Higher Alcohol Synthesis

Forzatti, Pio; Tronconi, Enrico; Pasquon, I.

doi:10.1080/01614949108020298

Cited by 231 publications

(154 citation statements)

References 70 publications

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“…Methanol can be formed from synthesis gas via reaction (1). Methanol synthesis catalysts, however, also catalyze water±gas shift reactions (2).…”

Section: Methanol Synthesismentioning

confidence: 99%

“…Mixtures of higher alcohols and methanol are preferred over pure methanol because of their higher water tolerance, reduced fuel volatility and lower vapor lock tendency, and also because their volumetric heating values are higher than for pure methanol [1].…”

Section: Introductionmentioning

confidence: 99%

“…The addition of alkali to Cu-based methanol synthesis catalysts leads to the formation of higher alcohols from H 2 /CO mixtures [1,2]. Cs appears to be the best promoter for higher alcohol synthesis, but Rb and K also increase the selectivity to higher alcohols [3±5].…”

Section: Introductionmentioning

confidence: 99%

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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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“…Methanol can be formed from synthesis gas via reaction (1). Methanol synthesis catalysts, however, also catalyze water±gas shift reactions (2).…”

Section: Methanol Synthesismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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“…20,37 Several papers also describe the chemocatalytic conversion of syngas into ethanol and higher alcohols. 20,[38][39][40][41][42] Three different pathways from syngas to ethanol are reported: direct selective hydrogenation of CO over a solid catalyst, homologation of methanol which involves reductive carbonylation on a redox catalyst, or a classical methanol synthesis reaction followed by carbonylation to acetic acid and subsequent hydrogenation to ethanol. Although carbonylation of methanol to ethanol is a promising step (TCX Technology by Celanese 43 ), none of these routes have been practiced commercially.…”

Section: -36mentioning

confidence: 99%

Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

Gabriëls

Hernández

Sels

et al. 2015

Catal. Sci. Technol.

249

233

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The Guerbet condensation reaction is an alcohol coupling reaction that has been known for more than a century. Because of the increasing availability of bio-based alcohol feedstock, this reaction is of growing importance and interest in terms of value chains of renewable chemical and biofuel production. Due to the specific branching pattern of the alcohol products, the Guerbet reaction has many interesting applications. In comparison to their linear isomers, branched-chain Guerbet alcohols have extremely low melting points and excellent fluidity. This review provides thermodynamic insights and unravels the various mechanistic steps involved. A comprehensive overview of the homogeneous, heterogeneous and combined homogeneous and heterogeneous catalytic systems described in published reports and patents is also given. Technological considerations, challenges and perspectives for the Guerbet chemistry are discussed.

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“…Adding Co to alkalized MoS 2 catalysts increases the production of ethanol and other higher alcohols because Co promotes the homologation of methanol to ethanol (Forzatti et al 1991). Activity of the sulfide catalysts can also depend on the catalyst support 79 material (Avila et al 1995;Bian et al 1998;Li et al 1998).…”

Section: Alkali-doped Sulfides Mainly Mosmentioning

confidence: 99%

Preliminary screening: Technical and economic assessment of synthesis gas to fuels and chemicals with emphasis on the potential for biomass-derived syngas

2003

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Executive Summary/ConclusionsIn principle, syngas (primarily consisting of CO and H 2 ) can be produced from any hydrocarbon feedstock, including: natural gas, naphtha, residual oil, petroleum coke, coal, and biomass. The lowest cost routes for syngas production, however, are based on natural gas, the cheapest option being remote or stranded reserves. Economic considerations dictate that the current production of liquid fuels from syngas translates into the use of natural gas as the hydrocarbon source. Nevertheless, the syngas production operation in a gas-to-liquids plant amounts to greater than half of the capital cost of the plant. The choice of technology for syngas production also depends on the scale of the synthesis operation. Syngas production from solid fuels can require an even greater capital investment with the addition of feedstock handling and more complex syngas purification operations. The greatest impact on improving the economics of gasto liquids plants is through 1) decreasing capital costs associated with syngas production and 2) improving the thermal efficiency with better heat integration and utilization. Improved thermal efficiency can be obtained by combining the gas-to-liquids plant with a power generation plant to take advantage of the availability of low-pressure steam.

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Higher Alcohol Synthesis

Cited by 231 publications

References 70 publications

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

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

Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

Preliminary screening: Technical and economic assessment of synthesis gas to fuels and chemicals with emphasis on the potential for biomass-derived syngas

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