Hydrogenation Of Acetone Research Articles

ChemInform Abstract: Hydrogenation of Acetone to Isopropanol with High Efficiency and Selectivity at 330 K over Pt‐TiO2.

Chemischer InformationsdienstVolume 15, Issue 51 Preparative Organic Chemistry ChemInform Abstract: Hydrogenation of Acetone to Isopropanol with High Efficiency and Selectivity at 330 K over Pt-TiO2. J. CUNNINGHAM, J. CUNNINGHAMSearch for more papers by this authorG. H. AL. SAYYED, G. H. AL. SAYYEDSearch for more papers by this author J. CUNNINGHAM, J. CUNNINGHAMSearch for more papers by this authorG. H. AL. SAYYED, G. H. AL. SAYYEDSearch for more papers by this author First published: December 18, 1984 https://doi.org/10.1002/chin.198451157AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume15, Issue51December 18, 1984 RelatedInformation

Preparation and Hydrogenation Activities of Plate Type Raney Iron Catalysts

This paper describes the surface structure and hydrogenation activity of plate-type Raney iron catalysts. When molten aluminum was sprayed onto surface of iron plate and the plate was heated, an alloy layer was formed at the boundary. Raney iron catalyst was prepared by leaching aluminum from the alloy with an aqueous sodium hydroxide. The characteristics of the alloy phase and the surface of the catalyst were determined by means of an electron probe microanalyzer and X-ray diffractometer. The alloy phase was FeAl3 and Fe2Al5. Catalyst based on alloy from SUS 304 (stainless steel containing 8% Ni and 18% Cr) substrate exhibted greater activity in hydrogenation of acetone than a similar catalyst based on SUS 430 (Stainless steel containing 16% Cr).

Kinetics and mechanism of acetone hydrogenation on nickel and palladium catalysts

Kinetic studies of the gas-phase hydrogenation of acetone and IR spectroscopic investigations of the adsorption of acetone and propanol-2 on a Ni-catalyst have been performed. A mechanism consistent with the experimental data is suggested.

Fibrous hydrogenation catalysts derived from NiAl eutectic alloys

The directional solidification (DS) of eutectic Ni-Al alloys was investigated as a new route for the synthesis of catalytic materials of the Raney (trade-mark) type with improved properties. Critical surface properties of the caustic-activated alloys, such as specific surface area, pore structure and available catalytic nickel surface area for active nickel derived from DS precursor alloys, were found to be superior to those of commercial bulk-cast Raney alloys activated in the same manner. Microporosites derived from low temperature nitrogen adsorption isotherms on caustic-activated alloys are significantly greater and pore distributions occur not only in both the small pore sizes with radii of less than about 10 Å and the sizes with radii of about 40–70 Å, which typical of Raney nickles, but also in the coarse pore sizes, with radii of about 90 Å, which are not typical of commercial activated Raney nickels. The enhanced pore structure of these DS caustic-activated alloys was demonstrated to be quite stable toward sintering by air oxidation at temperatures of about 500 °C. The Brunauer-Emmett-Teller surface area and available nickel metal surface area were found also to provide promising stability toward sintering in hot (about 350 °C) reducing atmospheres typical for methanation catalysis. The catalytic performance of caustic-activated DS Ni-Al eutectic alloys, compared with commercial Raney alloys, was found to be consistently superior by factors of 1.14–12.9 for initial reaction rates at low temperature (22 and 80 °C) for six selected liquid phase hydrogenation reactions, i.e. hydrogenation of acetone to isopropanol, nitrobenzene to aniline, toluene to methyl cyclohexane, butyronitrile to butylamine, itaconic acid to methyl succinic acid and dextrose to sorbitol. This superiority was due principally to the greater available catalytic nickel surface but in two instances (butyronitrile and nitrobenzene) the hydrogenation rates on a specific area basis are superior by factors of about 7 and 3 respectively, indicating that selectivity also plays a role.

