Allied Corporation

Allied Chemical Corporation

Alliedsignal Inc.

John N Armor

Emery J Carlson

Jean Yamanis

Anthony J Fanelli

Addison Miles Smith

Gary B Marsh

William J Cunningham

Patrick M Zambri

Guido P Pez

Chromium(III) oxide and hydroxide aerogels are produced by the reaction of chromium(VI) oxide with a solvent which is reducing to chromium(VI), such as methanol, heating the solution to hypercritical conditions, and venting the solvent hypercritically. The product aerogels exhibit surface areas above 400 m.sup.2 /g, pore volumes of at least 2 cm.sup.3 /g and a substantially uniform pore size distribution. Also disclosed is a unique process which employs high pore volume, high surface area chromium(III) oxide or hydroxide as a fluorination catalyst. More particularly, reaction of C.sub.2 Cl.sub.3 F.sub.3 with HF over these catalysts produced high yields of C.sub.2 Cl.sub.2 F.sub.4 and C.sub.2 ClF.sub.5.

Chromia aerogel, method of producing same and fluorination process

Chromium aerogel method of producing same and fluorinating process

Inorganic metal oxides having high surface area and pore volume are prepared by spray drying. The admixture which is spray dried to yield the metal oxides is produced from reactants comprising at least one hydrolyzable metal compound, a sufficient amount of water to at least partially hydrolyze the metal compound and an organic solvent. The admixture is supplied as a plurality of droplets to a reaction zone operated under conditions of temperature and pressure below the critical temperature and pressure of the reactants but sufficient to produce a product comprising metal oxide powders and a gas comprising organic solvent vapors. The powders are separated from the gas in a known fashion and collected. Spray drying of non-aqueous systems unexpectedly produces metal oxides having properties generally intermediate conventionally produced oxides and aerogels.

Spray-dried inorganic oxides from non-aqueous gels or solutions

A widely applicable and simple technique has been discovered for preparing aerogels in more durable forms. By the exposure of a variety of support structures to a pregel heated to hypercritical conditions, the resulting aerogel is produced and retained on the supporting structure. Thus, the aerogels are prepared and 'pelletized' in one step.

Production of aerogels on a support

Improved processes for the conversion to oximes by selective oxidation, in the vapor phase, of saturated primary aliphatic or alicyclic amines having 2 to 12 carbon atoms especially cyclohexylamine to cyclohexanone oxime with elemental oxygen, in a reaction zone, in the presence of an effective amount of a catalyst comprising an oxygen-containing tungsten compound and alumina by (1) periodically regenerating the oxygen-containing tungsten catalyst by heating same at about 250.degree. C.-300.degree. C. in the presence of elemental oxygen, or (2) maintaining the temperature of the oxygen-containing tungsten catalyst in a range of about 100.degree. C.-145.degree. C. or (3) employing higher mol fractions of oxygen and of amine in a range of about 0.2-0.4 in the vapor phase are disclosed. An improved method of preparing an oxygen-containing tungsten on an alumina catalyst is also disclosed.

Catalyst and method of making same for oxidation of primary amines to

A process is disclosed for the preparation of metallic products from metal salts admixed with solvent wherein at least one of the metal salt and the solvent is easily reducible. The admixture is heated under hypercritical conditions of temperature and pressure to produce metallic products and a hypercritical fluid. The hypercritical fluid is subsequently removed from the reaction zone and the metallic product is collected. The metallic product includes pure metals selected from the group of silver, gold, platinum, palladium, ruthenium, rhodium, mercury, arsenic, rhenium, tellurium, iridium, osmium, and copper, and alloys and mixtures thereof. The metallic product ordinarily exists as finely divided powders which may be highly porous.

