碳酸盐炼制共热耦合甲烷干重整制高附加值化学品发展展望

传统过程工业，诸如我国水泥、钢铁、耐材和电石等行业，都涉及碳酸盐高温热分解过程，其导致的CO₂排放量超过了全国工业碳排放总量的50%，大量CO₂排放对全球气候产生了不可逆转的影响。因此，如何减少过程工业排放的CO₂并且充分利用碳酸盐热分解的余热面临着巨大挑战。为进一步降低该类过程工业的CO₂排放量同时降低其热分解的能耗，通过利用地球上储量丰富的温室气体CH₄，对碳酸盐进行共热耦合重整制备合成气等高附加值产品，有望成为一种环保经济的技术路线。本文总结了(光/热)碳酸盐炼制耦合甲烷干重整反应、醇类重整反应以及CO₂捕获反应的最新进展，并且对碳酸盐炼制耦合甲烷干重整反应在理论计算方面的研究进展进行了介绍，进一步结合本课题组近期关于碳酸盐共热耦合甲烷重整的最新结果，我们提出了该类耦合反应的发展展望，为实现CO₂的高效转化和减排增效提供了思路。

Thermal Decomposition of Carbonates Coupled with Dry Reforming of Methane to Synthesize High-Value Products: A Perspective

Traditional industries, such as the production of cement, steel, refractory materials, and calcium carbide, involve the thermal decomposition of carbonates. Large amounts of carbon dioxide (CO₂) emitted by these processes comprise more than 50% of the total industrial carbon emissions in China. Furthermore, to ensure the complete decomposition of carbonates, the input of excess heat is required, leading to the generation of residual heat. Notably, the reduction in CO₂ emissions and complete utilization of the produced residual heat in the above processes are considerable challenges. However, co-thermal coupling of carbonate decomposition with H₂, CH₄, and other gases containing hydrogen molecules enables the production of high-value-added products such as syngas. Furthermore, this approach is environmentally friendly and economical, with potential for realization in the near future. This paper summarizes recent advances in the coupling of the thermal decomposition of carbonates with dry reforming of methane, dry reforming of alcohols, and CO₂ capture. Combining CO₂-emitting thermal decomposition of carbonates with the CO₂-consuming methane reforming reaction allows the simultaneous reduction of CO₂ emissions and syngas production. Although many experimental studies have been conducted on the coupling of the thermal decomposition of carbonates with dry reforming of methane, few reports have revealed the mechanism theoretically. At present, the theoretical research is limited to the adsorption of methane on carbonate surfaces without a clearly understood mechanism; this paper briefly introduces recent research progress in the thermal decomposition of carbonates coupled with H₂ reduction and dry reforming of methane. Notably, alcohols are promising hydrogen donors for coupling with the thermal decomposition of carbonates because they can be produced by fermentation of biomass or renewable raw materials, including energy plants, waste materials from agro-industry or forestry residue materials, and organic municipal solid waste. In addition, CO₂ can also be captured and converted using metal oxides (e.g., CaO, MgO); these are typical CO₂ solid sorbents, which can capture CO₂ by calcium looping and be regenerated in CH₄. Our group has also recently made progress in the co-thermal coupling of the decomposition of carbonates with dry reforming of methane. By regulating the concentration of CH₄, adding O₂ to the CH₄ atmosphere, and using catalysts, CO₂ emissions can be decreased with the evolution of syngas. In this perspective, we summarize the latest results on the coupling of the thermal decomposition of carbonates with dry reforming of methane, including the results obtained by our research group, which allows efficient utilization of CO₂ and emissions reduction.