Homogeneous hydrogenation of ketones to alcohols with ruthenium complex catalysts

A number of ruthenium triphenylphosphine complexes catalyse the reduction of ketones to their corresponding alcohols in the presence of water. The most convenient catalyst precursors are carbonyl containing complexes which do not promote decarbonylation of the substrate. The hydrogenation of acetone with hydridochlorocarbonyltris(triphenylphosphine)ruthenium is first order with respect to the substrate concentration, the catalyst concentration, the hydrogen pressure and the water concentration. Turnover numbers up to 15,000 have been achieved with this catalyst. Other ketones are also reduced by RuHCl(CO)(PPh 3) 3 and the rate of the reaction is dependent on the nature of the substrate.

SODIUM HYDROXIDE-ACTIVATED CATALYST OF COLLOIDAL NICKEL BORIDE FOR ATMOSPHERIC HYDROGENATION OF KETONES AND ALDEHYDES

Abstract Addition of sodium hydroxide to colloidal nickel boride in ethanol resulted in a marked enhancement of its catalytic activity for atmospheric hydrogenation of acetone at 30°C by a factor of more than 20. Other ketones and aldehydes with bulky substituents were smoothly hydrogenated by the activated colloidal catalyst.

Activity and hydrogen content of a plate-type raney nickel catalyst

A constant-potential electrolysis technique was found to be applicable to determination of the hydrogen content of a plate-type Raney nickel catalyst. The hydrogen was anodically removed in a definite amount according to the potential applied. Relationships between the hydrogen content, the BET surface area, and the activity for acetone hydrogenation were also investigated for the cases of electrolytic and thermal removal. On the basis of the data, combined with observation by means of an electron scanning microscope, it was concluded that removal of the hydrogen originally held by the catalyst inevitably caused a decrease in the activity. Electrolytic removal did not change the fine-structure of the bulk of the catalyst layer as remarkably as thermal removal. Though the catalyst that partly or completely lost its original hydrogen was able to resorb a considerable amount of hydrogen, it had no relation to the activity for acetone hydrogenation. A rough estimate of the atom ratio for the catalyst, H ads:H abs:Ni:Al, was 2:22:22:1.

Rhodium phosphine complexes as homogeneous catalysts. 7. Effect of phosphine structure on catalytic activity in acetone hydrogenation

The activity of catalysts for acetone hydrogenation formed in situ from [Rh(norbornadiene)Cl]2 and phosphines or phosphinic acid esters is determined by the electronic and steric effects of the ligand. The electronic parameter used was the infrared νco value of Rh(PR3)2(CO)Cl complexes containing the same P(III)-ligands. Catalytic activity increases with decreasing νco (i.e., increasing basicity of the ligand) and reaches its highest level with PEt3. Phosphines with larger, or branched, alkyl groups show still lower νco values but yield catalysts of lower, or even zero, activity because of the steric effects of the bulky ligands.

Liquid phase catalytic hydrogenation of acetone

The hydrogenation of acetone in various solvents on Raney nickel was studied at different temperatures and concentrations. Initial reaction rates in n-octane, isooctane, isopropanol and water were represented by a Langmuir-Hinshelwood type kinetic equation, where the concentration of hydrogen in solution was calculated from a correlation developed for its solubility in mixtures of solvents. A very good agreement between the experimental and calculated rates of reaction is observed and the effect of the solvent is interpreted in terms of the rate constants.

The coulometric determination of the amount of adsorbed hydrogen as a method of measuring the surface area of platinum powders

A study was made of the use of the coulometrically determined amount of hydrogen that would adsorb on platinum black as a measure of the catalytic activity of the platinum. This study was concerned with the use of the technique to measure the surface area of platinum black powders as catalysts for the oxidation of formaldehyde and the hydrogenation of acetone. The technique was shown to be unsuitable for determining relative catalytic activity of catalysts prepared by different techniques. It was concluded that this failure was caused by the inability to separate the areas of the different catalytic sites on the powders. It was also concluded that the oxidation of formaldehyde occurs on sites associated with the strongly bonded hydrogen while the hydrogenation of acetone occurs primarily on sites associated with the weakly bonded hydrogen.

