富碳精灰梯级功能化催化纤维素合成γ-戊内酯的机理研究

The froths obtained after the flotation of municipal solid waste incineration (MSWI) fly ash is rich in carbon constituents, dioxins and heavy metals. At present, the treatments of carbon-rich froths were limited to the decomposition of dioxins and regenerated carbon constituents, ignoring the potential of high value conversion of heavy metals. Besides, the synthesis of γ-valerolactone is an important subject of biomass utilization, and the high price of the metal used in the catalytic hydrogenation restricted its large scale production. In view of the above two problems, a new idea was proposed, that the detoxification carbon-rich froths-based bifunctional catalyst which is for the synthesis of γ-valerolactone was prepared from carbon-rich froths by step functionalization and synchronous detoxification (the first step is gas activation, the second step is sulfonation). The key research contents are as follows: (1) The preparation and optimization of detoxification carbon-rich froths-based bifunctional catalyst; (2) The formation mechanism of active sites was revealed by the grafting behavior of -SO3H and the change of Cu and other metal forms; (3) Using glucose→γ-valerolactone as the model, the reaction conditions were optimized by kinetic simulation; The catalytic mechanism of synthesis of γ-valerolactone was revealed by the interaction between two active groups (acid and metal groups) and reaction production. The implementation of this project will provide new ideas and theoretical basis for high value conversion from carbon-rich froths to bifunctional catalyst, and synthesis of γ-valerolactone at low cost.

垃圾焚烧飞灰经浮选所得精灰富含碳组分、二恶英和重金属，目前针对富碳精灰的处理仅限于分解二恶英和再生碳组分，忽略了重金属高值转化的潜力。此外，γ-戊内酯合成属生物质利用的重要课题，其中涉及的催化加氢金属因价格昂贵制约其规模化生产。针对上述问题，本项目提出以富碳精灰为研究对象，通过梯级功能化同步解毒的方法（一步气体活化、二步磺化）制备适用于催化合成γ-戊内酯的解毒富碳精灰基双功能催化剂的思路。重点研究：（1）解毒富碳精灰基双功能催化剂制备与优化；（2）通过研究-SO3H的嫁接行为以及Cu等金属形态的变化规律，揭示催化剂活性位点形成机理；（3）以葡萄糖→γ-戊内酯为模型反应，研究酸性和金属两种活性基团的变化与产物间的互动规律，揭示γ-戊内酯的合成催化机理；通过动力学模拟，优化反应条件。本项目的实施将为富碳精灰制备双功能催化剂、实现高值转化以及低成本催化合成γ-戊内酯提供新思路与理论基础。

垃圾焚烧飞灰经浮选所得精灰富含碳组分、二恶英和重金属，目前针对富碳精灰的处理仅限于分解二恶英和再生碳组分，忽略了重金属高值转化的潜力。此外，γ-戊内酯合成属生物质利用的重要课题，其中涉及的催化加氢金属因价格昂贵制约其规模化生产。针对上述问题，本项目以富碳精灰为研究对象，通过梯级功能化（一步气体活化、二步磺化）同步解毒的方法成功制备出了适用于催化合成γ-戊内酯的解毒富碳精灰基双功能催化剂，并确定了最佳制备条件（气体活化条件、磺化条件），在最佳制备条件下二恶英的分解率达到99.87%，实现了精灰解毒；通过FT-IR、EDS、XPS等表征手段揭示了催化剂活性位点的形成机理；通过催化反应实验研究了解毒富碳精灰基双功能催化剂的催化性能，并确定了催化反应的最佳条件；进一步地，明确了酸性和金属两种活性基团的变化与产物间的互动规律，揭示了γ-戊内酯的合成催化机理。项目所得成果为富碳精灰制备双功能催化剂、实现高值转化以及低成本催化合成γ-戊内酯提供了理论基础。