Enhanced catalytic performance of Zr modified CuO/ZnO/Al₂O₃ catalyst for methanol and DME synthesis via CO₂ hydrogenation

Journal Article · Fri Nov 15 23:00:00 EST 2019 · Journal of CO2 Utilization

DOI:https://doi.org/10.1016/j.jcou.2019.11.013· OSTI ID:1617852

Ren, Shoujie ^[1]; Fan, Xiao ^[1]; Shang, Zeyu ^[1]; Shoemaker, Weston R. ^[1]; Ma, Lu ^[2]; Wu, Tianpin ^[2]; Li, Shiguang ^[3]; Klinghoffer, Naomi B. ^[3]; Yu, Miao ^[4]; Liang, Xinhua ^[1]

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1. Missouri Univ. of Science and Technology, Rolla, MO (United States)
2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division
3. Gas Technology Inst., Des Plaines, IL (United States)
4. Rensselaer Polytechnic Inst., Troy, NY (United States)

Zirconium (Zr) modified CuO/ZnO/Al₂O₃ (CZA) catalysts with different aluminum (Al) and Zr contents were synthesized by the co-precipitation method. The synthesized CuO/ZnO/ZrO₂/Al₂O₃(CZZA) catalysts were comprehensively characterized and studied for methanol synthesis via CO₂ hydrogenation. The CZZA catalyst showed the highest methanol yield of 12.4 % at 220 °C and 2.76 MPa with an optimized catalyst composition of Cu/Zn/Zr/Al (atomic ratio) at 4:2:1:0.5. The CZZA catalyst showed better activity than that of the CZA catalyst and a superior stability for methanol synthesis. There was no decrease in the BET surface area and very little coke formation for the spent CZZA catalyst, after 300 h of methanol synthesis. Bifunctional catalysts, composed of CZZA and HZSM-5, were investigated for dimethyl ether (DME) synthesis directly from CO₂ hydrogenation, and a maximum DME yield of 18.3 % was obtained at a reaction temperature of 240 °C and a pressure of 2.76 MPa. The stability of the bifunctional CZZA and HZSM-5 catalyst during the DME synthesis also significantly improved, as compared to that of the CZA and HZSM-5. A significant decrease in the BET surface area and an increase in coking on the spent CZZA catalyst were observed after 100 h of DME synthesis, indicating a detrimental effect on CZZA stability when a HZSM-5 catalyst was present. The changes in structural properties (e.g., BET surface area and crystallinity) and coking for HZSM-5 could be responsible for the deactivation of the bifunctional catalyst.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE Office of Environment, Health, Safety and Security (AU)
• Grant/Contract Number: AC02-06CH11357; AR0000806
• OSTI ID: 1617852
• Alternate ID(s): OSTI ID: 1593512
• Journal Information: Journal of CO2 Utilization, Journal Name: Journal of CO2 Utilization Journal Issue: C Vol. 36; ISSN 2212-9820
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO(2)hydrogenation
CuO/ZnO/ZrO2/Al2O3 (CZZA)
Dimethyl ether
Methanol
Stability