子电池热处理产物催化热解生物质，升级生物油和合成气
DOI：
10.1016/j.fuel.2022.125018
复制
发表时间：
2022
期刊：
影响因子：
7.4
通讯作者：
Qiang Liao
中科院分区：
文献类型：
--
作者：
Xianqing Zhu;Zhipeng Shi;Xun Zhu;Yiming Lai;Jingjing Ma;Ao Xia;Yun Huang;Qiang Liao
热处理是回收废旧锂离子电池的一种有效方法，热处理产物中富含Co、Ni等具有催化活性的有价金属。因此，本研究探索了废旧三元锂电池（NCM）和钴酸锂电池（LCO）热处理产物（PyNCM和PyLCO）作为生物质（麦草）廉价热解催化剂的可行性。为了比较的目的，还研究了PyNCM和PyLCO的典型组分（Ni、Co、NiO和CoO）对生物质热解过程的催化效果。结果表明，PyNCM和PyLCO均能促进麦草的挥发分脱除。基于Coats-Redfern方法建立的二级反应动力学模型能够较好地描述麦草催化热解过程，其活化能在79.00 ~ 83.90 kJ/mol之间。PyNCM和PyLCO对生物油裂解具有良好的催化活性，尤其是PyNCM，其气体产率从15.70%提高到22.26%。对于生物油组成，PyNCM和PyLCO都促进了烃类化合物的形成并降低了所得生物油的氧含量。烃含量的增加主要归因于PyNCM和PyLCO中的NiO和CoO组分。此外，PyNCM和PyLCO均提高了合成气中H2的含量和产率。特别是PyNCM，与未加催化剂的麦草直接热解相比，H2的含量和产率分别提高了1.6倍和5.5倍。提出并讨论了PyLCO和PyNCM存在下生物质催化热解的机理。PyNCM对麦草热解的催化作用比PyLCO更明显，这可能是由于PyNCM中Ni和Co化合物的正协同作用。本研究表明，废旧锂离子电池热处理产物可作为生物质热解产物改性的高效催化剂。
Thermal treatment is an efficient method to recycle spent lithium-ion batteries and the thermal treatment products are rich in valuable metals with catalytic activity such as Co and Ni. Therefore, the feasibility of using the thermal treatment products (PyNCM and PyLCO) of spent ternary lithium batteries (NCM) and lithium cobalt oxide batteries (LCO) as the cheap catalysts for biomass (wheat straw) pyrolysis was explored in this study. The catalytic effect of the typical components of PyNCM and PyLCO (Ni, Co, NiO and CoO) on the biomass pyrolysis process was also investigated for comparison purposes. The results showed that PyNCM and PyLCO could promote the devolatilization process of wheat straw. The Second order model could well describe the catalytic pyrolysis process of wheat straw based on the Coats-Redfern method, and the obtained activation energy was in the range of 79.00 kJ/mol to 83.90 kJ/mol. The PyNCM and PyLCO had good catalytic activity for enhancing the cracking of bio-oil to produce more gaseous products (syngas), especially for PyNCM, whose gas yield increased significantly from 15.70% to 22.26%. As for bio-oil compositions, the PyNCM and PyLCO both promoted the formation of hydrocarbon compounds and reduce the oxygen content of the obtained bio-oils. The increase of the hydrocarbon content was mainly attributed to the NiO and CoO components in PyNCM and PyLCO. In addition, both PyNCM and PyLCO increased the content and yield of H2in the syngas. Especially for PyNCM, the content and yield of H2increased 1.6 times and 5.5 times respectively compared with direct pyrolysis of wheat straw without catalyst. The mechanism of biomass catalytic pyrolysis in the presence of PyLCO and PyNCM was proposed and discussed. The catalytic effect of PyNCM on wheat straw pyrolysis was more distinct than that of PyLCO, which might be attributed to the positive synergistic effect of Ni and Co compounds in PyNCM. This study demonstrated that the thermal treatment products of spent lithium-ion batteries could be used as efficient catalysts for biomass pyrolysis products upgrading.