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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)是碳一化学的关键技术,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。为了系统梳理反应机理与催化剂开发前沿,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现状。在机理层面,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。在催化剂层面,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。尽管以上领域取得系列进展,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: Catalytic conversion of syngas (CO+H2) into low-carbon alcohols (C2+ alcohols) in C1 chemistry is of great strategic significance to alleviate the global energy crisis, particularly for the resource utilization of agricultural and forestry wastes. Clean and efficient utilization of coal and natural gas can be realized with high atomic economy and low carbon dioxide emissions in green carbon science and the recycling economy. This study systematically reviewed the recent research progress on catalysts to synthesize higher alcohols from syngas, with emphasis on the reaction mechanisms and high-efficiency catalysts. The synergistic effect of bifunctional active sites dominated the adsorption and conversion pathways of CO at the mechanism level. Dissociative adsorption sites promoted carbon chain growth for non-dissociative adsorption sites, facilitating the formation of oxygen-containing intermediates. Alkali metal promoters (Li, Na, and K) and key process parameters (H2/CO ratio, reaction temperature, pressure) effectively regulated the generation of key intermediates and the distribution of target products. A multi-system pattern was found in the catalyst field, such as Mo-based, Rh-based, modified methanol synthesis, modified Fischer-Tropsch synthesis and Cu-based bimetallic catalysts. CO conversion rate, C2+ alcohol selectivity and catalyst stability were significantly improved after component regulation, structural (core-shell, confinement structures) and promoter modification. Industrial application also included single-tube tests, 100-ton pilot-scale experiments and 1000-ton industrial sideline demonstrations. Cu-based catalysts achieved over 85% in CO conversion and C2+ alcohol selectivity of 70%. Mo-based catalysts maintained stability for up to 1 700 h. Techno-economic analysis showed that green hydrogen accounted for 58%-83% of the total production cost, while non-noble metal catalysts reduced the preparation cost by 30%-50%, compared with noble metal catalysts; Agricultural waste gasification increased the system energy efficiency to 43.0%, indicating a significant reduction in greenhouse gas emissions. Some challenges included the synchronous high CO conversion and C2+ alcohol selectivity, harsh high-temperature and high-pressure reaction conditions, insufficient catalyst stability, and weak adaptability to agricultural application. 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, optimization for agricultural carbon sequestration and green hydrogen, and large-scale engineering. Technical barriers between basic research and agricultural applications can be broken to accelerate the industrialization of syngas-to-low-carbon-alcohol technology. The findings can provide strong support for clean energy production and the carbon circular economy in the resource utilization of agricultural wastes.

     

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