Abstract: A process for the preparation of a fluid bed vinyl acetate (VAM) catalyst comprising impregnating a support comprising a mixture of substantially inert microspheroidal particles with a solution comprising a metal salt of Pd and M, wherein M comprises Ba, Cd, Au, La, Nb, Ce, Zn, Pb, Ca, Sr, Sb or mixtures thereof, reducing the metal salts to form a deposit of Pd and M on the support surface and impregnating the support with at least one alkali metal salt. At least 50% of the particles used for the microspheroidal support have a particle size below 105 microns.

Abstract: The invention relates to a process for producing supported shell catalysts comprising noble metals by UV photoreduction of noble metal salt precursors fixed to a support. For this purpose, the shaped supported body is impregnated with suitable noble metal salts which are then reduced to the metals in a zone close to the surface by means of UV radiation, preferably in the absence of a chemical reducing agent. The metal salts in the interior of the pellets which have not been irradiated and therefore have not been reduced are extracted using a solvent. The noble metal shell catalysts produced in this way can be used for many heterogeneously catalyzed reactions such as hydrogenations and oxidations. According to the invention, Pd/Au shell catalysts on porous ceramic supports, e.g. SiO2 shaped bodies, produced by this process can be used in the synthesis of vinyl acetate.

Abstract: Lower hydrocarbons are converted to carboxylic acids and/or dehydrogenated hydrocarbon product by contacting a feed mixture containing lower hydrocarbons, oxygen source, diluent, and sulfur-containing compound, with a multifunctional, mixed metal catalyst at a temperature from about 150° C. up to about 400° C. The lower hydrocarbons include C2-C4, and the presence of sulfur compound in the feed mixture results in increased yield of carboxylic acid and/or dehydrogenated hydrocarbon product.

Abstract: Process for the production of vinyl acetate in which ethylene, acid and oxygen-containing gas are combined at elevated temperature in the presence of a catalyst material to produce (i) a product mixture comprising vinyl acetate, (ii) a liquid by-product comprising acetic acid and (iii) a gaseous by-product comprising carbon dioxide. The liquid by-product is separated from the product mixture and treated to reduce the water content therein before being recycled to the reactor such that the water entering the reactor comprises less than 6 wt %, (preferably less than 4 wt %, more preferably less than 3 wt %) of the total of acetic acid and water entering the reactor.

Abstract: One aspect of the present invention relates to a method of making vinyl acetate monomer, involving contacting reactant gases with a catalyst containing palladium, gold and a support in the presence of clean steam, the clean steam present from about 2 to about 10 psia, with the proviso that the support does not contain alumina or zinc oxide and the support is not treated with a sulfur containing compound. For example, the method of making vinyl acetate monomer may involve the reaction scheme:O.sub.2 +H.sub.2 O+CH.sub.2 CH.sub.2 +CH.sub.3 CO.sub.2 H.fwdarw.CH.sub.3 CO.sub.2 CH.dbd.CH.sub.2 +H.sub.2 O.

Abstract: Methods for the catalytic production of vinyl acetate monomer from ethane, ethylene or an ethane/ethylene mixture using a first catalyst containing MoVNbPd, MoVLaPdNbX (where X is Al, Ga, Ge or Si) or MoVNbX (where X is P, B, Hf, Te, As or mixtures thereof) in the first step of oxidation and using a conventional VAM catalyst for the second step. The method produces high yields to acetic acid and vinyl acetate without the coproduction of carbon monoxide.

Abstract: A process and apparatus for vinyl acetate production. A membrane unit containing a membrane selectively permeable to ethylene over argon is used to recover ethylene from the argon purge stream.

Abstract: A catalyst for preparing vinyl acetate in the gas phase from ethylene, acetic acid and oxygen or oxygen-containing gases with, at the same time, low-high boiler formation which catalyst comprises palladium and/or its compounds, gold and/or its compounds, moron or boron compounds and alkali metal compounds on a particular support.