Preparation of metal powders

Oxidation of primary amines to oximes by elemental oxygen with catalyst

A process for the production of oximes which comprises contacting, in the vapor phase, a primary saturated aliphatic or alicyclic amine of 2 to 12 carbon atoms with an elemental oxygen gas in the presence of an effective amount of a catalyst comprising an alumina or oxygen-containing tungsten substance on a metal oxide support using temperatures between about 130.degree. and 230.degree. C. at atmospheric pressure is disclosed. Preferred alumina catalysts are alumina xerogels, .gamma.-alumina and acidic, fluorinated alumina. Preferred oxygen-containing tungsten catalysts are WO.sub.3 on .gamma.-alumina or WO.sub.3 on alumina xerogels.

Catalytic oxidation of primary amines to oximes by elemental oxygen

A catalyst composition comprising a uniform dispersion of individual metallic palladium particles, substantially free of clusters of said particles, on and throughout an alumina aerogel support, said composition having a BET surface area in the range of about 20 to about 700 m.sup.2 /g, a pore volume in the range of about 1.5 to about 12 cm.sup.3 /g, a bulk density in the range of about 0.003 to about 0.5 g/cm.sup.3 and having a Pd.degree./Al.sub.2 O.sub.3 weight ratio of about 1:1000 to about 1:5 is disclosed. A process of preparing the catalyst composition having metallic palladium impregnated on alumina aerogel and a process of using same as a hydrogenation catalyst are also disclosed.

Palladium on alumina aerogel catalyst composition and process for making

Primary saturated aliphatic and alicyclic amines are oxidized by elemented oxygen to oximes, especially cyclohexylamine to cyclohexanone oxime, in vapor phase using silica gel catalyst; preferably using concentrations by volume such as 1% to 5% of amine and 5% to 30% of oxygen, and using temperatures between about 120.degree. C. and 250.degree. C. at atmospheric pressure.

Process for oxidizing primary amines to oximes by elemental oxygen

An amorphous silica/alumina gel catalyst obtained by coprecipitating orthosilicate tetraester and aluminate triester in about 2.5:1 mole ratio, via rapid addition of about 0.4 to 5 moles of water per molecular equivalent of total ester groups, and drying at not over about 275.degree. C. is an effective catalyst for vapor phase reaction of cyclohexanone, ammonia and oxygen to form cyclohexanone oxime. This oxime can be rearranged to caprolactam, the starting material for nylon-6.

Process for ammoximation of cyclohexanone

Ammonia, oxygen e.g., as air, and a ketone react in contact with a gallium oxide catalyst at temperatures such as 50.degree.-500.degree. C., especially such catalyst obtained by heating hydrated gallium nitrate in air at about 350.degree. C. for several hours. The oximes have known utilities, including uses as oxidation inhibitors and as intermediates for production of amides. In particular, when the ketone is cyclohexanone, the cyclohexanone oxime in the reaction product can further be converted to the cyclic amide, caprolactam, e.g. by contacting the product with an aluminosilicate catalyst (treated with boric acid) having average pore diameter of at least 7 angstroms, especially a molecular sieve, suitably downstream in the same direction vessel. Caprolactam is the monomer starting material for nylon 6.

Direct oximation of ketones using gallia catalysts

Ammonia, oxygen e.g., as air, and a ketone react in contact with a catalyst such as porous, amorphous silica or alumina which may or may not have a coating to form an oxime, at temperatures such as 50.degree.-500.degree. C. The oximes have known utilities, including uses as oxidation inhibitors and as intermediates for production of amides. In particular, when the ketone is cyclohexanone, the cyclohexanone oxime in the reaction product can further be converted to the cyclic amide, caprolactam, e.g. by contacting the product with an aluminosilicate catalyst having average pore diameter of at least 7 angstroms, especially a molecular sieve, suitably downstream in the same reaction vessel. Caprolactam is the monomer starting material for nylon 6.

Direct oximation of ketones

A catalytically active compound or complex from the complex 'bis-titanocene' (U.S. Pat. No. 3,776,932 of Dec. 4, 1973 to G. P. Pez) by reaction thereof with ammonia at low temperature and in absence of contaminants, giving a characteristic powder x-ray diffraction pattern and characteristic radiation and e.s.r. spectra.

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Morris Plains, NJ, United States of America

John N Armor