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用于合成气制备低碳醇的催化技术研究进展

Research progress on catalysts for the synthesis of higher alcohols from syngas

  • 摘要: 合成气(CO+H2)催化制低碳醇(C2+醇)是碳一化学关键技术,对缓解能源危机、实现煤/天然气清洁利用、支撑“双碳”目标的实现及推动农业废弃物资源化具有重要意义。该文综述了合成气制备低碳醇催化技术研究进展,重点聚焦反应机理与高效催化剂开发。机理层面,双功能活性位点(CO解离吸附位点促碳链增长、CO非解离吸附位点生成含氧中间体)的协同作用主导CO吸附与转化路径,碱金属助剂(Li、Na、K等)及工艺参数(H2/CO比、温度、压力)可有效调控关键中间体生成与产物分布。催化剂领域,Mo基、Rh基、改性甲醇/费托合成及Cu基双金属催化剂形成多体系并行发展格局,通过组分调控、结构设计(核壳/限域结构)及助剂改性,显著提升了CO转化率、C2+醇选择性与催化剂稳定性。尽管取得系列进展,该技术仍面临CO转化率与C2+醇选择性难以同步提升、反应条件苛刻、催化剂稳定性不足及农业场景适配性薄弱等挑战。未来需聚焦精准设计农业废弃物衍生合成气适配型非贵金属催化剂、原子级机理解析、农业固碳与绿氢耦合工艺优化及工程化验证,打通基础研究与农业工程应用壁垒,推动技术工业化落地,为清洁能源生产、碳循环经济及农业资源化发展提供支撑。

     

    Abstract: The catalytic conversion of syngas (CO+H2) to low-carbon alcohols (C2+ alcohols) is a core technology in C1 chemistry, which is of great strategic significance for alleviating the global energy crisis, realizing the clean and efficient utilization of coal and natural gas, supporting the achievement of China’s “dual carbon” goals, and promoting the resource utilization of agricultural wastes. This technology features high atomic economy and low carbon dioxide emissions, which is highly compatible with the development concept of green carbon science and the recycling of agricultural and forestry wastes. This paper systematically reviews the recent research progress in this field, focusing on the in-depth analysis of reaction mechanisms and the development of high-efficiency catalysts. At the mechanism level, the synergistic effect of bifunctional active sites dominates the adsorption and conversion pathways of CO, in which dissociative adsorption sites promote carbon chain growth while non-dissociative adsorption sites facilitate the formation of oxygen-containing intermediates. Alkali metal promoters (Li, Na, K, etc.) and key process parameters (H2/CO ratio, reaction temperature, pressure) can effectively regulate the generation of key intermediates and the distribution of target products. In the catalyst development field, Mo-based, Rh-based, modified methanol synthesis, modified Fischer-Tropsch synthesis and Cu-based bimetallic catalysts have formed a multi-system parallel development pattern. Through component regulation, structural design (core-shell, confinement structures) and promoter modification, the CO conversion rate, C2+ alcohol selectivity and catalyst stability have been significantly improved. In terms of industrial application, breakthroughs have been made in single-tube tests, 100-ton pilot-scale experiments and 1000-ton industrial side-line demonstrations, with Cu-based catalysts achieving CO conversion over 85% and C2+ alcohol selectivity above 70%, and Mo-based catalysts maintaining stable operation for up to 1700 hours. Techno-economic analysis shows that green hydrogen accounts for 58%~83% of the total production cost, while non-noble metal catalysts reduce the preparation cost by 30%~50% compared with noble metal catalysts; the coupling with agricultural waste gasification can increase the system energy efficiency to 43.0% and bring significant greenhouse gas emission reduction benefits. Despite the above progress, the technology still faces prominent challenges, including the difficulty in synchronously improving CO conversion and C2+ alcohol selectivity, harsh high-temperature and high-pressure reaction conditions, insufficient catalyst stability, and weak adaptability to agricultural application scenarios. Future research priorities should be placed on the precise design of non-noble metal catalysts suitable for agricultural waste-derived syngas, atomic-level mechanism analysis via in-situ characterization and DFT calculations, process optimization coupling agricultural carbon sequestration and green hydrogen, and large-scale engineering verification. These efforts will break the technical barriers between basic research and agricultural engineering applications, accelerate the industrialization of syngas-to-low-carbon-alcohol technology, and provide strong support for clean energy production, carbon circular economy and the resource utilization of agricultural wastes.

     

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