Mechanistic aspects of the higher alcohol synthesis over K[sub 2]O-promoted ZnCr oxide: Temperature-programmed reaction and flow experiments of C[sub 3], C[sub 4], and C[sub 5] oxygenates

Journal Article · Mon Jun 01 04:00:00 EDT 1992 · Journal of Catalysis; (United States)

DOI:https://doi.org/10.1016/0021-9517(92)90042-G· OSTI ID:6991863

Lietti, L; Tronconi, E; Forzatti, P ^[1]

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1. Industriale ed Ingegneria Chimica, Milano (Italy)

Mechanistic aspects of the higher alcohol synthesis (HAS) over a K[sub 2]O-promoted ZnCrO catalyst are investigated by temperature-programmed surface reaction (TPSR) of C[sub 3] oxygenates (1-propanol, n-propanal, and n-propanoic acid) and by flow microreactor experiments of 1-propanol, 3-pentanone, and 2-butanone. A number of chemical functions are identified by the TPSR study and those prevailing under steady-state conditions. TPSR and continuous-flow experiments lead to the identification of a general reaction network for C[sub N] oxygenate molecules, based on the following routes: (i) hydrogenation/dehydrogenation reactions of oxygenate molecules: (ii) aldolic-type condensations of aldehydes and ketones, both in the normal and in the reversal mode, leading to the formation of higher aldehydes and ketones, both in the normal and in the reversal mode, leading to the formation of higher aldehydes and ketones; (iii) ketonization reactions, leading to the formation of 2-ketones and CO[sub 2]; (iv) reversal [alpha]-addition reactions, which result in the formation of 2-ketones; (v) dehydration of oxygenates, and particularly of secondary alcohols, leading to the formation of olefins. Olefins may also be formed by decarboxylation of surface carboxylate species. The reactivity of the species participating in the various reactions is discussed on the basis of their molecular structure, and results are compared with catalytic tests performed under HAS conditions.

• OSTI ID: 6991863
• Journal Information: Journal of Catalysis; (United States), Journal Name: Journal of Catalysis; (United States) Vol. 135:2; ISSN 0021-9517; ISSN JCTLA5
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
100200* -- Synthetic Fuels-- Production-- (1990-)
ALCOHOLS
ALDEHYDES
ALKALI METAL COMPOUNDS
ALKENES
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CARBOXYLIC ACIDS
CATALYSIS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPOUNDS
CHROMIUM OXIDES
CONTROL
CRACKING
DECARBOXYLATION
DECOMPOSITION
DEHYDRATION
DEHYDROCYCLIZATION
DEHYDROGENATION
HYDROCARBONS
HYDROGENATION
HYDROXY COMPOUNDS
KETONES
KINETICS
MOLECULAR STRUCTURE
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POTASSIUM COMPOUNDS
POTASSIUM OXIDES
PROPANOLS
PYROLYSIS
REACTION KINETICS
SYNTHESIS
TEMPERATURE CONTROL
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPOUNDS
ZINC COMPOUNDS
ZINC OXIDES