Abstract: Synthesying vinyl acetate utilizing a catalyst for the production of vinyl acetate by reaction of ethylene, oxygen and acetic acid comprising a porous support on the porous surfaces of which is deposited metallic copper in a zone surrounded by deposits of catalytically effective amounts of metallic palladium and gold, neither of which is substantially intermingled with said copper.

Abstract: Disclosed is a continuous process for the production of 3,4-diacetoxy-1-butene (DAcB) by the reaction of 3,4-epoxy-1-butene (EpB) with acetic anhydride (Ac.sub.2 O) in the presence of potassium acetate (KOAc) wherein the KOAc is formed in situ by contacting EpB, acetic anhydride and a potassium salt selected from potassium carbonate, potassium bicarbonate, potassium hydroxide or a mixture of any two or more thereof at elevated temperatures.

Abstract: A catalyst for the production of vinyl acetate by reaction of ethylene, oxygen and acetic acid as reactants comprising a porous support on the porous surfaces of which is deposited catalytically effective amounts of metallic palladium and gold, copper as the free metal or cupric acetate, and a fourth metal selected from the group consisting of magnesium calcium, barium, and zirconium, as its oxide or mixture of oxide and free metal.

Abstract: The invention relates to a process for producing supported shell catalysts comprising noble metals by UV photoreduction of noble metal salt precursors fixed to a support. For this purpose, the shaped supported body is impregnated with suitable noble metal salts which are then reduced to the metals in a zone close to the surface by means of UV radiation, preferably in the absence of a chemical reducing agent. The metal salts in the interior of the pellets which have not been irradiated and therefore have not been reduced are extracted using a solvent.The noble metal shell catalysts produced in this way can be used for many heterogeneously catalyzed reactions such as hydrogenations and oxidations.According to the invention, Pd/Au shell catalysts on porous ceramic supports, e.g. SiO.sub.2 shaped bodies, produced by this process can be used in the synthesis of vinyl acetate.

Abstract: A process for the production of vinyl acetate (VA) by reaction in the vapor phase of ethylene, oxygen and acetic acid as reactants, comprising passing at a temperature sufficient to initiate the reaction, a feed gas comprising said reactants and continuously or intermittently containing liquid acetic acid and/or non-volatile components, through a filter and distribution bed of inert material having throughout its volume substantial intercommunicating open spaces among the solid portions, and thence through a plurality of tubes each containing a bed of catalyst for the reaction, and withdrawing a product gas comprising VA. The filter and distribution bed acts to filter out the liquid acetic acid and/or non-volatile components and distribute more evenly the feed gas into the tubes.

Abstract: The invention relates to a catalyst and a process for preparing vinyl acetate in the gas phase from ethylene, acetic acid and oxygen or oxygen-containing gases over a catalyst comprising palladium and/or its compounds, cadmium compounds and alkali metal compounds on a support, wherein the catalyst additionally contains at least one rhenium and/or at least one zirconium compound.

Abstract: A process for the production of vinyl acetate which comprises contacting ethylene, acetic acid and an oxygen-containing gas with a supported palladium catalyst prepared by a process comprising the steps of (a) impregnating a catalyst support with a palladium compound, (b) converting the palladium compound to substantially metallic palladium, and (c) sintering the supported palladium at a temperature of greater than 500.degree. C.

Abstract: A catalyst particularly useful in the preparation of unsaturated esters such as the reaction of ethylene, oxygen and acetic acid in a vapor phase to form vinyl acetate. The catalyst comprises a honeycomb carrier coated with silica and containing palladium and gold throughout the silica coat. Such catalysts show reduced pressure drop and a high space time yield for vinyl acetate.

Abstract: A process for the production of vinyl acetate which comprises reacting at elevated temperature in a fluid bed reactor ethylene, acetic acid and an oxygen-containing gas in the presence of a fluid bed catalyst material wherein a liquid is introduced into the fluidised bed reactor for the purpose of removing heat therefrom by evaporation of the liquid.

