Na/Ca/Fe金属间相互作用对高碱煤热解氮变迁的影响  

Effects of Na/Ca/Fe intermetallic interactions on nitrogen transformations in high-alkali coal pyrolysis

作　　者：刘一文 魏砾宏 周艳玲 赵永昊 尚吉锋 娄堃堃 LIU Yiwen;WEI Lihong;ZHOU Yanling;ZHAO Yonghao;SHANG Jifeng;LOU Kunkun(College of Energy and Environment,Shenyang Aerospace University,Shenyang 110136,China;Guiyang Engine Research Institute,Aero Engine Corporation of China,Guiyang 550081,China)

机构地区：[1]沈阳航空航天大学能源与环境学院,辽宁沈阳110136 [2]中国航空发动机基团有限公司贵阳发动机设计研究所,贵州贵阳550081

出　　处：《煤炭学报》2025年第3期1769-1780,共12页Journal of China Coal Society

基　　金：国家重点研发计划资助项目(2020YFC1909305);沈阳航空航天大学创新创业训练计划资助项目(202310143003)。

摘　　要：我国新疆高碱低阶煤具有低灰、高钠和高反应活性的特点,开发高碱煤清洁高效转化为高值化学品技术,将对解决高碱煤资源利用、助力“双碳”目标的实现具有重要战略意义。高碱煤中活性矿物组分Na、Ca、Fe对煤热解具有催化活性,对氮的演化有显著影响。目前尚缺乏矿物组分之间相互作用对燃料氮热转化的影响机制研究。阐明金属间相互作用对高碱煤热解过程中氮变迁的影响,对制定高碱煤梯级利用过程中氮在气、液、固三相中分配的调控策略具有重要的指导意义。通过等体积浸渍法与顺序浸渍法分别将Na、Ca、Fe单金属和双/三金属负载到脱灰煤上,开展高碱煤固定床热解氮转化研究。利用GC-MS、XPS、溶液吸收法,定量分析单金属与双/三金属对煤热解含氮产物分布影响,对比分析热解试验结果与理论计算值,研究双/三金属间相互作用关系。通过分析煤样热解含氮产物的产率/残留率变化,研究双/三金属对高碱煤热解氮转移路径的影响。结果表明:双/三金属通常对氮向气相的迁移具有金属间拮抗作用,对HCN、NH_(3)的抑制强于单金属。Na/Ca、Fe/Ca组合对半焦中N-6、N-5组分向焦油中杂环氮、胺-N等物质的转化具有金属间的协同作用,其对焦油中含氮物质生成的促进作用往往强于单金属。Na/Fe、Na/Fe/Ca组合对半焦内部N-6向N-Q的转化起到金属间的协同作用,促进了氮的固定。China Xinjiang high-alkali low-rank coal has the characteristics of low ash,high sodium content and high react-ivity.Developing clean and efficient conversion technology for high alkali coal into high-value chemicals will have im-portant strategic significance for solving its resources utilization and helping to achieve the“dual carbon”goal.The miner-al components Na,Ca and Fe in high-alkali coal have catalytic activity in coal pyrolysis,which has a significant influence on nitrogen transformation.There is still a lack of research on the effects of interactions between mineral components on the thermal conversion mechanisms of fuel-N.This study aims to elucidate the effects of intermetallic interactions on ni-trogen transformation during pyrolysis of high-alkali coal.The results have significant implications for formulating con-trol strategies of nitrogen distribution in gas,liquid and solid phases during the cascade utilization of high-alkali coal.Na,Ca,Fe mono-metal and poly-metals were added to deashed coal by equal volume impregnation and sequential impregna-tion methods,and nitrogen transformation was studied in fixed-bed pyrolysis of high-alkali coal.GC-MS,XPS and solu-tion absorption method were used to quantitatively analyze the effects of mono-metals and polymetals on the distribution of nitrogen-containing products in coal pyrolysis,and interactions between them were analyzed by comparing the results of experiments results with theoretical calculations results.The effect of poly-metals on the pathway of N transformation in pyrolysis of high-alkali coal was studied by analyzing yield/residual rate of nitrogen-containing products.The results in-dicate that poly-metals usually exhibit an intermetallic antagonism on the migration of nitrogen into the gas phase,with stronger inhibition of HCN,NH_(3) than monometallic.The synergistic effects of Na/Ca and Fe/Ca significantly enhance the conversion of N-6 and N-5 in char to heterocyclic nitrogen and amine-N in tar,which demonstrates stronger promotion of ni

关 键 词：高碱煤 热解 氮转化 钠 钙 铁 金属间相互作用 

分 类 号：TQ530.2[化学工程—煤化学工程]