Catalysts for the Formation of Alcohols from carbon Monoxide and Hydrogen

Cryder, D. S.; Frolich, Per K.

doi:10.1021/ie50237a019

Cited by 15 publications

(9 citation statements)

References 8 publications

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“…In the early investigation on methanol synthesis over ZnO/Cr 2 O 3 catalysts prepared by coprecipitation followed by calcination, the synergy observed between ZnO and Cr 2 O 3 in comparison to the pure component oxides was mainly ascribed to an increase in the specific surface area . In addition, ZnO had been generally identified as the only active component, and the promoting role of Cr 2 O 3 was attributed to spinel formation, which prevented the sintering of small ZnO crystallites by providing a considerably larger surface area and better distribution of ZnO particles .…”

Section: Introductionmentioning

confidence: 99%

Spinel-Structured ZnCr₂O₄ with Excess Zn Is the Active ZnO/Cr₂O₃ Catalyst for High-Temperature Methanol Synthesis

et al. 2017

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A series of ZnO/Cr 2 O 3 catalysts with different Zn:Cr ratios was prepared by coprecipitation at a constant pH of 7 and applied in methanol synthesis at 260−300 °C and 60 bar. The X-ray diffraction (XRD) results showed that the calcined catalysts with ratios from 65:35 to 55:45 consist of ZnCr 2 O 4 spinel with a low degree of crystallinity. For catalysts with Zn:Cr ratios smaller than 1, the formation of chromates was observed in agreement with temperature-programmed reduction results. Raman and XRD results did not provide evidence for the presence of segregated ZnO, indicating the existence of Zn-rich nonstoichiometric Zn−Cr spinel in the calcined catalyst. The catalyst with Zn:Cr = 65:35 exhibits the best performance in methanol synthesis. The Zn:Cr ratio of this catalyst corresponds to that of the Zn 4 Cr 2 (OH) 12 CO 3 precursor with hydrotalcitelike structure obtained by coprecipitation, which is converted during calcination into a nonstoichiometric Zn−Cr spinel with an optimum amount of oxygen vacancies resulting in high activity in methanol synthesis. Density functional theory calculations are used to examine the formation of oxygen vacancies and to measure the reducibility of the methanol synthesis catalysts. Doping Cr into bulk and the (10−10) surface of ZnO does not enhance the reducibility of ZnO, confirming that Cr:ZnO cannot be the active phase. The (100) surface of the ZnCr 2 O 4 spinel has a favorable oxygen vacancy formation energy of 1.58 eV. Doping this surface with excess Zn charge-balanced by oxygen vacancies to give a 60% Zn content yields a catalyst composed of an amorphous ZnO layer supported on the spinel with high reducibility, confirming this as the active phase for the methanol synthesis catalyst.

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Section: Introductionmentioning

confidence: 99%

Spinel-Structured ZnCr₂O₄ with Excess Zn Is the Active ZnO/Cr₂O₃ Catalyst for High-Temperature Methanol Synthesis

et al. 2017

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“…Much more active copper-based catalysts were studied and described in the 1920s and 1930s [4][5][6][7][8][9]. These early studies identified copper as a very active metal * Corresponding author.…”

Section: Introductionmentioning

confidence: 99%

“…Tab 8. Qualities of methanol product International methanol producers and consumers association.13.13.8.12 Concepts Circumventing the Equilibrium Limitations…”

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confidence: 99%

Methanol Synthesis

Hansen¹,

Nielsen²

2008

Handbook of Heterogeneous Catalysis

133

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The sections in this article are Introduction Thermodynamics Methanol Synthesis Catalysts Introduction Zn O / Cr 2 O 3 Catalyst Copper‐Based Catalysts Cu / Zn O + Element ( Al , Cr , … ) Promotion of Cu / Zn O / MOx Catalysts Cu / Zr O 2 Other Cu , Cu / Me , Cu / Me Ox Catalysts Pd ‐Based Catalysts Sulfide Catalysts Other Catalysts Activation of Cu / Zn Catalyst Activity as a Function of the Nature of Copper‐Based Catalysts Catalyst Deactivation Sintering Sulfur Poisoning Other Poisons By‐Product Formation Reaction Mechanism(s) and Active Sites Cu + in a Zn O Matrix as the Active Center The S chottky Junction Theory Partly Oxidized Copper Independent of Support as Active Sites Metallic Copper in Dynamic Interaction with the Support Cu –Zinc Surface Alloy Model Water Gas Shift Reaction Kinetics Reaction Rate Equations Diffusion Restrictions Kinetics in Slurry Phase Methanol Synthesis Methanol Synthesis Technology Synthesis Gas Preparation Natural Gas Reforming Adiabatic Pre‐Reforming Tubular, Fired Reforming Autothermal Reforming and Oxygen‐Fired Secondary Reforming Gasification of Heavy Oil, Coal or Biomass Coproduction in Ammonia Plants and Use of Off‐gases Economics of Synthesis Gas Preparation Reactor Systems and Synthesis Loop Layout Slurry Phase Reactor Types Methanol Purification Concepts Circumventing the Equilibrium Limitations Other Methanol Synthesis Routes and Technologies Methanol Synthesis by Methane Activation Conclusion

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“…(8) Franz and Lutze, Ber., 67B, 768 (1924). (9) Griswold, University of Illinois thesis, 1928. (10) I. G. Farbenindustrie, French Patent 662,968 (1928).…”

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confidence: 99%