秸秆液化产物中羰基化合物催化加氢制醇研究

China has abundant resources of biomass which can be converted to bio-based polyols through liquefaction process. It is very important to develop and utilize the bio-based polyols for alleviating the increasing shortage of energy supply and reducing the environment pollutions. However, the bio-based polyols contain many carbonyl compounds including furans, phenols, aldehydes, ketones, etc., which can greatly influence the properties of the polyurethane. It is very necessary to selectively reduce carboxide from the bio-based polyols via the hydrogenation to improve the quality of the upgraded bio-based polyols. In this study, Ni, Co and Cu were selected as active components to prepare a serial of Co-Cu-B, Co(Ni)-Cu-B, Ni-Cu-B, Co-Ni-Cu-B amorphous catalysts by chemical reduction method, and their catalytic activities were tested using bio-based polyol of cornstalk and its model compounds such as butyl levulinate, furfural, acetic acid, etc. The hydrogenation mechanism of carbonyl compounds to alcohols from bio-based polyol of cornstalk was studied by the modern characterization techniques. Moreover, the lumping kinetic model of hydrogenation of bio-based polyol was developed, which will provide guidance for high value-added products preparation from lignocellulose. The project has great theoretical value and application value in remitting the shortage of petroleum resources in China.

我国拥有丰富的秸秆类生物质资源，秸秆通过热化学液化可得到液化产物（生物基多元醇），利用该生物基多元醇可以制备聚氨酯等多种化工产品，发展和利用生物基多元醇对缓解石油供需紧张和环境污染问题具有重要意义。然而，生物基多元醇中含有大量的羰基化合物，对所制备的材料性能有较大的影响，必须对生物基多元醇进行催化加氢精制以提高产品的性能。本课题拟通过化学还原法制备一系列的Co(Ni)-Cu-B非晶态催化剂，考察催化剂分别对乙酰丙酸丁酯、糠醛、乙酸等模型化合物和玉米秸秆制备的生物基多元醇加氢精制的催化反应性能。利用先进的分析测试手段以及原位和连续流动状态下的程序升温测试技术，探索生物基多元醇中羰基化合物催化加氢制醇的催化反应机理；采用集总的方法，建立生物基多元醇催化加氢的集总动力学模型,为生物质制备高品质化工产品的研究提供理论指导，具有重要的理论意义和应用价值。

发展和利用秸秆资源通过催化液化得到生物基多元醇，进而制备生物质基聚氨酯产品，对缓解石油供需紧张和环境污染问题具有重要意义。本项目针对生物基多元醇中含有大量的醛、酮、酸、酯等羰基化合物，易对聚氨酯产品的结构和性能产生较大影响的问题，通过开发一种高活性、高稳定性的Cu-Co(Ni)-B非晶态催化剂，用于催化羰基化合物加氢制醇，从而实现生物基多元醇的高效精制。为此，本项目首先对秸秆资源催化液化制备生物基多元醇进行了工艺条件优化和动力学研究，获得了理想的液化条件。然后，以生物基多元醇中含有醛基（-CHO）、酰基（R˗C═O）和酯基（-COO-R）的典型羰基化合物——糠醛和乙酰丙酸丁酯为研究对象，对NiCoB非晶态合金催化剂制备过程中所使用的还原剂、制备溶剂、Cu助剂和酸改性凹凸棒土（H+-ATP）载体等进行了优化考察，筛选获得了具有高活性、高稳定性、低成本的羰基化合物加氢制醇催化剂—酸改性凹凸棒土负载20%Cu0.5Ni1Co1B。当该催化剂中CuNiCoB加氢活性位用量为生物基多元醇质量的4 wt%-6 wt%时，在反应温度120-140 ℃、初始氢气压力1-2 MPa、搅拌转速200-400 rpm条件下，可以实现生物基多元醇中70%以上的羰基化合物饱和加氢制醇，羟值可以提高139.5 mgKOH/g，生物基多元醇的颜色可以得到明显改善。生物基多元醇加氢精制后用于制备聚氨酯泡沫，可以有效调节泡孔尺寸，提高泡沫的力学性能和热稳定性。最后，建立了生物基多元醇催化加氢的集总动力学模型，为催化剂的优化制备提供了理论指导。项目执行过程中，共发表标注论文6篇，均为SCI/EI收录；申请国家发明专利4项，授权发明专利3项；已培养博士、硕士研究生各1名，在读博士研究生1名，按期完成了研究任务，达到了预期研究目标。