Synthesis of Methanol

Chinchen, G.C.; Denny, P. J.; Jennings, J. R.; Spencer, Michael S.; Waugh, Kenneth C.

doi:10.1016/s0166-9834(00)80103-7

Cited by 571 publications

(237 citation statements)

References 85 publications

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“…When these phases are calcined, CuO and ZnO are formed and have a smaller crystal size than those material oxides derived from single phases like malachite (pure Cu-hydroxycarbonate) and hydrozincite (pure Znhydroxycarbonate). [1][2][3] Moreover, a small amount of Cu(II) cations (ca. 2 atom%) can be dissolved in the ZnO lattice, 27 a situation that can clearly introduce some disorder into the framework, as evidenced by the broad XRD peaks for the ZnO phase.…”

Section: Characterisation Of the Calcined Cza Precursormentioning

confidence: 99%

See 1 more Smart Citation

Thermal decomposition of a hydrotalcite-containing Cu–Zn–Al precursor: thermal methods combined with an in situ DRIFT study

Melián‐Cabrera

Granados

Fierro

2002

Phys. Chem. Chem. Phys.

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Section: Characterisation Of the Calcined Cza Precursormentioning

confidence: 99%

“…The calcination temperature mentioned in the literature is 623-673 K, which is usually chosen on the basis of sintering restrictions. [1][2][3] Higher calcination temperatures are close to the thermal limit to avoid thermal sintering of the CuO phase. This would have an adverse effect on the catalytic activity for methanol synthesis.…”

Section: Introductionmentioning

confidence: 99%

Thermal decomposition of a hydrotalcite-containing Cu–Zn–Al precursor: thermal methods combined with an in situ DRIFT study

Melián‐Cabrera

Granados

Fierro

2002

Phys. Chem. Chem. Phys.

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“…Vedage et al [4] have shown that methanol synthesis rates on Cu/ZnO increased when 2±6% CO 2 was added to H 2 /CO mixtures, but much smaller rate enhancements were observed when such catalysts were modi®ed with Cs. Steady-state oxygen coverages on Cu surfaces during methanol synthesis depend on the relative rates of addition and removal of oxygen during CO hydrogenation reactions [35]. At high CO 2 concentrations and in the presence of alkali, the rate of surface oxidation increases relative to reduction, leading to higher steady-state oxygen coverages and to a (reversible) decrease in the number of surface Cu metal atoms available for methanol synthesis steps.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides

Hilmen

Ginés

et al. 1998

Applied Catalysis A: General

102

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K±Cu y Mg 5 CeO x and Cs±Cu/ZnO/Al 2 O 3 are selective catalysts for the synthesis of alcohols from an H 2 /CO mixture at relatively low pressures and temperatures. CO 2 produced in higher alcohol synthesis and water±gas shift (WGS) reactions reversibly inhibits the formation of methanol and higher alcohols by increasing oxygen coverages on Cu surfaces and by titrating basic sites required for aldol-type chain growth steps. Inhibition effects are weaker on catalysts with high Cu-site densities. On these catalysts, the abundance of Cu sites allows reactants to reach methanol synthesis equilibrium and maintain a suf®cient number of Cu surface atoms for bifunctional condensation steps, even in the presence of CO 2 . The addition of Pd to K±Cu 0.5 Mg 5 CeO x weakens CO 2 inhibition effects, because Pd remains metallic and retains its hydrogenation activity during CO hydrogenation. Basic sites on Mg 5 CeO x are stronger than on ZnO/Al 2 O 3 and they are more ef®ciently covered by CO 2 during alcohol synthesis. K and Cs block acid sites that form dimethylether and hydrocarbons. Alcohol addition studies show that chain growth occurs predominantly by aldol-type addition of methanol-derived C 1 species to ethanol and higher alcohols, following the rules of base-catalyzed aldol condensations. The initial C±C bond formation required for ethanol synthesis, however, proceeds directly from CO, at least on K±Cu y Mg 5 CeO x catalysts. A detailed kinetic analysis shows that chain growth probabilities are very similar on K±Cu y Mg 5 CeO x and Cs±Cu/ZnO/Al 2 O 3 catalysts. The growth probabilities of C 1 chains to ethanol and of iso-C 4 chains to higher alcohols are much lower than for other chain growth steps. # 1998 Elsevier Science B.V.

