Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects ...Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects of catalystscreening and exploring reaction conditions, with few accurate descriptions of the reaction kinetics and determination ofthe reaction mechanism. Here, we combined kinetics experiments and theoretical calculations to elucidate the kinetics andmechanism of acrylic acid hydration on a resin catalyst. The pseudo-homogeneous model, and Langmuir-Hinshelwood-Haugen-Watson and Elie-Riedel (ER) heterogeneous models were used to explain the experimental kinetics data. TheER model can explain the experimental data very well, suggesting strong adsorption of acrylic acid on the surface of theresin catalyst. Furthermore, density functional theory calculations show that the hydration follows a stepwise, rather than aconcerted, reaction pathway. The present study provides theoretical insights into the reaction mechanism and kinetics, fillingthe gap in our understanding of the reaction on a fundamental level.展开更多
With increasing strict regulation on single-use plastics,lactic acid(LA)and alkyl lactates,as essential monomers for bio-degradable polylactic acid(PLA)plastic products,have gained worldwide attention in both academia...With increasing strict regulation on single-use plastics,lactic acid(LA)and alkyl lactates,as essential monomers for bio-degradable polylactic acid(PLA)plastic products,have gained worldwide attention in both academia and industry.While LA is still dominantly produced through fermentation processes from start,chemical synthesis from cellulosic biomass remains a grand challenge,owing to poor selectivity in activating CAH and CAC bonds in sugar molecules.To our best knowledge,recent publications have been focused on hydrothermal conversion of glucose to LA,while this review summarizes the highlights on direct thermal conversion of fructose as starting material to LA and derivatives.In particular,the synergies of metal/metal cations and acid/base catalysts will be critically revised on retro-aldol and dehydration reactions.This work will provide insights into rational design of active and selective catalysts for the production of carboxylic acids from biomass feedstocks.展开更多
文摘Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects of catalystscreening and exploring reaction conditions, with few accurate descriptions of the reaction kinetics and determination ofthe reaction mechanism. Here, we combined kinetics experiments and theoretical calculations to elucidate the kinetics andmechanism of acrylic acid hydration on a resin catalyst. The pseudo-homogeneous model, and Langmuir-Hinshelwood-Haugen-Watson and Elie-Riedel (ER) heterogeneous models were used to explain the experimental kinetics data. TheER model can explain the experimental data very well, suggesting strong adsorption of acrylic acid on the surface of theresin catalyst. Furthermore, density functional theory calculations show that the hydration follows a stepwise, rather than aconcerted, reaction pathway. The present study provides theoretical insights into the reaction mechanism and kinetics, fillingthe gap in our understanding of the reaction on a fundamental level.
基金the funds from National Natural Science Foundation of China (22078365, 21706290)Natural Science Foundation of Shandong Province (ZR2017MB004)+2 种基金Innovative Research Funding from Qingdao City, Shandong Province (17-1-1-80-jch)Fundamental Research Funds for the Central Universities and Development Fund of State Key Laboratory of Heavy Oil Processing (17CX02017A, 20CX02204A)New Faculty Start-Up Funding from China University of Petroleum (YJ201601059)
文摘With increasing strict regulation on single-use plastics,lactic acid(LA)and alkyl lactates,as essential monomers for bio-degradable polylactic acid(PLA)plastic products,have gained worldwide attention in both academia and industry.While LA is still dominantly produced through fermentation processes from start,chemical synthesis from cellulosic biomass remains a grand challenge,owing to poor selectivity in activating CAH and CAC bonds in sugar molecules.To our best knowledge,recent publications have been focused on hydrothermal conversion of glucose to LA,while this review summarizes the highlights on direct thermal conversion of fructose as starting material to LA and derivatives.In particular,the synergies of metal/metal cations and acid/base catalysts will be critically revised on retro-aldol and dehydration reactions.This work will provide insights into rational design of active and selective catalysts for the production of carboxylic acids from biomass feedstocks.
