水热预处理对黄陵煤与酶解木质素共热解协同效应机制的研究OA
Study on the mechanism of enhanced synergistic effect in co-pyrolysis of Huangling coal and enzymatic hydrolysis lignin by hydrothermal pretreatment
富油煤与生物质共热解是实现富油煤油气属性最大化的有效途径.实验聚焦于富油煤与生物质共热解过程中协同效应强化作用机制不清晰的难题,以黄陵煤(H)和酶解木质素(E)为研究样品,采用工业分析、元素分析、扫描电镜(SEM)、电感耦合等离子体发射光谱仪(ICP-OES)和核磁共振(13C-NMR)等技术,解析了水热预处理(HTP)前后原料的结构演变规律,并结合固定床热解实验探究了水热预处理对黄陵煤和酶解木质素共混物共热解协同效应的增强机制.结果表明,水热预处理后,原料的氧含量减少,孔隙结构更为发达,水相中钙、钾、铁等无机金属离子浓度上升.黄陵煤和酶解木质素的结构发生明显改变,两者在脂肪碳、芳香碳和羰基/羧基碳相对含量的差距缩小,桥碳比增加,使酶解木质素的热稳定性提高,热解温度区间向黄陵煤趋近.黄陵煤和酶解木质素共混物,经水热预处理后,共热解焦油产率普遍增加,当H/E比为8:2、水热预处理24 h时,共热解焦油产率提高了80.52%,且焦油中脂肪族化合物和单环芳烃等含量明显增加.同时,煤气中H2、CO和CH4的产率分别提高了5.47%、10.98%和9.27%,抑制了CO2和热解水的生成,丰富了半焦的孔隙结构.这主要归因于水热预处理过程"组分交互-结构改造-催化裂化"的多重机制,增强了H/E共混物共热解的协同效应.研究结果为富油煤与生物质共热解协同效应强化技术发展提供了理论支撑,拓展了富油煤低碳高质化利用新途径.
Co-pyrolysis of oil-rich coal and biomass is an effective approach to maximize the oil and gas production from oil-rich coal.To address the challenge of unclear mechanisms for the enhancement of synergistic effects during the co-pyrolysis of oil-rich coal and biomass,a Huangling coal(H)and an enzymatic hydrolysis lignin(E)were used as the research samples and the structural evolution of raw materials and those by hydrothermal pretreatment(HTP)was systematically investigated using a suite of techniques such as proximate analysis,ultimate analysis,scanning electron microscopy(SEM),inductively coupled plasma optical emission spectrometry(ICP-OES)and nuclear magnetic resonance(13C-NMR).Combined with fixed-bed pyrolysis experiments,the mechanism by which hydrothermal pretreatment strengthens the co-pyrolysis synergistic effect of the Huangling coal and enzymatic hydrolysis lignin blend was explored.The results indicate that after hydrothermal pretreatment,the oxygen content of the raw materials decreases,the pore structure becomes more developed,and the concentrations of inorganic metal ions(e.g.,calcium,potassium,and iron)in the aqueous phase increase.The structure of Huangling coal and enzymatically hydrolyzed lignin undergoes significant modification,with the contents of aliphatic carbon,aromatic carbon and carbonyl/carboxyl carbon in enzymatically hydrolyzed lignin approaching those in Huangling coal,and with the bridge carbon ratio increasing,resulting in improved thermal stability for the enzymatically hydrolyzed lignin and a pyrolysis temperature approaching that of Huangling coal.By the hydrothermal pretreatment,the co-pyrolysis of Huangling coal and enzymatic hydrolysis lignin generally exhibit an increase in tar yields.When the H/E ratio is 8:2 and hydrothermal pretreatment is conducted for 24 h,the co-pyrolysis tar yield increases by 80.52%,with significant increases in the contents of aliphatic compounds and monocyclic aromatic hydrocarbons in the tar.Meanwhile,the yields of H2,CO and CH4 in the gas increase by 5.47%,10.98%and 9.27%,respectively,the generation of CO2 and pyrolysis water is inhibited,and the pore structure of semi-coke is enriched.This is primarily attributed to the multiple mechanisms of"component interaction-structural modification-catalytic cracking"during hydrothermal pretreatment,which enhance the co-pyrolysis synergistic effect of the H/E blend.The findings provide theoretical support for developing the technologies to enhance the co-pyrolysis synergistic effect between oil-rich coal and biomass,and expand new avenues for the low-carbon,high-quality utilization of oil-rich coal.
白状伟;周安宁;张怀青;张致;惠栋;陈福欣;贺新福
西安科技大学 化学与化工学院,陕西西安 710054西安科技大学 化学与化工学院,陕西西安 710054||自然资源部煤炭资源勘查与综合利用重点实验室,陕西西安 710021西安科技大学 化学与化工学院,陕西西安 710054西安科技大学 化学与化工学院,陕西西安 710054西安科技大学 化学与化工学院,陕西西安 710054西安科技大学 化学与化工学院,陕西西安 710054||自然资源部煤炭资源勘查与综合利用重点实验室,陕西西安 710021西安科技大学 化学与化工学院,陕西西安 710054||自然资源部煤炭资源勘查与综合利用重点实验室,陕西西安 710021
化学化工
共热解协同效应水热预处理多重机制高质化
co-pyrolysissynergistic effectshydrothermal pretreatmentmultiple mechanismshigh-quality
《燃料化学学报(中英文)》 2026 (6)
160-177,18
Supported by the National Natural Science Foundation of China(U24A20552)and the Shaanxi Provincial Key Special Project of"Dual-Chain"Integration(2023-LL-QY-05).
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