Abstract: The invention relates to a process for producing metal carbonyls, wherein a reaction with a reaction mixture containing the following components is conducted in a reactor: (a) at least one metal carboxylate of formula (MeRx)w, wherein Me is a transition metal, R is a monocarboxylate having 6 to 12 carbon atoms, x=1, 2, 3, or 4, and w=1, 2, or 3, (b) carbon monoxide, (c) an aliphatic alcohol having 4 to 7 carbon atoms—preferably, butanol—and (d) a solvent, wherein the average dwell time in the reactor is less than 60 minutes.

Abstract: The present invention is a method for producing dodecacarbonyl triruthenium (DCR) including a process of carbonylating ruthenium chloride with carbon monoxide, in which an amine is added to a reaction system at 0.8 molar equivalent or more with respect to chlorine of the ruthenium chloride and the carbonylation is conducted at a reaction temperature of 50 to 100° C. and a reaction pressure of 0.2 to 0.9 MPa. According to the present invention, it is possible to produce dodecacarbonyl triruthenium having less residual impurity metals without applying a reaction condition of a high pressure.

Abstract: Method and apparatus of making 99.99% pure gaseous carbon monoxide comprising the steps of degassing liquid formic acid producing degassed liquid formic acid; reacting the degassed liquid formic acid or a degassed gaseous formic acid with a liquid mineral acid at an elevated temperature producing a gas phase comprising carbon monoxide gas and water vapor and a liquid phase; condensing the gas phase producing liquid water and gaseous carbon monoxide; scrubbing the carbon monoxide gas producing a gaseous 99.99% pure carbon monoxide having a purity of at least 99.99%, and, compressing the gaseous 99.99% pure carbon monoxide producing the 99.

Abstract: The present invention is directed to the synthesis of novel stable open metal clusters by selective oxidation of bound ligands. The synthesis comprises, for example, using an amine based oxidant for decarbonylation of specific carbonyl ligands. The synthesis can also comprise further removal of a bound amine group by an acid. The resulting metal cluster contains a coordinatively unsaturated site comprising a carbonyl vacancy. The resulting metal cluster can be used as a catalyst in a variety of chemical transformations.

Abstract: A fuel cell reformer includes a main body having a first pipe with a second pipe inside the first pipe, a thermal source unit in the second pipe, a reforming reaction unit in a first region between the first pipe and the second pipe to generate a reforming gas containing hydrogen through a reforming reaction of a fuel, and a carbon monoxide reduction unit in a region other than the first region between the first pipe and the second pipe to reduce a concentration of carbon monoxide contained in the reforming gas. A thermal treatment unit in the main body supplies thermal energy to the reforming reaction unit and the carbon monoxide reduction unit at a time of initial driving of the reformer such that the supplied thermal energy corresponds to a unique operational temperature range in the reforming reaction unit, and to a unique operational temperature range in the carbon monoxide reduction unit.

Abstract: The invention concerns a method for producing a gas mixture containing hydrogen and carbon monoxide, and optionally nitrogen, from at least a hydrocarbon such as methane, propane, butane or LPG or natural gas, which comprises performing a partial catalytic oxidation of one or several hydrocarbons, at a temperature of 500° C., at a pressure of 3 to 20 bars, in the presence of oxygen or a gas containing oxygen, such as air, to produce hydrogen and carbon monoxide. Recuperating the gas mixture, which can subsequently be purified or separated, by pressure swing adsorption, temperature swing adsorption or by permeation, to produce hydrogen having a purity of at least 80% and a residue gas capable of supplying a cogeneration unit. In another embodiment, the gas mixture can subsequently be purified of its water vapor impurities and carbon dioxide to obtain a thermal treatment atmosphere containing hydrogen, carbon monoxide and nitrogen.

Abstract: A sol-gel process for producing layers of zirconium oxide is described which comprises the following stages: (i) production of a soluble, zirconium-containing powder by: (a) reaction of a zirconium alcoholate of the general formula Zr(OR)4, in which the residues R are the same or different and represent straight-chain, branched or cyclic alkyl or alkenyl residues with 1 to 10 carbon atoms, which optionally exhibit one or more carbonyl and/or ester and/or carboxyl functions, with one or more polar compounds having complexing, chelating properties, (b) heating the solution, (c) mixing the solution with water, optionally in the presence of a catalyst, (d) concentrating the solution until a powder is obtained, (ii) dissolving the powder forming a sol, (iii) coating a substrate with the sol, and (iv) annealing the coated substrate.

