Laura Barberis, Christiaan I. Versteeg, Johannes D. Meeldijk, Joseph A. Stewart, Bart D. Vandegehuchte and Petra E. de Jongh*,
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引用次数: 0
摘要
通过反向水-气变换反应(rWGS)将二氧化碳和清洁的 H2 转化为 CO 和 H2O,可产生可持续的合成气,并通过后续的传统工艺(如通常在 200 至 350 °C 之间进行的费托合成)开辟了获得低碳燃料的途径。然而,其他二氧化碳加氢产物(如甲烷和甲醇)在低于 600-700 °C 的温度和更高的压力下热力学性质更为稳定。因此,开发在低温下具有活性的 CO 选择性 rWGS 催化剂以促进工艺集成是非常理想的。我们研究了在不同压力(20-40 bar(g))、温度(180-260 °C)和 H2:CO2 进料比(1:1、3:1、9:1)条件下的碱促进 Cu 基催化剂。添加 K 或 Na 可使碳支撑铜催化剂的二氧化碳转化率提高约 3 倍,并在 260 °C 时达到平衡转化率,而硅支撑催化剂则没有这种效果。即使在高压和进料中 H2 含量较高的情况下,对 CO 的选择性仍接近 100%,这表明 K 和 Na 促进剂完全抑制了这些体系中甲醇和甲烷的生成。这些催化剂出色的整体性能为 rWGS 反应的低温运行开辟了前景,可用于生产可持续燃料和建筑砌块。
K and Na Promotion Enables High-Pressure Low-Temperature Reverse Water Gas Shift over Copper-Based Catalysts
The conversion of CO2 and clean H2 to CO and H2O via the reverse water–gas shift reaction (rWGS) yields sustainable synthesis gas and opens up routes to low-carbon fuels via subsequent conventional processes such as Fischer–Tropsch synthesis which typically takes place between 200 and 350 °C. However, other CO2 hydrogenation products, such as methane and methanol, are thermodynamically much more stable at temperatures below 600–700 °C and at higher pressures. It is hence highly desirable to develop CO-selective rWGS catalysts that are active at low temperatures to facilitate process integration. We studied alkali-promoted Cu-based catalysts at varying pressure (20–40 bar(g)), temperature (180–260 °C), and H2:CO2 feed ratio (1:1, 3:1, 9:1). The addition of either K or Na boosted the CO2 conversion about 3-fold for carbon-supported Cu catalysts reaching equilibrium conversion at 260 °C, an effect that was not observed for silica-supported catalysts. Even at high pressures and high H2 content in the feed, the selectivity to CO remained close to 100%, showing that the K and Na promoters completely suppressed methanol and methane formation in these systems. The remarkable overall performance of these catalysts opens perspectives on the low-temperature operation of the rWGS reaction to produce sustainable fuels and building blocks.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.