MOF型Ca0.7Nd0.3CoO3对木质素热解的催化性能研究

Study on the Catalytic Performance of Metal⁃Organic Framework⁃Type Ca0.7Nd0.3CoO3 on Pyrolysis of Lignin

王海英 王程昊 张文成 王晓鹏 陈彦广 张雷 韩洪晶

Haiying Wang Chenghao Wang Wencheng Zhang Xiaopeng Wang Yanguang Chen Lei Zhang Hongjing Han

东北石油大学 化学化工学院，黑龙江 大庆 163318 中国石油大庆化工研究中心，黑龙江 大庆 163714 中国石油大庆石化分公司，黑龙江 大庆 163714 中国石油集团安全环保技术研究院有限公司，北京 102206

School of Chemistry and Chemical Engineering，Northeast Petroleum University，Daqing Heilongjiang 163318，China PetroChina Daqing Petrochemical Research Center，Daqing Heilongjiang 163714，China PetroChina Daqing Petro?Chemical Corporation，Daqing Heilongjiang 163714，China CNPC Safety and Environmental Technology Research Institute Co. ，LTD. ，Beijing 102206，China

催化热解是木质素资源化利用的一种有效途径。采用溶剂热法合成三元金属?有机框架（MOF）前驱体，通过焙烧调控制得钙钛矿Ca1?x Nd x CoO3（CNC?x），考察了其催化甘蔗渣木质素（BL）热解性能和再生性能，分析了气液相产物组成分布规律。结果表明，800 ℃焙烧制得的CNC?0.3表现出良好的催化BL热解性能，在温度为200~500 ℃时，热解活化能由64.24 kJ/mol降低至58.92 kJ/mol；与BL热解相比，气相产物收率降低，固相产物收率增加，液相产物收率由15.11%提高至17.94%；液相产物主要包括苯酚类、愈创木酚类、紫丁香酚类、苯醚类等芳香基含氧化合物，芳香基含氧化合物的总选择性比纯BL热解时提高了11.0%；经过5次循环再生，CNC?0.3仍具有良好的结构和催化稳定性。

Catalytic pyrolysis is an effective way to use lignin resource.A ternary metal?organic framework (MOF) precursor was synthesized by using the solvothermal method, and then the perovskite Ca1-x Nd x CoO3 (CNC?x) was prepared by controllable calcination.The performance of the perovskite for catalyzing bagasse lignin (BL) pyrolysis and regeneration was investigated,and the distribution law of the compositions of gaseous and liquid phase products was analyzed. The results show that CNC?0.3 calcined at 800 ℃ shows excellent performance in catalyzing BL pyrolysis.Under a temperature of 200~500 ℃,the pyrolysis activation energy is reduced from 64.24 kJ/mol to 58.92 kJ/mol.Compared with BL pyrolysis,the yield of gaseous phase products decreases,while that of solid phase products increases.The yield of liquid phase products is increased from 15.11% to 17.94%,and the liquid phase products are mainly aromatic oxygenated chemicals including phenols,guaiacols,syringols,and phenyl ethers.The total selectivity of aromatic oxygenated chemicals is 11.0% higher than that under pyrolysis.After five times of regeneration,CNC?0.3 still shows satisfactory structural and catalytic stability.

国家自然科学青年基金项目(21908021);黑龙江省中央支持地方高水平人才项目(2020GSP17);中国石油科技创新基金项目(2021DQ02?0701);东北石油大学引导性创新基金项目(2021YDL?03);东北石油大学新能源新领域培育项目(XNYXLY202102);东北石油大学人才引进科研启动经费资助项目(2021KQ07)

10.3969/j.issn.1006-396X.2022.05.006