Abstract: A catalyst and method of its production for use in making vinyl acetate monomer. The carrier is impregnated with a basic solution and a solution containing gold salts and palladium salts and finally impregnated with alkali acetate. The activity and selectivity of the catalyst, its mechanical strength, the noble-metal adhesion and the dispersion of noble metal on the carrier can be improved if the carrier is impregnated in a pretreatment with salts containing as cation elements of groups IA, IIA, IIIA and IVB of the periodic table and as anions elements of group VIIA or complex anions such as nitrate, sulfate or anions of organic acids such as acetate and lactate and is subsequently dried and calcined at temperatures of at least 160.degree. C.

Abstract: The invention relates to Pd/K/Au, Pd/K/Ba or Pd/K/Cd supported catalysts built up in the form of an outer layer, the production thereof and the use thereof for preparing vinylacetate from ethylene, acetic acid and oxygen in the gas phase. The specified catalysts are produced by impregnating the support particles with a solution of salts of the corresponding elements and then drying them, with the dynamic viscosity of the solution being at least 0.003 Pa.s and the solution volume in impregnation being more than 80% of the pore volume of the support particles and the duration of the impregnation and also the time until commencement of the drying being selected so as to be sufficiently short for, after completion of the drying, the specified metal salts to be present in an outer layer of from 5% to 80% of the pore volume of the support particles.

Abstract: A process is disclosed for the production of vinyl acetate by reaction of ethylene, oxygen and acetic acid as reactants comprising contacting said reactants and a non-halogen containing copper compound with a catalyst comprising a porous support on the porous surfaces of which is deposited catalytically effective amounts of metallic palladium, gold and copper. During the process to prepare vinyl acetate, a stream of alkali metal acetate is preferably passed over the catalyst. The process results in higher vinyl acetate selectivity and productivity due to lower CO.sub.2 selectivity during the life of the catalyst, and/or longer catalyst life.

Abstract: A fluid bed process for the manufacture of vinyl acetate from ethylene, acetic acid and oxygen comprising feeding a gaseous mixture comprising ethylene and acetic acid into a fluid bed reactor through a first inlet, introducing the oxygen into the reactor through a second inlet, co-joining the oxygen, ethylene and acetic acid in the reactor in contact with a fluid bed catalyst to produce vinyl acetate. The particle size diameter of the particulate catalyst material has a range of 60% of the particles being below 200 microns (0.1 mm) with no more than 40% of the particles being below 40 microns (0.04 mm).

Abstract: A catalyst particularly useful in the preparation of unsaturated esters such as the reaction of ethylene, oxygen and acetic acid in a vapor phase to form vinyl acetate. The catalyst comprises a honeycomb carrier coated with silica and containing palladium and gold throughout the silica coat. Such catalysts show reduced pressure drop and a high space time yield for vinyl acetate.

Abstract: An improved method for synthesizing vinyl acetate by the gas phase reaction of acetic acid with ethylene in the presence of oxygen. At least two catalyst modifiers are used, each causing a different level of catalyst activity. The relative mounts of the catalyst modifiers are used to fine tune the productivity of the catalyst.

Abstract: The invention relates to Pd/K/Au, Pd/K/Ba or Pd/K/Cd supported catalysts built up in the form of an outer layer, the production thereof and also the use thereof for preparing vinyl acetate from ethylene, acetic acid and oxygen in the gas phase. The catalysts specified are produced by impregnating the support particles, while mixing intimately, with a solution of salts of the corresponding elements and then drying the support particles immediately, with the dynamic viscosity of the solution being at least 0.003 Pa.s and the solution volume in impregnation being from 5 to 80% of the pore volume of the support particles.

Abstract: The invention relates to Pd/K/Au, Pd/K/Ba, or Pd/K/Cd supported catalysts having an impregnated layer structure, the production thereof and also the use thereof for preparing vinyl acetate from ethylene, acetic acid and oxygen in the gas phase. The catalysts specified are produced by spraying the support particles, while mixing intimately with a solution of salt of the corresponding elements in the form of drops having an average diameter of at least 0.3 mm or in the form of liquid jets and then drying the support particles immediately, with the dynamic viscosity of the solution being at least 0.003 Pa.cndot.s and the solution volume in spraying being from 5 to 80% of the pore volume of the support particles.

