Efficient and New Production Methods of Chemicals and Liquid Fuels by Carbon Monoxide Hydrogenation

Abstract

Carbon monoxide (CO) hydrogenation is an important step for efficient utilization of carbon resources in C1 (one carbon) chemistry. Over recent years, this direction has been a hot research area in academia and industry and has also been one of the most challenging routes for the nonoil carbon resources utilization process. A large number of novel reaction routes and catalysts have been studied and reported. Efficient activation and directional conversion of CO are key aspects in the process of CO utilization. Furthermore, effectively activating C-O and C-C bond formation as well as controlling carbon chain growth is the current technical bottleneck of CO hydrogenation. This mini-review introduces the latest research progress for different catalyst systems and processes in CO hydrogenation and analyzes the factors that control the performance of catalysts in different reaction systems. Here, much focus is put on the synthesis of long-chain hydrocarbons, light olefins, C₂₊ oxygenates, and aromatics, essentially in comparison with the previous reports. Finally, the present challenges and future research directions have been discussed.

Figure 1

Catalytic performance. (a) Fischer–Tropsch performance over the catalysts with conventional supports or Y_meso zeolites. (b–d) Detailed product distribution of Y_meso catalysts: Co/Y_meso–Ce (b), Co/Y_meso–La (c), and Co/Y_meso–K (d). Reaction conditions: temperature, T = 523 K; pressure, P = 2.0 MPa; H₂/CO = 1.0; flow rate, W_cat/F = 10 gh^–1 mol^–1; catalyst weight, 0.5 g; time on stream, 10 h. The calculation of hydrocarbon selectivity was based on the weight fraction of a product with respect to the total hydrocarbons. Reproduced with permission from ref (5). Copyright 2018. Nature Catalysis.

Figure 2

Catalytic process of OX-ZEO. (A) CO conversion and product distribution at different H₂/CO ratios in syngas over a catalyst with a mass ratio of ZnCrOx/MSAPO = 1.4 at a space velocity of 4800 mL/h·gcat. (B) Hydrocarbon distribution in OX-ZEO in comparison to that reported for FTTO and that in FTS predicted by the ASF model at a chain growth probability of 0.46, with the yellow bar representing selectivity of C2–C4 hydrocarbons. Reproduced with permission from ref (6). Copyright 2016. Science.

Figure 3

Possible reaction mechanism for the conversion of syngas into lower olefins over the Zn-ZrO₂/SSZ-13 catalyst. Reproduced with permission from ref (8). Copyright 2018. Chemical Science.

Figure 4

Proposed reaction pathway for oxygenate formation over the multifunctional catalyst. Reproduced with permission from ref (17). Copyright 2019. Angewandte Chemie International Edition.

Figure 5

(A) Schematic diagram of dimethyl ether direct synthesis from syngas on a single zeolite capsule catalyst. Reported by ref (18). Copyright 2010. Journal of American Chemical Society. (B) Direct conversion of syngas into methyl acetate, ethanol, and ethylene by relay catalysis using combinations of catalysts with different functions. Reported by ref (22). Copyright 2018. Angewandte Chemie International Edition.

Figure 6

(A) Illustration on the one-pass selective conversion of syngas into para-xylene over the designed hybrid catalyst Cr/Zn–Zn/Z5@S1. (B) The distribution of total xylene and isomers (ortho-xylene, meta-xylene, and para-xylene) over varied catalysts. Reproduced with permission from ref (26). Copyright 2017. Chemical Science.