Abstract: Reticulated vitrified carbon compositions which contain particles of Cu, Sn, Zn, Pb, Ni, Fe, or alloys or mixtures thereof dispersed therein and reticulated vitreous carbon compositions wherein some or all of said metal or alloy particles have been converted into salts or mixtures of salts thereof. Processes for the preparation of such compositions.

Abstract: Primarily dedicated to the production of ultrafine particles with good dispersion stability on a industrial scale, the invention provides ultrafine particles characterized in that each of its constituent particles comprises a shell substantially composed of a metal organic compound and a core substantially composed of the metal derived from the metal organic compound, the ultrafine particles having a mean diameter of 1-100 nm, and a process for producing the ultrafine particles.

Abstract: A carbon dioxide and water adsorbent comprises a carbonized and activated precursor material having first functional sites that adsorb carbon dioxide and second functional sites that adsorb water independently of the first functional sites. The adsorbent is characterized by a total pore volume of between about 1.50 to 2.50 cm3/g, a median pore diameter between about 0.5 to 1.2 nm, and a BET surface area between about 2000 to 2500 m2/g.

Abstract: Glass vessels are coated by spraying a solution containing 86 to 1,290 g/L of (HO).sub.x Sn(C.sub.2 O.sub.4).sub.y on the 500.degree. to 600.degree. C. hot outer surface of the vessels. The solution may contain oxalic acid, HCl and a portion of the (HO).sub.x Sn(C.sub.2 O.sub.4).sub.y compound may be substituted by a compound (OH).sub.2 SnCl.sub.2. The coatings are uniform.

Abstract: Metal carbides can be formed by the pyrolysis of a composition comprising metal and carboxylic acid residues bonded therein, the composition being substantially free of extraneous carbon and also having metal moieties that are not in the substituent position. Dicarboxylic acids, for example, can be reacted with either metal alkoxides or metal halides to form an oligomer or polymer which can be calcined to the metal carbide. Alternatively, a metal alkoxide can be reacted with a monocarboxylic acid to form a metal alkoxide carboxylate which can be heated to the metal carbide. Finally, a metal carboxylate can be heated to form the desired metal carbide.

Abstract: A method for producing oxygen and methane from carbon dioxide, and hydrogen utilizing a methanation reactor, a reforming reactor, and an electrolyzer. Carbon dioxide and hydrogen are reacted to produce methane and water. A portion of the water along with a portion or all of the methane is directed to a reforming reactor where it is reacted to produce hydrogen and carbon monoxide, while the remaining portion of the methane is stored. The hydrogen is recycled to the methanation reactor while the carbon monoxide is vented or stored for use as a fuel. The second portion of the water is electrolyzed to its constituents, hydrogen and oxygen. The oxygen is stored or used for life support while the hydrogen is recycled to react with additional carbon dioxide.

Abstract: Molybdenum hexacarbonyl is prepared by carbonylating diammonium oxopentachloromolybdate (V) (NH.sub.4).sub.2 (MoOCl.sub.5) at pressures up to about 2000 psig and temperatures up to about 150.degree. C. in a solvent such as tetrahydrofuran, using a metallic reductant such as magnesium and an oxygen scavenger such as aluminum trichloride.

Abstract: Alkali or alkaline earth metal cobalttetracarbonylates well suited for catalyzing carbonylation reactions, e.g., the carbonylation of organic compounds comprising halomethyl functions, are facilely prepared by reacting a cobalt (II) compound with carbon monoxide in the presence of (i) an inorganic base which comprises an alkali or alkaline earth metal hydroxide or an alkali or alkaline earth metal bicarbonate and (ii) at least one sulfur compound having at least one sulfur atom, the oxidation state of which being no greater than +3, and in a reaction medium comprising water, an alcohol, an ether, or admixture of water and an alcohol or an ether.

Abstract: The invention provides the novel ruthenium carbonylate anions [Ru.sub.4 (CO).sub.11 ].sup.6- and [Ru.sub.6 (CO).sub.17 ].sup.4- and [Ru.sub.6 (CO).sub.16 ].sup.6-, together with the salts and acids of these anions. The former anion can be prepared by reduction of either Ru.sub.3 (CO).sub.12 or [Ru.sub.4 (CO).sub.12 ].sup.4- with controlled amounts of an alkali metal in the presence of an electron carrier compound, while the latter two anions are prepared by a similar reduction of [Ru.sub.6 (CO).sub.18 ].sup.2-. [Ru.sub.6 (CO).sub.16 ].sup.6- can also be prepared by a similar reduction of [Ru.sub.6 (CO).sub.17 ].sup.4-.

