双功能炭基固体酸的制备及其催化纤维二糖醇解
Preparation of Bifunctional Carbon-based Solid Acid and Its Catalytic Alcoholysis of Cellobiose
范腾 1张荣花 1王奎 2潘晖 1冯君锋1
作者信息
- 1. 南京林业大学 化学工程学院,江苏 南京 210037
- 2. 中国林业科学研究院林产化学工业研究所,江苏 南京 210042
- 折叠
摘要
以壳聚糖为碳源,通过金属浸渍、高温炭化制备负载铁的含氮活性炭(ACN-Fe),再进一步水热磺化制备了一系列金属负载型双功能炭基固体酸(ACN-Fe-SO3H),并将其应用于催化纤维二糖醇解反应,利用X射线衍射(XRD)、拉曼(Raman)光谱、红外(FT-IR)光谱、N2 吸附/脱附、X射线光电子能谱(XPS)、电感耦合等离子体发射光谱(ICP-OES)和酸碱滴定等手段对催化剂进行了详细的表征.研究结果显示:固体酸中的不饱和三价铁离子具有路易斯酸性,磺酸基具有布朗斯特酸性,炭化温度 800℃下制备的固体酸(800-ACN-Fe-SO3 H)具有最强的酸性(酸度0.81 mmol/g)和最大的比表面积(85.7 m2/g),催化性能最佳.800-ACN-Fe-SO3 H用量0.20 g时,在反应温度200℃,反应时间5h的条件下,纤维二糖的转化率为 99.6%,产物乙酰丙酸(LA)和乙酰丙酸甲酯(ML)产率分别为15.6%和62.1%.催化剂经过5 次循环回收,纤维二糖的转化率为93.1%,LA和ML的总产率为51.1%,表明催化剂具有良好的重复使用性,此外还初步探索了纤维二糖醇解的反应机理.
Abstract
Chitosan was used as a carbon source to prepare iron-loaded nitrogen-containing activated carbon(ACN-Fe)through metal impregnation and high-temperature carbonization.A series of metal-loaded dual-functional carbon-based solid acid(ACN-Fe-SO3H)catalysts were further prepared by hydrothermal sulfonation.The catalysts were applied to catalyze the alcoholysis of cellobiose.The catalysts were characterized in detail using X-ray diffraction(XRD),Raman spectroscopy,Fourier-transform infrared spectroscopy(FT-IR),N2 adsorption/desorption,X-ray photoelectron spectroscopy(XPS),inductively coupled plasma optical emission spectrometry(ICP-OES),and acid-base titration.The results showed that the unsaturated trivalent iron ions in the catalyst had Lewis acidity,while the sulfonic acid groups exhibited Brønsted acidity.The catalyst prepared at a carbonization temperatureof800℃(800-ACN-Fe-SO3H)possessed the strongest acidity(acidity of 0.81 mmol/g)and the best structural characteristics(specific surface area of 85.7 m2/g),showing the best catalytic performance.With a catalyst dosage of 0.20 g,a reaction temperature of 200℃,and a reaction time of 5 h,the cellobiose conversion rate reached99.6%,with yields of levulinic acid(LA)and methyl levulinate(ML)of 15.6%and 62.1%,respectively.After 5 cycles,the cellobiose conversion rate remained 93.1%,with a product yield of 51.1%,indicating good catalyst reusability.Additionally,a preliminary exploration of the reaction mechanism of cellobiose alcoholysis was conducted.
关键词
生物质催化转化/碳基固体酸/纤维二糖/乙酰丙酸/乙酰丙酸甲酯Key words
catalytic conversion of biomass/carbon-based solid acid/cellobiose/levulinic acid/methyl levulinate引用本文复制引用
基金项目
国家自然科学基金资助项目(32101469)
出版年
2024
国家科技期刊平台
NSTL
万方数据