scholarly journals The initial stages of the dehydrogenation and isomeric change of allyl alcohol

The catalytic decomposition of allyl alcohol has been studied by Ipatiev, who passed the vapour through a brass tube filled with brass filings maintained at 600° C. He found hydrogen and acrolein, some propylene and carbon monoxide, with a little divinyl in the reaction products, showing that under these conditions of elevated temperature very little hydrogenation of the double bond of the unsaturated alcohol takes place. Sabatier and Senderensf used reduced copper as catalyst at temperatures varying from 180-300° C. They found that a yield of over 50 per cent, of propionaldehyde could be obtained and only a little acrolein and hydrogen. The lower temperature seems to favour the production of the saturated aldehyde. The observations of Moureu and Boismenu have shown that acrolein is very appreciably hydrogenated by copper at temperatures between 110 and 250° C. At 300° C. the destruction of the acrolein is very rapid. It is evident, therefore, that there are two reactions to be followed in the initial stages of the dehydrogenation of allyl alcohol by copper CH 2 ═ CH . CH 2 OH— ↗CH 3 . CH 2 . CHO ↘ CH 2 = CH. CHO + H 2 A detailed study was made of these two reactions to attempt to throw light on the state of the adsorbed molecules, and to consider in detail the mechanism of the two reactions and the connection between them.

Carbon ◽  
1969 ◽  
Vol 7 (1) ◽  
pp. 47-57 ◽  
Author(s):  
W.R. Ruston ◽  
M. Warzee ◽  
J. Hennaut ◽  
J. Waty

1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.


1989 ◽  
Vol 67 (5) ◽  
pp. 862-866 ◽  
Author(s):  
Guenter A. Scholz ◽  
S. Roy Morrison

The methanation reaction on MoS2 exfoliated to a thickness of a few layers or less and adsorbed onto alumina is found to be very small. However, by calcining and resulfiding the exfoliated MoS2 catalysts, greatly improved performance is achieved that is at least equal to the commercial catalysts based on ammonium heptamolybdate. The creation of molybdenum oxysulflde surface species therefore appears to be a necessary step toward producing significant methanation rates with exfoliated and supported MoS2. The methanation products are almost exclusively CO2 and CH4, their mole ratios near unity, with otherwise only very much smaller amounts of longer chain hydrocarbons. The activation energy for methanation is generally observed to be near 100 kJ/mol, with the overall reaction being first order in the carbon monoxide concentration and third order in the hydrogen concentration. In contrast to the transition-metal catalysts, no water could be detected in the reaction products of the molybdenum based catalyst. Keywords: methanation reaction on MoS2, exfoliated and supported MoS2 as catalyst.


ChemCatChem ◽  
2019 ◽  
Vol 11 (3) ◽  
pp. 997-1001 ◽  
Author(s):  
Alejandro Mata ◽  
Christopher A. Hone ◽  
Bernhard Gutmann ◽  
Luc Moens ◽  
C. Oliver Kappe

2014 ◽  
Vol 14 (1) ◽  
pp. 79-84 ◽  
Author(s):  
J. Mocek

Abstract Drops of molten cast iron were placed on moulding sand substrates. The composition of the forming gaseous atmosphere was examined. It was found that as a result of the cast iron contact with water vapour released from the sand, a significant amount of hydrogen was evolved. In all the examined moulding sands, including sands without carbon, a large amount of CO was formed. The source of carbon monoxide was carbon present in cast iron. In the case of bentonite moulding sand with seacoal and sand bonded with furan resin, in the composition of the gases, the trace amounts of hydrocarbons, i.e. benzene, toluene, styrene and naphthalene (BTX), appeared. As the formed studies indicate much higher content of BTX at lower temperature it was concluded that the hydrocarbons are unstable in contact with molten iron.


2007 ◽  
Vol 72 (8) ◽  
pp. 1037-1045 ◽  
Author(s):  
Marianna Fekete ◽  
Ferenc Joó

The Ru(II)-N-heterocycle carbene complexes [RuCl2(η6-p-cymene)L] (L = 1-butyl-3-methylimid- azol-2-ylidene) and [RuCl(η6-p-cymene)L(pta)]Cl (pta = 1,3,5-triaza-7-phosphaadamantane) showed excellent catalytic activities (with turnover frequencies up to 1116 h-1) in the hydrogen transfer reduction of cinnamaldehyde and several ketones using propan-2-ol/KOH as a H-donor. Similar hydrogenations of trans-stilbene and cyclohexene were characterized by low conversions. The hydrogenation of 4-phenylbut-3-en-2-one and cinnamaldehyde proceeded with moderate selectivities of the formation of the saturated alcohol or of the of C=C hydrogenation (giving saturated ketone or saturated aldehyde). In the case of cinnamaldehyde, the unsaturated alcohol is initially formed; however, subsequent redox isomerization to the saturated aldehyde with the same catalyst diminishes its yield. The hydrogen transfer from formate to 4-phenylbut-3-en-2-one in an aqueous-organic two-phase mixture was also demonstrated.


1956 ◽  
Vol 34 (4) ◽  
pp. 502-514 ◽  
Author(s):  
Roger Gaudry ◽  
Louis Berlinguet ◽  
André Langis ◽  
Gérard Paris

A systematic investigation of the synthesis of 4-hydroxy-DL-proline and 2-amino-4-dihydroxyvaleric acid has been made, starting from the following derivatives of 2-amino-4-pentenoic acid: ethyl allylacetamidomalonate, ethyl allylacetamidocyanoacetate, 2-phthalimidopentenoic acid, allylacetamido-malonic acid, acetylallylglycine, 5-allylhydantoin, and 3-phenyl-5-allylhydantoin. Chlorine or bromine was added to the double bond of these compounds, and the reaction products were either derivatives of 5-halogenated-4-valerolactones or derivatives of 4,5-dihalogenated pentanoic acids, depending on whether the carboxyl group of the pentanoic acid was free or not when the halogenation reaction was carried out. Acid hydrolysis followed by treatment with barium hydroxide always gave mixtures, in different ratio, of 4-hydroxy-DL-proline and 2-amino-4,5-dihydroxyvaleric acid which were analyzed and isolated as the copper salts. In the case of 5-(2,3-dibromopropyl)hydantoin and 3-phenyl-5-(2,3-dibromopropyl)hydantoin, no cyclization could be obtained.


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