赵发军, 邓奇根.纳米Fe₃O₄在煤微生物降解产CH₄过程中的催化作用[J].河南理工大学学报（自然科学版）,2024,43(1):42-50.

ZHAO F J, DENG Q G.Catalysis effect of nano-magnetite on methane production from microbial degradation[J].Journal of Henan Polytechnic University(Natural Science) ,2024,43(1):42-50.

纳米Fe₃O₄在煤微生物降解产CH₄过程中的催化作用

赵发军1,2,3, 邓奇根1

1.河南理工大学 安全科学与工程学院，河南 焦作  454000;2.河南理工大学 河南省瓦斯地质与瓦斯治理重点实验室-省部共建国家重点实验室培育基地，河南 焦作  454000;3.河南理工大学 煤炭安全生产河南省协同创新中心，河南 焦作  454000

摘要:目的 为了研究纳米Fe₃O₄在微生物降解煤产甲烷（CH₄）过程中的催化作用，方法 采用晋城矿区矿井水和中原油田土壤中的两种菌群（厌氧消化菌，义马矿区）的煤样，考查温度和纳米Fe₃O₄添加量对反应体系产CH₄摩尔浓度的影响，分析产CH₄过程中伴随气体CO₂和H₂的摩尔浓度变化及其对CH₄摩尔浓度的影响，评估厌氧消化产CH₄反应体系中铁的作用和最大负载量。结果 通过分析厌氧性产CH₄古菌和多环芳烃分解菌共营降解煤的生物化学过程，认为煤降解产CH₄厌氧反应由两个主要步骤组成：一是稠环芳烃活化的羧化反应，该反应使煤被多环芳烃分解菌降解为甲苯酚和2-萘甲酸等化合物；二是产甲烷古菌利用煤分解产生的有机酸、甲基和气体等，通过辅酶的生物化学反应生成CH₄，该过程CH₄产气量随温度升高而增大，起始反应需要大量CO₂气体。在产甲烷古菌和多环芳烃分解菌共营系统中添加纳米Fe₃O₄后，产CH₄量增加了39.6%~50.8%。纳米Fe₃O₄对生物化学过程的催化作用表现在促进中间产物（H₂和CO₂等）的生成，同时生物化学反应通过消耗H₂和含氧有机物并生成液态水以降低密闭实验系统的气体总压力，使催化反应持续正向进行。结论 纳米Fe₃O₄对微生物降解煤产CH₄的催化作用需要多菌种互营环境，催化过程中存在最佳负载量。

关键词:采空区遗煤;纳米FeO;产甲烷古菌;细菌共营;煤层气;催化

doi:10.16186/j.cnki.1673-9787.2022030006

基金项目:国家自然科学基金资助项目（51404099）；河南省科技攻关计划项目（182102310828）

收稿日期:2022/03/02

修回日期:2023/02/27

出版日期:2024/01/25

Catalysis effect of nano-magnetite on methane production from microbial degradation

ZHAO Fajun1,2,3, DENG Qigen1

1.College of Safety Science and Engineering，Henan Polytechnic University，Jiaozuo  454000，Henan，China;2.State Key Laboratory Cultivation Base for Gas Geology and Gas Control，Henan Polytechnic University，Jiaozuo  454000，Henan，China;3.Collaborative Innovation Center of Coal Work Safety，Henan Province，Henan Polytechnic University，Jiaozuo  454000，Henan，China

Abstract: Objective To study the catalytic effect of nano-Fe₃O₄ on producing methane（CH₄）in the process of microbial degradation of coal， Methods  two types of microbial communities，which were come from the mine water from Jincheng mining area and soil from Zhongyuan oilfield，were used to anaerobic digest coal samples from Yima mining area.The effects of temperature and nano Fe₃O₄ addition quantity on the molar concentration of CH₄ produced in the reaction system were investigated.The changes of the molar concentrations of CO₂ and H₂ were also analyzed during the process of CH₄ production； their effects on the molar concentration of CH₄ were evaluated.The role and maximum loading of iron were also evaluated in the anaerobic digestion reaction system and CH₄ production. Results Basing on analysis of co-cultivation results of anaerobic methanogenic archaea and polycyclic aromatic hydrocarbon decomposing bacteria；it was believed that the anaerobic reaction of coal degradation and methanogenesis were consisting of two main steps，the first step was the carboxylation reaction of fused-ring aromatic hydrocarbon activation，which degraded coal into pmethylphenol and 2-naphthalenecarboxylic acid-；the second step was that organic acids，methyl groups and gases produced by coal decomposition were used to generate methane through the biochemical reaction of coenzymes，the yield of methane in this process increased with the increasing of temperature，and a large amount of CO₂ had been existed in the initiating reaction of the process.The production of methane gas increased 39.6%~50.8% after adding nano-Fe₃O₄ into the bacteria co-cultivation system.The catalytic effect of nano-Fe₃O₄ on the process of production of methane gas was to promote the production of intermediate products（hydrogen，CO₂ etc.），which were consumed by methanogenic archaea and liquid water was generated to reduce the gas pressure of the reaction system，so the catalytic reaction could continue in a positive direction. Conclusion The catalytic effect of nano-Fe₃O₄ on microbial degradation of coal producing CH₄ requires a multi-bacterial environment，and there is an optimal loading amount during the catalytic process.

Key words:residual coal in goaf;nano-magnetite;methanogenic archaea;bacteria co-cultivation;coalbed methane;catalysis