Abstract: The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided.The novel compositions and others made according to the process of the invention are useful as hydrocarbon conversion catalysts; for example, for the oxidation of alkanes and the decomposition of hydroperoxides.

Abstract: Organic hydroperoxides are decomposed by drying a reaction mixture containing the organic hydroperoxide and an organic solvent such that said dried reaction mixture comprises approximately 1 weight percent or less of water and contacting the dried reaction mixture with a metal organic ligand catalyst under hydroperoxide decomposition conditions. An organic co-solvent for the hydroperoxide may also be used. Particularly effective catalysts are cobalt acetylacetonates and ruthenium acetylacetonates and combinations thereof.

Abstract: The invention provides novel methods for the oxidation of hydrocarbons with oxygen-containing gas to form hydroxy-group containing compounds and for the decomposition of hydroperoxides to form hydroxygroup containing compounds. The catalysts used in the methods of the invention comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The catalyst compositions are prepared by halogenating a transition metal complex of a porphyrin.

Abstract: Transition metal complexes of Gable porphyrins having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

Abstract: Process and apparatus are provided for oxidation of oxidation of organic compounds in which a reaction zone is provided, containing an open space and a bed of solid granular catalyst, an organic feedstock and oxygen are passed in gas phase through the open space and then into contact with the catalyst bed, and reaction products are removed from the open space after relatively less contact with the catalyst, and from at least one other location after relatively greater contact with the catalyst. Greater yield of desired product may be obtained in such operation than in operation where all of the reaction products are removed after the greater contact with the catalyst.

Abstract: Organic hydroperoxides are decomposed by drying a reaction mixture containing the organic hydroperoxide and an organic solvent and contacting the dried reaction mixture with a metal organic ligand catalyst under hydroperoxide decomposition conditions. An organic co-solvent for the hydroperoxide may also be used.

Abstract: Barium peroxide in which has been incorporated a transition metal compound is used as a catalyst for the oxidative dehydrogenation of organic compounds in the presence of terminal oxidants.

Abstract: New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

Abstract: As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.

Abstract: A process for the direct catalytic oxidation of methane to methanol comprises separately contacting chromium chemically bound to the oxygen of a metal oxide support surface with (1) methane and (2) oxidant. The support may comprise silica, alumina, magnesia, titania, or zirconia.

Abstract: Aluminophosphates containing manganese in the structural framework are employed for the oxidation of alkanes, for example the vapor phase oxidation of methane to methanol.

Abstract: Hydroperoxides are decomposed by contact with metalloporphyrin coordination complex catalysts in which hydrogen in the porphyrin molecule has been substituted with at least one nitro group and may be further substituted with other electron-withdrawing elements or groups, for example, halogen or halocarbons, or with hydrocarbon groups. Preferred catalysts are iron tetranitro-.beta.-octaethylporphyrins and iron tetrakispentafluorophenyl-.beta.-nitroporphyrins.

Abstract: Alkanes are catalytically oxidized using heteropolyacids (HPAs) or polyoxoanions (POAs) deposited on a graphite surface. The HPAs and POAs are framework-substituted with a different metal in place of a metal-oxygen unit.

Abstract: An improved cooling cover is disclosed for use in bell shaped annealing furnaces. The cooling cover includes a jet nozzle orifice arrangement which develops jet streams from a low pressurized supply of air at ambient temperature in the plenum chamber of the cooling cover. A multitude of free standing jet streams thus impinge the inner cover of the bell shaped annealing stand to produce improved cooling times. Importantly, the plenum chamber includes strategically placed axial jet pump outlets which are effective to draw the jet streams from the cooling cover after they have been in heat transfer contact with the inner cover in a distribution pattern which is not altered so that the work or coils within the inner cover can be more uniformly cooled than heretofore possible.

Abstract: Modifications are provided to a standard, batch type industrial heat treat furnace of a hot wall design which permit the furnace to be operated efficiently at high temperatures. The furnace is of a cylindrical design having a forward heat treat chamber and a rearward plenum chamber with a flat bulkhead plate in-between the chambers. The bulkhead has exit and inlet openings permitting wind mass to flow to the heat treat chamber and back to the plenum chamber. The bulkhead has a plurality of radially extending slits formed therein which permit the bulkhead to remain flat despite temperature and pressure gradients resulting in expansion/contraction of the bulkhead. Additionally, the furnace includes a closed end muffle within the heat treat chamber into which work to be heat treated is placed. A water cooled spring biasing support is provided for the closed end of the muffle to resist downward deformation of the muffle at high temperatures.

Abstract: Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

Abstract: Barium peroxide oxidizer, together with a transition metal from Group I, III, IV, V, VII or VIII or compound thereof is used as stoichiometric reagent in the oxidative dimerization of hydrocarbons having three or four carbon atoms. Barium peroxide oxidizer, together with a transition metal from Group I, III, IV, V, VI, VII or VIII or compound thereof is used as stoichiometric reagent in the dehydrogenation of hydrocarbons having three or four carbon atoms.

Abstract: As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Method of oxidizing alkanes by contact with a catalyst comprising diazido derivative of a metal phthalocyanine, including halogenated phthalocyanines. Method of oxidizing alkanes by contact with a catalyst comprising a metal phthalocyanine or halide thereof, including halogenated phthalocyanines, and an alkali metal or ammonium or tetraalkylammonium azide.

Abstract: Barium peroxide oxidizer, together with a transition metal from Group I, III, IV, V, VII or VIII or compound thereof is used as stoichiometric reagent in the oxidative dimerization of hydrocarbons having three or four carbon atoms. Barium peroxide oxidizer, together with a transition metal from Group I, III, IV, V, VI, VII or VIII or compound thereof is used as stoichiometric reagent in the dehydrogenation of hydrocarbons having three or four carbon atoms.

Abstract: A process for the direct catalytic oxidation of methane to methanol comprises chromium chemically bound to the oxygen of a metal oxide catalytic support surface. The support may comprise silica, alumina, magnesia, titania, or zirconia.