|Place of Conferral||北京|
|Keyword||双环戊二烯 氢甲酰化 氧化裂解 杂多酸 纤维素材料 有机碱 葡萄糖异构|
The background of China's energy structure is “much more coal than oil”, thus it is of great significance to high-valued existed coal-industry byproducts. Meanwhile, in term of the non-renewability of fossil fuel, broaden the source and further catalytic conversion of biomass is of strategic significance. Based on this, the present thesis focus on an important coal-industry byproduct dicyclopentadiene conversion by hydroformylation, and extraction and transformation of cellulose from real biomass.In the first part, SiO2 supported Co-Rh bimetallic catalysts were prepared by impregnation method and used for dicyclopentadiene (DCPD) hydroformylation to monoformyltricyclodecenes (MFTD) and diformyltricyclodecanes (DFTD). The reaction route of DCPD-MFTD-DFTD, also the rate-determining step of MFTD-DFTD were investigated and conformed. Also, the mass production of MFTD is realized. Besides, the catalysts recovered at different reaction stages of DCPD-DFTD, also fresh catalysts treated by different syngas pressures, were used for MFTD hydroformylation reaction. By detecting moment pressures, the relationship between the catalytic performance and the structure of the catalysts was observed. In the second part, nanopowder supported super lower loading (0.006%, w/w) Co-Rh bimetallic catalysts were prepared by co-precipitation method and used for MFTD hydroformylation to DFTD. The types of carrier and the ratio of Co/Rh were investigated, and ZnO nanopowder with Rh as main catalyst metal were determined. Then optimum temperature, dynamic parameters and reusability were tested. Results reveal the nanopowder supported super lower Co-Rh bimetallic catalysts have good cycle performance. This work will be of great importance to broaden the hydroformylation catalysts support range, also lower the cost of metal catalysts.In the third part, further high valued of DFTD was conducted, and C6-C8 alkenes and alkenes were obtained by DFTD oxidative cracking under ultra-low temperature and catalyst-free conditions. Mainly in the perspective of industry, some important factors, such as the oxygen pressure and contents, the effects of solvent and water contents, also the raw material loading were investigated. Meanwhile, the reaction route was proposed and dynamics fitting and analyzation also were performed. This work firstly demonstrated the oxidative cracking of DFTD, broaden the application of DCPD and will have significant and positive influence on the coal chemical industry.In the fourth part, three widely-available heteropoly acids (HPAs), silicotungstic, phosphotungstic and phosphomolybdic acid, were used as catalysts in GVL/H2O green solvent system to degrade lignin and obtain cellulose-enriched material from raw wood. HPAs concentration, reaction time and temperature were investigated to obtain the optimal lignin removal effect. Furthermore, cellulose-enriched material were characterized by SEM and FTIR, showing that HPAs are able to effectively degrade lignin while having little effect on overall tissue structure, which is important for wood-based materials. Finally, digestibility experiments demonstrated that thus obtained cellulose-enriched material is suitable for used as starting material for sugar production from wood. This work provides a direct strategy to obtain cellulose and sugar from real biomass.In the last part, six SBA-15 supported solid organic base catalysts were prepared and used for the isomerization of glucose to fructose in water. The relationships between the catalytic performance and the structure of organic base were initial discussed. Then, the effects of temperature, catalysts dosage, glucose concentration were optimized and the activation energy of 30.38 kJ/mol for the reaction is determined, which is lower than previous papers. During the reuse test, catalysts deactivation were observed. According to the characterization of FTIR, XRD and BET, the combined action of water and supported organic base is regarded to lead to the collapse of SBA-15 porous structure. Also the byproduct during the reaction that adsorbed onto catalysts surface confirmed by FTIR. This work provides some deeper understand on glucose isomerization by organic bases.
|张立波. 煤化工副产物双环戊二烯高附加值化及生物质原料催化转化[D]. 北京. 中国科学院大学,2018.|
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