Abstract: A catalyst useful for the manufacture of vinyl acetate from acetic acid, oxygen and ethylene which contains palladium, calcium, and at least one of zirconium and rhenium and the method of manufacture of vinyl acetate using the catalyst.

Abstract: In a process for the preparation of palladium and palladium/gold shell type catalysts for vinyl acetate production, the improvement comprises using a barium salt to precipitate water-insoluble palladium and optional gold compounds onto a support prior to reduction with a reducing agent. A barium salt additive may also be introduced to the catalyst after reduction to reduce the tendency of the catalyst to deactivate with use.

Abstract: A fluid bed process for the manufacture of vinyl acetate from ethylene, acetic acid and oxygen comprising feeding a gaseous mixture comprising ethylene and acetic acid into a fluid bed reactor through a first inlet, introducing the oxygen into the reactor through a second inlet, co-joining the oxygen, ethylene and acetic acid in the reactor in contact with a fluid bed catalyst to produce vinyl acetate. The particle size diameter of the particulate catalyst material has a range of 60% of the particles being below 200 microns (0.1 mm) with no more than 40% of the particles being below 40 microns (0.04 mm).

Abstract: Supported catalyst, process for its preparation and its use for the preparation of vinyl acetateThe invention relates to improved Pd/K/Au, Pd/K/Ba and Pd/K/Cd supported catalysts, their preparation and their use for the preparation of vinyl acetate from ethylene, acetic acid and oxygen in the gas phase. The stated catalysts are prepared by atomizing a solution of corresponding metal salts by means of ultrasonics and then applying them in such limited amounts and within such a limited time to the carrier particles, and beginning to dry them, so that the catalytically active metal salts cannot penetrate into the carrier particles as far as the core but only into a larger or smaller outer part.

Abstract: Provided are a carrier having at least one passing-through channel used for a catalyst for producing unsaturated esters, and a catalyst for producing unsaturated esters comprising an element belonging to Group VIII of the periodic table or compounds thereof carried on said carrier and a process for producing unsaturated esters characterized by the use of said catalyst. The use of the above catalyst markedly increase the space time yield of the obtained unsaturated esters.

Abstract: Disclosed are catalyst compositions comprising (i) one or more palladium group metals and/or compounds thereof; (ii) gold and/or compounds thereof; and (iii) optionally, an effective amount of one or more promoters selected from the group consisting of copper, nickel, cobalt, iron, manganese, lead, silver and compounds thereof. Preferably these catalyst compositions contain one or more promoters wherein the gram ratio of metal in the promoter to palladium group metal is up to about 0.4, wherein the catalysts are deposited on a support material and said support material is treated with one or more alkali metal bases and one or more alkali metal silicates prior to said deposition.Also described are processes for preparing ethylenically unsaturated esters comprising reacting in the vapor phase at least one olefinic compound with at least one carboxylic organic acid and molecular oxygen in the presence of an effective amount of the foregoing catalyst compositions.

Abstract: This invention provides a process for producing improved catalysts for the production of alkenyl alkanoates by the reaction of an alkene, an alkanoic acid and an oxygen-containing gas. The catalysts contain palladium, gold and a potassium promoter and are characterized by a reduced sodium content which results in increased catalyst activity. The reduced sodium content is obtained by washing the catalyst, at a particular intermediate point in its production, with a cation exchange solution.

Abstract: A method for pretreatment of a palladium-gold catalyst useful in the synthesis of vinyl acetate. A virgin catalyst, following reduction to the metallic palladium and gold, is first heated at elevated temperatures in the presence of an oxidizing agent such as air. The oxidizing agent is withdrawn and an inert gas such as nitrogen is introduced. The catalyst is heated again at a temperature up to 500.degree. C. in the presence of a reducing agent such as hydrogen or ethylene. Improvements in selectivity and yield are obtained.