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“…The role attributed to ZnO is basically to increase the degree of dispersion of the copper phase in the calcined sample, in such a way that a high dispersion of copper metal can be attained when the system is activated by reduction. Its presence, therefore, leads to a higher concentration of active sites exposed to the reaction mixture (Bart and Sneden 1987;Chinchen et al 1989Chinchen et al , 1990. The addition of aluminium oxide has been reported to increase the BET surface area and the copper dispersion and to decrease the sintering of copper particles that occurs under normal working conditions (Bart and Sneden 1987;Chinchen et al 1989Chinchen et al , 1990.…”

Section: Introductionmentioning

confidence: 99%

Surface and Catalytic Properties of the CuO/Al₂O₃ System as Influenced by Treating with Trace Amounts of MoO₃

Mokhtar

2003

Adsorption Science & Technology

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A CuO/Al 2 O 3 solid containing 0.2 mol% CuO (0.2CuO/Al 2 O 3 ) and three MoO 3 -doped variants of this material were all prepared via the wet impregnation method, the amount of dopant added to the CuO/Al 2 O 3 solid being 0.25, 1.0 or 2.0 mol% MoO 3 , respectively. All the samples prepared were heated in air to 350, 450 or 600°C, respectively, before being cooled to room temperature and stored.X-Ray studies of these materials showed that the undoped (pure) solid calcined at 350°C exhibited all the diffractions lines associated with the AlO(OH) and CuO phases with an excellent degree of crystallinity. Doping the pure solid resulted in the effective progressive decrease in the degree of crystallinity of both the above-mentioned phases to an extent proportional to the amount of dopant added. Increasing the calcination temperature of the pure and doped solids to 650°C led to a significant decrease in the degree of ordering of CuO due to the formation of poorly crystalline g-Al 2 O 3 having a much better dispersion power relative to AlO(OH).The specific surface areas of the various samples were found to decrease progressively as the amount of dopant added was increased, especially for samples calcined at 650°C. Increasing the calcination temperature of the pure sample within the range 350-650°C led to a small increase in their catalytic activities in H 2 O 2 decomposition. In contrast, MoO 3 treatment followed by calcination of the resulting materials in the range 350-650°C resulted in a significant increase in their catalytic activities in the same catalytic reaction. The maximum increase in the catalytic activity at 30°C attained values of 720%, 735% and 976% for the doped solids calcined at 350, 450 and 650°C, respectively. In contrast, however, such doping brought about a progressive measurable decrease in the catalytic activity of the treated solids towards CO oxidation by O 2 when this latter reaction was conducted over the temperature range 150-250°C.

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Synthesis of Methanol

Cited by 571 publications

References 85 publications

Thermal decomposition of a hydrotalcite-containing Cu–Zn–Al precursor: thermal methods combined with an in situ DRIFT study

Thermal decomposition of a hydrotalcite-containing Cu–Zn–Al precursor: thermal methods combined with an in situ DRIFT study

Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides

Surface and Catalytic Properties of the CuO/Al₂O₃ System as Influenced by Treating with Trace Amounts of MoO₃

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Synthesis of Methanol

Cited by 571 publications

References 85 publications

Thermal decomposition of a hydrotalcite-containing Cu–Zn–Al precursor: thermal methods combined with an in situ DRIFT study

Thermal decomposition of a hydrotalcite-containing Cu–Zn–Al precursor: thermal methods combined with an in situ DRIFT study

Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides

Surface and Catalytic Properties of the CuO/Al2O3 System as Influenced by Treating with Trace Amounts of MoO3

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Surface and Catalytic Properties of the CuO/Al₂O₃ System as Influenced by Treating with Trace Amounts of MoO₃