Investigation of the catalytic conversions of acetone on cationic forms of faujasite and mordenite

1. At 200–450° and a pressure of 30 atm, type-Y zeolites, containing cations of metals of groups I, II, and the rare earth elements are active in the hydrogenation of acetone. A correlation of the activity of the catalysts with the value of the electrostatic potential of the anions (e/r2) was noted. 2. The activity of samples of NaHY and NaHM, produced by decationization of Na forms of zeolites and recationization of NH4Y and NH4M, increases with increasing concentration of Na+ cations, which indicates the participation of these cations in hydrogenation reactions. 3. The catalytic properties of decationized and recationized forms of mordenite of the same composition do not differ. NaHY zerolites, produced by recationization of NH4Y, are more active than HNaY prepared by decationization of NaY, which is evidently due to the different arrangement of the Na+ ions in the structure of the indicated catalysts.

Hydrogenation of acetone in a vibrating slurry reactor

AbstractThe behavior of a vibrating column of liquid as a slurry reactor and the dependence of the mass transfer resistances on the frequency of oscillation and liquid temperature were studied. The hydrogenation of liquid acetone over Raney nickel was chosen as the model reaction. The tortuosity factor of the catalyst was determined from measurements with two different particle sizes.

ChemInform Abstract: REACTIONS IN THE ADSORBED LAYER, HYDROGENATION OF ACETONE ON NICKEL CATALYSTS

The hydrogenation of acetone adsorbed and the dehydrogenation of isopropanol adsorbed on silica-supported nickel catalyst have been studied by following the changes of hydrogen pressure and the reaction products as well as the IR spectra of adsorbed species. It was found that the formation of isopropanol proceeds via a precursor composed of acetone and hydrogen. The activation energies of hydrogenation of acetone adsorbed and of dehydrogenation of isopropanol adsorbed were 11–13 and 4–8 kcal/mol, respectively. The activation energy of the desorption was 13 kcal/mol for isopropanol and 19 kcal/mol for acetone. From the results the potential energy change during the hydrogenation of acetone was determined.

Reactions in the Adsorbed Layer: Hydrogenation of Acetone on Nickel Catalysts

Abstract The hydrogenation of acetone adsorbed and the dehydrogenation of isopropanol adsorbed on silica-supported nickel catalyst have been studied by following the changes of hydrogen pressure and the reaction products as well as the IR spectra of adsorbed species. It was found that the formation of isopropanol proceeds via a precursor composed of acetone and hydrogen. The activation energies of hydrogenation of acetone adsorbed and of dehydrogenation of isopropanol adsorbed were 11–13 and 4–8 kcal/mol, respectively. The activation energy of the desorption was 13 kcal/mol for isopropanol and 19 kcal/mol for acetone. From the results the potential energy change during the hydrogenation of acetone was determined.

Hydrogenation of acetone on cationic forms of zeolites

1. Zeolites that contain the cations of the nontransition elements exhibit catalytic activity in the hydrogenation of acetone. 2. The activity and selectivity of zeolite catalysts depend on the nature of the cations, and the composition and structure of the zeolites.

Formation of lsobutyl Methyl Ketone in Acetene Hydrogenation over Nickel on Titanium Carbide Catalyst

Catalytic properties of nickel supported on stoichiometric titanium carbide in acetone hydrogenation have been studied at 150C.Over the catalyst (I) which was rcduced with hydrogen after calcination in nitrogen isobutyl methyl ketone was formed as a minor product, whereas over the catalyst (II) which was reduced after calcination in air the ketone was formed predominantly along with a small amount of 2-propanol. X-Ray analysis showed the existence of nickel oxide in I in addition to metallic nickel and stoichiometric titanium carbide, whereas in asmall amount of titanium dioxide in rutile form existed in addition to the above species. Both nickel oxide on the carbide (III) and nickel on rutile (IV) exhibited some activity for the acetone hydrogenation; the main product was the alcohol over and the ketone over IV. Over unsupported nickel the ketone was not formed.It is concluded from the experimental results that the catalyst systems which consisted of nickel with or without its oxide and titanium carbide with or without titanium dioxide caused the simultaneous formation of the alcohol and the ketone in the hydrogenation of acetone.