Abstract: The invention relates to a process for the preparation of a catalyst which contains palladium and/or compounds thereof and alkali metal compounds, and additionally cadmium compounds and/or gold and/or compounds thereof, on support particles which have been pressed from SiO.sub.2 or an iO.sub.2 -Al.sub.2 O.sub.3 mixture with the aid of a binder which comprisesa) washing the roasted support particles with an acid which does not react with SiO.sub.2 or SiO.sub.2 -Al.sub.2 O.sub.3 mixtures, until no further cations of the binder employed during pressing of the support particles are released from the support particles;b) then impregnating the support particles with palladium, and gold or cadmium;c) then bringing the impregnated support particles into contact with a solution of a base at least until the thickness of the nobel metal shell generated in this way on the support particles no longer changes substantially; andd) then impregnating the support particles with an alkali metal compound.

Abstract: A shell impregnated catalyst for use in the production of vinyl acetate from ethylene, acetic acid and an oxygen containing gas is provided. The catalyst has a productivity of greater than 661 grams of vinyl acetate per hour per liter of catalyst at 150.degree. C. and consists essentially of:(1) a catalyst support having a particle diameter from about 3 to about 7 mm and a pore volume of 0.2 to 1.5 ml per gram(2) palladium and gold distributed in the outermost 1.0 mm thick layer of the catalyst support particles, and(3) from about 3.5 to 9.5% by weight of potassium acetate.The catalyst is characterised by having a gold to palladium weight ratio in the range 0.60 to 1.25.

Abstract: This invention provides a process for producing improved catalysts for the production of alkenyl alkanoates by the reaction of an alkene, an alkanoic acid and an oxygen-containing gas. The catalysts contain palladium, gold and a potassium promoter and are characterized by a reduced sodium content which results in increased catalyst activity. The reduced sodium content is obtained by washing the catalyst with water or with an aqueous solution of a potassium promoter after it has been impregnated with a potassium promoter.

Abstract: A lower fatty acid ester such as ethyl acetate or ethyl acrylate is prepared by a process in which a lower fatty acid such as acetic acid or acrylic acid is reacted with a lower olefin such as ethylene by using as solid catalyst a heteropoly-acid or its salt. The esterification is carried out in gaseous phase.

Abstract: A shell impregnated catalyst for use in the production of vinyl acetate from ethylene, acetic acid and an oxygen containing gas is provided. The catalyst has a productivity of greater than 661 grams of vinyl acetate per hour per liter of catalyst at 150.degree. C. and consists essentially of:(1) a catalyst support having a particle diameter from about 3 to about 7 mm and a pore volume of 0.2 to 1.5 ml per gram(2) palladium and gold distributed in the outermost 1.0 mm thick layer of the catalyst support particles, and(3) from about 3.5 to 9.5% by weight of potassium acetate.The catalyst is characterized by having a gold to palladium weight ratio in the range 0.60 to 1.25.

Abstract: This invention provides a process for producing improved catalysts for the production of alkenyl alkanoates by the reaction of an alkene, an alkanoic acid and an oxygen-containing gas. The catalysts contain palladium, gold and a potassium promoter and are characterized by a reduced sodium content which results in increased catalyst activity. The reduced sodium content is obtained by using essentially sodium-free starting materials in the process for producing the catalysts.

Abstract: This invention provides a process for producing improved catalysts for the production of alkenyl alkanoates by the reaction of an alkene, an alkanoic acid and an oxygen-containing gas. The catalysts contain palladium, gold and a potassium promoter and are characterized by a reduced sodium content which results in increased catalyst activity. The reduced sodium content is obtained by washing the catalyst, at a particular intermediate point in its production, with a cation exchange solution.

Abstract: A catalyst prepared by (a) impregnating a catalyst carrier with an aqueous solution of a palladium salt and a salt of at least one metal selected from the group consisting of copper, lead, ruthenium and rhenium in an amount corresponding to 90 to 95% of the water absorption of the carrier, (b) treating the impregnated carrier with an aqueous solution of an alkali metal salt in an amount corresponding to 120 to 500% of the water absorption of the carrier to precipitate water-insoluble compounds of palladium and at least one metal selected from the group consisting of copper, lead, ruthenium and rhenium on the carrier, (c) treating the metal compounds-deposited carrier with a reducing agent to convert the compounds to the corresponding metals, and (d) further supporting an alkali metal acetate on the carrier, had a high catalytic activity for the reaction of forming allyl acetate by reacting propylene, acetic acid and oxygen in the gas phase, and the selectivity to allyl acetate is very high and the life of thi