Abstract: Disclosed are the novel cluster compounds [HRu.sub.4 (CO).sub.13 ].sup.1-, [Ru.sub.4 (CO).sub.13 ].sup.2-, [Ru.sub.4 (CO).sub.12 ].sup.4-, [HRu.sub.4 (CO).sub.12 ].sup.3-, and salts thereof, and H.sub.4 Ru.sub.4 (CO).sub.12. Also disclosed are novel procedures for synthesizing these cluster compounds in high yield. Further disclosed is a novel procedure for making H.sub.2 Ru.sub.4 (CO).sub.13 and H.sub.4 Ru.sub.4 (CO).sub.12 in high yield. Also disclosed are [Ru.sub.3 (CO).sub.11 ].sup.2- and the corresponding osmium dianion.

Abstract: H.sub.2 Os.sub.3 (CO).sub.10 has apparent Lewis base character and can be made to react with electron deficient iron, cobalt and nickel carbonyls, including salts of [Fe(CO).sub.4 ].sup.2-, Fe.sub.2 (CO).sub.9, (.eta..sup.5 -C.sub.5 H.sub.5)Co(CO).sub.2, Co.sub.2 (CO).sub.8 and [(.eta..sup.5 -C.sub.5 H.sub.5)Ni(CO)].sub.2, to give heteronuclear tri-osmium carbonyl hydrides, some of which are new compounds. New compounds disclosed include H.sub.2 Fe.sub.2 Os.sub.3 (CO).sub.16,H.sub.2 Fe.sub.2 Os.sub.3 (CO).sub.15, H.sub.2 (.eta..sup.5 -C.sub.5 H.sub.5)CoOs.sub.3 (CO).sub.10 and H.sub.3 (.eta..sup.5 -C.sub.5 H.sub.5)NiOs.sub.3 (CO).sub.9.

Abstract: Disclosed is the new pentanuclear bimetallic cluster complex H.sub.2 Fe.sub.2 Os.sub.3 (CO).sub.15. Such complex is made by reacting a salt of [HFe(CO).sub.4 ].sup.1- and H.sub.2 Os.sub.3 (CO).sub.10 in a solvent which solubilizes said salt to generate an [HFe(CO).sub.4 ].sup.1- anion. Addition of a protic acid then causes the formation of H.sub.2 Fe.sub.2 Os.sub.3 (CO).sub.15.

Abstract: A novel class of extractants and a method of using the extractants in the hydrometallurgical recovery of nickel and cobalt metal. The extractants comprise a water immiscible organic solvent system containing solubilized mercaptide anions. In an important embodiment of the invention, the mercaptide anions are generated by solubilizing an alkali metal mercaptide in a polar organic solvent capable of solvating alkali metal ions. Alternatively, an organic solution of a mercaptan is exposed to an aqueous solution of NaOH or KOH to produce the mercaptide anion.The extractants are used by being contacted with cobalt, nickel, or cobalt and nickel pregnant aqueous solutions. On mixing, the cobalt and/or nickel values are taken up by the organic as cobalt or nickel mercaptides. These may then be stripped of cobalt and nickel by treatment with an aqueous alkaline solution and carbon monoxide.

Abstract: A novel class of extractants and a method of using the extractants in the hydrometallurgical recovery of nickel and cobalt metal. The extractants comprise a water immiscible organic solvent system containing solubilized mercaptide anion. In an important embodiment of the invention, the mercaptide anions are generated by adding compounds containing both a thiol group and an amine group such as aminoethanethiols or amides of thioglycolic acids to water immiscible organic solvents, preferably of polar character. These systems generate the required mercaptide anions by undergoing an internal acid dissociation.The extractants are used by being contacted with cobalt, nickel, or cobalt and nickel pregnant aqueous solutions. On mixing, the cobalt and/or nickel values are taken up by the organic as cobalt and nickel mercaptides. These may then be stripped of cobalt and nickel by treatment with an aqueous alkaline solution and carbon monoxide.