The Effect of the Addition of Alcohols on the Hydrogenation of Acetone with Raney Nickel

It had only been pointed eut in the previous paper that the difference in the stationary rate of the hydrogenation of acetene with varying alcohol used as the solvent must have been due to the difference in the rate eonstant, and that the rate ef the hydregenation had increased further in the range of the higher concentration of acetone as shown in Fig 1.In this paper, detail of the change of rate constant was made clear by the investigatien of the effect of the addition of alcohol on the rate of the hydrogenation of acetone with Raney nickel and the rate equation was proposed, available over full range ef the concentration of acetone.When an aicohol was added, the rate of the hydrogenation could be expressed as followsiIt was concluded that alcohols acted as poisons decreasing a part of the active sites for the hydrogenation of acetone as well as diluents aRd the difference in the stationary rate of the hydrogenatien, re(1-A), among alohels were due to the difference in the value of A ameng alcohols.The rate of the hydrogenation of acetone could be expressed as fellows.

Properties of Various Nickel Hydroxide Precipitates and the Activity of Supported Nickel Catalysts prepared from Them

Nickel catalyst for hydrogenation of organic compounds is usually prepared by precipitation method.In this paper, we studied the precipitation process of nickel hydroxide. Then, some kinds of supported nickel catalysts were prepared from various nickel hydroxides, which were aged in various ways to give different properties. And we studied the physical structures and the characteristics of these catalysts.Consequently, it was found that the precipitation process of nickel hydroxide resembled to that of magnesium hydroxide. Namely, in the first place, hydrated nickel, hydroxide Ni (OH), n H20, was obtained which was semicrystalline and appeared like a petal under electron microscope and in the second place, this precipitate was changed into nickel hydroxide crystal Ni(OH), which consisted of fine particles belonging to bluecite type. Several catalysts were prepared by kneading these two kinds of nickel hydroxides.Asa result, nickel catalyst from bluecite type of nickel hydroxide changed by reduction in the following way: Ni(OH)2→ NiO→ Ni, and showed high activityfor hydrogenation of acetone. But in the case of catalyst obtained from Ni(OH)2. n H2O, NiO chemically combined with the support and was hardly reduced tmetallic Ni. Consequently, it showed higher activity for aldor-condensation of acetonethan for hydrogenation of acetone.

Study of Sandwich Type Raney Nickel Catalyst by Electron Microprobe X-Ray Analyzer

The thickness of layer of sandwich type Raney nickel alloy was measured, and the distribution of sulfur bound to the catalyst surface was observed by means of an electron microprobe X-ray analyzer.The alloy layer, heated at 650°C under a nitrogen atmosphere and then pressed by a dental roller, was about 20 μ thick. The Raney nickel catalyst prepared from this alloy was active in hydrogenation of acetone. When the catalyst was immersed for 15 sec. in a saturated aqueous solution of H2S at 20°C, a large amount of sulfur was found distributed uniformly on its surface (Fig.3(c)). The catalyst thus treated lost its activity. The amount of surface sulfur detected after immersing an ordinary nickel plate, which was inactive for the hydrogenation of acetone, in a H2S solution was very small.When the catalyst was annealed at various temperatures up to 800°C in a hydrogen stream, the catalytic activity decreased abruptly at 400°C. The more the decrease in activity by the annealing, the less the amount of sulfur found on the surface after immersion in a H2S solution.These observations may lead to a conclusion that, as sulfur poisons active centers on the catalyst surface, the relation between the catalytic activity and the amount of sulfur is qualitatively parallel.

Hydrogenation of Benzene and Acetone by Supported Ruthenium Catalysts

The relation between the preparation conditions of supported ruthenium catalyst and the hydrogenation activity for benzene and acetone was investigated. The supports used were SiO2, Al2O3, and C. The hydrogenation was performed at 20°C (or 40°C) under the pressure of 4030kg/cm2. The catalysts were prepared by impregnating the supports with an agueous ruthenium chloride. The Ru-SiO2 and Ru-Al2O3 thus prepared are very preferable for the hydrogenation of benzene, but their activities for the acetone hydrogenation are low. In case of the acetone hydrogenation Ru-C is appropriate and a highly active catalyst is obtained by reducing it with hydrogen at 400500°C before hydrogenation.