Abstract: The invention relates to a process for the preparation of vinyl acetate in the gas phase from ethylene, acetic acid and oxygen or oxygen-containing gases on a catalyst which contains palladium and/or compounds thereof and if appropriate additionally gold and/or gold compounds and, as activators, alkali metal compounds and if appropriate additionally cadmium compounds, on a support. The support consists of cylindrical particles with curved front faces. The support material is aerogenic SiO.sub.2 or an aerogenic SiO.sub.2 -Al.sub.2 O.sub.3 mixture having a surface area of 50-250 m.sup.2 /g and a pore volume of 0.4-1.2 ml/g, which is formed to the extent of at least 50% by pores having a diameter of 50-200 .ANG..

Abstract: The invention relates to the use of metal cation-exchangeable layered clays in organic reactions which are catalysed by protons in which intercalated water is not a stoichiometric reactant. Such organic reactions include the production of esters by the reaction of an olefin or an olefin oxide with a carboxylic acid, the production of ethers by reaction of an alcohol with an olefin or an olefin oxide, the production of ethers by the reaction of a primary or secondary aliphatic alcohol or an olefin oxide, the production of bis-sec-alkyl ethers from alkenes, the production of alkyl aromatic compounds by the reaction of an aromatic hydrocarbon with an olefin or alcohol and the production of alcohols by the hydration of olefins.

Abstract: Unsaturated esters of carboxylic acids are prepared by reacting olefines or cycloolefines with carboxylic acids and oxygen in the gaseous phase in the presence of a catalyst containing noble metal salts or noble metals of the VIII.sup.th group of the Periodic System and alcali metal salts and/or alcaline earth metal salts, as activators the content of noble metal being in the range of from 1.2 to 5% by weight and the proportion of the metal fraction of each individual activator to the noble metal content being in the range of from 0.5 to 1 to 3:1.

Abstract: A process for the production of an ester comprises reacting an olefin with carbon monoxide, hydrogen and another ester at elevated temperature and pressure in the presence of a catalyst comprising (1) a rhodium source, (2) a ruthenium source, and (3) cobalt or zinc iodide. The product ester comprises the acid group of the ester used as reactant esterified with a hydrocarbyl group derived from the olefin, hydrogen and carbon monoxide.

Abstract: A process and catalyst for the acetoxylation of propylene, said catalyst consisting essentially of palladium, bismuth, potassium, and rubidium.

Abstract: A process and catalyst for the acetoxylation of propylene, said catalyst consisting essentially of palladium, bismuth, and rubidium on a support.

Abstract: A process for providing high space time yields in the acetoxylation of propylene involving the use of a catalyst consisting esssentially of palladium, potassium, bismuth, and a promoting amount of magnesium or a combination of magnesium and barium.

Abstract: A process for producing an allyl carboxylate comprising the step of reacting propylene, oxygen or oxygen-containing gas, and a lower saturated carboxylic acid in the presence of a catalyst at a temperature of 100.degree. C. to 300.degree. C. and a pressure of 0 to 30 atm (gauge) in a vapor phase. The catalyst is prepared by supporting, on a carrier, at least one alkali metal acetate and at least one bivalent palladium salt in the presence of: (A) at least one organic base selected from the group consisting of (i) aliphatic amines having the formula: ##STR1## wherein R.sup.1, R.sup.2, and R.sup.3 may be the same or different and represent hydrogen, or an alkyl group having 1 to 10 carbon atoms or benzyl group optionally substituted with --CN, --OR, --COOR, or a --N(R).sub.2 group wherein R is H or an alkyl group having 1 to 3 carbon atoms, or any two groups of R.sup.1, R.sup.2, and R.sup.3 may together form a ring provided that R.sup.1, R.sup.2, and R.sup.

Abstract: A process for providing high space time yields in the acetoxylation of propylene involving the use of a catalyst consisting essentially of palladium, potassium, bismuth, and a promoting amount of magnesium or a combination of magnesium and barium.