Isobutanol from synthesis gas

Keim, Wilhelm; Falter, W.

doi:10.1007/bf00765055

Cited by 52 publications

(33 citation statements)

References 6 publications

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“…Metal±oxygen bonds are weaker on PdO than on CuO, and, thus, Pd metal is less likely to oxidize than Cu±metal (ÁG%À170 and À100 kJ/mol, respectively [41]). Pd has been used as catalyst for the synthesis of higher alcohols [28], but at much higher temperatures and pressures than those in this study. Isobutanol synthesis rates are similar on the two catalysts only at high space velocities.…”

Section: Effect Of Pd On K±cu 05 Mg 5 Ceo X Catalystsmentioning

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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Section: Effect Of Pd On K±cu 05 Mg 5 Ceo X Catalystsmentioning

confidence: 99%

“…Other Cu-based catalysts, such as K±Cu x Mg y CeO z [26,27], have recently been shown to catalyze the synthesis of isobutanol at low temperatures. Li±Pd/ZrO 2 ±MnO 2 ±ZnO catalysts show very high isobutanol synthesis productivity at high temperatures (>673 K) and pressures (>10 MPa) [28].…”

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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“…The preparation of these complexes can also be achieved by, first, reaction with NiC12(PPh3), to generate complex 4a with the P,O ligand attached, then addition of PhMgBr to produce 3a having the necessary nickel carbon bond; this is summarized in eq. [3].…”

Section: Figmentioning

confidence: 99%

Coordination chemistry of a mixed donor bidentate ligand with nickel. A tetrameric enolate of sodium that binds a phosphine donor

Fryzuk¹,

Gao²,

Rettig³

1995

Can. J. Chem.

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The preparation of a mixed donor ligand consisting of an enolate and neutral phosphine is described and its coordination chemistry with nickel reported. The phosphino ketones R,PCH,COPh (R = Cy or Pri) are prepared by the reaction of the corresponding secondary phosphines with bromoacetophenone to form the corresponding phosphonium salts [R,P(H)CH,COPh]+Br-(R = Cy or Pi); subsequent deprotonation leads to the neutral ketones. The enolates are formed by addition of NaN(SiMe,), to the neutral ketone. The crystal structure of the sodium enolate having isopropyl substituents at phospho~us displays a tetrameric structure in the solid state and there is an interaction of the phosphorus donor with the sodium anion: Na-P, 2.852(2) A. The preparation of a series of nickel complexes was achieved by addition of the sodium enolate to the appropriate Ni(I1) starting material. The structures of the nickel derivatives are reported. The catalytic behaviour of one of these complexes in the polymerization and oligomerization of ethylene is briefly described. ' Author to whom correspondence may be addressed. Telephone: (604)

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“…(Spivey, 2005;Herman, 2000). The values up to 0.98 kg/kg cat /h have also been claimed in patents (Keim and Falter, 1989). The content of methanol in a raw mixture usually goes beyond 50 wt.%; it should be minimised, because the production of pure methanol is large, cheap and efficient.…”

Section: Higher Alcohol Synthesis (Has)mentioning

confidence: 98%