The transesterification of propylene carbonate (PC) or ethylene carbonate (EC) to dimethyl carbonate (DMC) by using catalytic reactive distillation (RD) is a promising approach for carbon dioxide utilization. However, there is still scarcity of comprehensive comparison between the two RD processes. Hence, using the UNIQUAC model and kinetics calibrated by literature and our experiments, we conduct an extensive comparison of the two RD processes. Based on the kinetic insights, laboratory RD processes for both reactions are modeled, analyzed, and experimentally validated. Consequently, two RD processes designed to produce 60 ktpy of DMC are optimized and compared. The interplay and control factors between reaction and separation are elucidated and clarified via investigating variations of the actual chemical equilibrium constant profile compared with theoretical values along the reactive section at various pressures, liquid holdups, etc. The results reveal that the optimized EC RD process achieves almost 50 % reductions in both total annual cost and carbon dioxide emission compared to the PC RD process. This work facilitates the carbon neutrality and provides an essential guide for quantitatively assessing the two routes.@en

Ethanol is used to produce various value-added chemicals and as automobile fuel. Acetic acid hydrogenation to ethanol is of practical significance to meet the increasing market. However, limited engineering research for reactor and crude separation process for the acetic acid hydrogenation to ethanol despite the increasingly mature catalyst system. Moreover, the traditional approach of industrial reactor design mainly relies on point data and inadequately quantifies the strong coupling between reaction rate and transfers within the reactor, which is prone to local and loose design and optimization. In this work, a coupled design approach that combines kinetics with transfers is proposed for designing and optimizing the multi-tubular fixed-bed reactor for the acetic acid hydrogenation to ethanol. To efficiently achieve the products crude separation, staged cooling/flash/absorption/desorption units featuring with N-methyl-2-pyrrolidone as an absorbent is proposed, numerically designed and optimized. Further heuristic heat integration is also investigated to conserve extra energy of the preliminary process, which features that a by-product steam generated from ethanol synthesis reactor is utilized to drive the reboiler of the desorption. It is demonstrated that the heat-integrated process presents significant economic and emission advantages compared with the preliminary process, specifically with 36.5 % and 10.9 % reductions in operating cost and total annual cost respectively, as well as 58.1 % reductions in CO₂ emissions. The cost of synthesizing ethanol with 100 ktpy production is as low as 14.25 $/t. This work could provide a feasible and promising reactor and crude separation process for acetic acid hydrogenation to ethanol, which features economic, high-efficient, energy-saving, and low-carbon.

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