Abstract: A novel class of extractants and a method of using the extractants in the hydrometallurgical recovery of nickel and cobalt metal. The extractants comprise a water immiscible organic solvent system containing solubilized mercaptide anions. In an important embodiment of the invention, the mercaptide ions are generated by adding a mercaptan to a mixed water immiscible solvent comprising a basic compound such as an amine, preferably a tertiary amine, and a polar component such as an alcohol, whereby the mercaptan undergoes acid dissociation.The extractants are used by being contacted with cobalt, nickel, or cobalt and nickel containing aqueous solutions. On mixing, the cobalt and/or nickel values are taken up by the organic as cobalt or nickel mercaptides. These may then be stripped of cobalt and nickel by treatment with an aqueous alkaline solution and carbon monoxide.

Abstract: A novel process for extracting, concentrating, and isolating nickel and cobalt from aqueous solution thereof. A cobalt and/or nickel bearing solution is contacted with an extractant comprising a substantially water immiscible organic solvent containing solubilized mercaptide anion to form water insoluble cobalt and nickel mercaptides in the organic phase. The organic phase is then separated from the raffinate and contacted with an alkaline solution and carbon monoxide to produce nickel and cobalt carbonyl compounds. Typically, the nickel carbonyl produced is gaseous Ni(CO).sub.4 which may be easily isolated by known methods from other components in the off-gas stream. Pure nickel metal is then obtained from the nickel tetracarbonyl by known methods. The cobalt carbonyl compound produced is typically water soluble carbonyl cobaltate ion, Co(CO).sub.4.sup.-, which may be oxidized to form water insoluble cobalt carbonyl compounds.

Abstract: The complexes [Ir(CO).sub.3 I], [HIr(CO).sub.3 I.sub.2 ], [HIr(CO).sub.2 I.sub.2 (H.sub.2 O)], [RIr(CO).sub.2 I.sub.2 ], [(RCO)Ir(CO).sub.2 I.sub.2 ] where R is an alkyl radical, are described. Processes for preparing the aforesaid complexes are described and in addition a new process for preparation of [Ir(CO).sub.3 I.sub.3 ] is described.

Abstract: The filterability of aluminum salts precipitated from an aqueous solution containing dissolved aluminum ion is improved by adjusting the pH of the solution to between about 4 and 6, adding less than a stoichiometric amount of a 1, 3-dicarbonyl compound such as acetylacetone to the solution to precipitate the aluminum dicarbonyl and then adding a sufficient amount of an alkaline hydroxide to precipitate the remaining dissolved aluminum ion in the form of aluminum hydroxide to obtain a mixed precipitate which can be readily filtered.

Abstract: Production of alkali metal tetracarbonylferrates by reaction of alkali metal with an iron carbonyl, preferably iron pentacarbonyl, in a suitable solvent and in the presence of an electron carrier, the alkali metal being present in the liquid phase. Also, solvated forms of alkali metal tetracarbonylferrates as new compositions of matter. The alkali metal tetracarbonylferrates are useful in the production of aldehydes, ketones, acids, esters and amides.

Abstract: This invention comprises a novel method for the preparation of metal hydrocarbonyls of metals of Groups 1b, 2b, 3b, 4b, 5b, 6b, 7b and 8 of the Periodic Table of the Elements and the attendant method for isolation of pure metals by the separation of a single metal as a metal hydrocarbonyl from any mixture and the subsequent decomposition of the metal hydrocarbonyl to metal powder. The methods of this invention are of particular value in recovering valuable metals in pure state from such sources as exhausted or poisoned metal-based catalysts, low grade ores, filter cakes or mining tailings. Gaseous metal hydrocarbonyl products of this invention also make possible isotope separation.

Abstract: Solutions of cobalt carbonyl and cobalt carbonyl hydride in organic solvents are prepared by treating aqueous solutions of cobalt salts with carbon monoxide and hydrogen at a temperature of from 50.degree. to 200.degree.C and a pressure of from 50 to 500 atmospheres in the presence of solvents which are sparingly water-miscible or are water-immiscible and which have a content of cobalt carbonyl, cobalt carbonyl hydride or mixtures thereof, the starting materials and the organic solvents being passed cocurrently through a zone in which a turbulent flow is maintained. The improvement includes using n-butanol as solvent. Solutions of cobalt carbonyl and cobalt carbonyl hydride in n-butanol are suitable as catalyst solutions for oxo syntheses.