Abstract: This invention relates to a process for the separation of a metal complex catalyst and any free ligand which may be present, from a homogeneous organic synthesis reaction mixture using sub-nanoporous, chemically stable membranes having discrete pores which allow organic products and by-products to pass through the membrane as permeate while retaining substantially all of the metal complex catalyst and free ligand, if any, as retentate.

Abstract: A process for the manufacture of citral is provided by the catalyzed rearrangement of dehydrolinalool to citral. The rearrangement is carried out in the presence of a molybdenum compound of the general formula MoO2X2 wherein X signifies an acetylacetonate or halide ion, and a dialkyl or diaryl sulphoxide as the catalyst system, in the presence of an organic acid having a pK value in the range of about 4.0 to about 6.5 and in an apolar aprotic organic solvent.

Abstract: A process for producing a brightness stabilization mixture of water-soluble organic compounds from biomass pyrolysis oils comprising: a) size-reducing biomass material and pyrolyzing the size-reduced biomass material in a fluidized bed reactor; b) separating a char/ash component while maintaining char-pot temperatures to avoid condensation of pyrolysis vapors; c) condensing pyrolysis gases and vapors, and recovering pyrolysis oils by mixing the oils with acetone to obtain an oil-acetone mixture; d) evaporating acetone and recovering pyrolysis oils; e) extracting the pyrolysis oils with water to obtain a water extract; f) slurrying the water extract with carbon while stirring, and filtering the slurry to obtain a colorless filtrate; g) cooling the solution and stabilizing the solution against thermally-induced gelling and solidification by extraction with ethyl acetate to form an aqueous phase lower layer and an organic phase upper layer; h) discarding the upper organic layer and extracting the aqueous

Abstract: A process for the manufacture of dihydrocitral, a valuable intermediate, through the catalyzed rearrangement of dihydrodehydrolinalool by carrying out the rearrangement in the presence of a molybdenum compound of the general formula MoO2X2 wherein X signifies an acetylacetonate or halide ion, and a dialkyl or diaryl sulphoxide as the catalyst system, in the presence of an organic acid having a pK value in the range of about 4.0 to about 6.5 and in an aprotic organic solvent.

Abstract: A method of stabilizing aliphatic C.sub.3 -C.sub.14 -aldehydes against polymerization and autocondensation by the addition of alkaline substances to the aldehydes wherein the alkaline substances used are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates or alkali metal carboxylates which are added to the aldehyde to be stabilized in amounts of 0.05-20 ppm, based on the aldehyde.

Abstract: The invention is directed toward preparation of (meth)acrylic acid, comprising condensation of a gas comprising (meth)acrylic acid, absorption with water, and extraction with an aqueous solution forming a miscibility gap.

Abstract: 3-Methyl-2-pentenal cannot be separated from 1-butanol by conventional rectification because of the proximity of their boiling points. 3-methyl-2-pentenal can be readily separated from n-butanol by azeotropic distillation. Effective agents are dimethoxymethane, petroleum ether and tetramethylortho-silicate.

Abstract: 3-Methyl-2-pentenal cannot be separated from n-butanol by conventioal rectification because of the proximity of their boiling points. 3-methyl-2-pentenal can be readily separated from n-butanol by extractive distillation. Effective agents are 1-methyl-2-pyrrolidinone, 1,4-butanediol and phenol.

Abstract: A method for producing butyraldehydes, by separating and purifying mixed butyraldehyde products formed by hydroformylation of propylene, into n-butyraldehyde and isobutyraldehyde by using a distillation column, wherein the distillation column is operated under such conditions that the pressure at the top of the distillation column is within a range of from 0.001 to 0.5 kg/cm.sup.2 G, and the pressure at the bottom of the column is within a range of from 0.05 to 1.0 kg/cm.sup.2 G.

Abstract: A process for removing acrolein from a gaseous or liquid mixture, in one case aqueous solutions, involving contacting the mixture with a compound selected from the group consisting of sodium hypochlorite; an acid salt of hydroxylamine; a urea compound such as urea itself or thiourea; sodium bisulfite and 4,4-dimethyl-1-oxa-3-azacyclopentane in an amount effective to substantially remove acrolein has been discovered. The process works particularly well in selectively scavenging acrolein from aqueous solutions containing acrylonitrile.

Abstract: A process for the condensation of an aldehyde with hydrogen cyanide in the presence of a buffer is disclosed. The buffer advantageously allows the condensation reaction to occur at a pH equal to or above 4.0 and in the absence of amines.

Abstract: The present invention provides a hydroformylation process comprising: (1) forming a reaction mixture containing: (a) an olefinic compound, (b) hydrogen, (c) carbon monoxide, (d) a phosphite in which each phosphorus atom is bonded to three oxygen atoms and at least one such oxygen atom is bonded to a carbon atom of an aromatic ring that is adjacent to another carbon atom of said ring having a pendant monovalent group having a steric hindrance at least as great as the steric hindrance of the isopropyl group, (e) a catalytic amount of rhodium, and (f) a Group VIII metal (other than a rhodium) in an amount sufficient to reduce the rhodium-catalyzed decomposition of the phosphite during the hydroformylation process; and (2) maintaining the reaction mixture under conditions at which the olefinic compound reacts with the hydrogen and carbon monoxide to form an aldehyde.

Abstract: Butyraldehyde cannot be separated from ethanol by conventional distillation or rectification because they form a minimum boiling azeotrope. Butyraldehyde can be readily separated from ethanol by extractive distillation. Effective agents are 2-propanol, m-xylene and dimethylsulfoxide.

Abstract: Disclosed herein is a process for removing acrolein from a gaseous or liquid mixture, in one case aqueous solutions, involving contacting the mixture with a compound selected from the group consisting of sodium hypochlorite; an acid salt of hydroxylamine; a urea compound such as urea itself or thiourea; sodium bisulfite and 4,4-dimethyl-1-oxa-3-azacyclopentane in an amount effective to substantially remove acrolein has been discovered. The process works particularly well in selectively scavenging acrolein from aqueous solutions containing acrylonitrile.

Abstract: Butyraldehyde cannot be separated from ethanol by conventional distillation or rectification because they form a minimum boiling azeotrope. Butyraldehyde can be readily separated from ethanol by azeotropic distillation. Effective agents are ethyl formate, hexane and isopropyl ether.

Abstract: An improved process for azeotropic distillation of chloral to anhydrous chloral containing as little as 0.1% water. An azeotropic mixture is used which contains chloral in at least a 1.4:1 ratio with the concentration (% of weight) of a azeotropic agent (preferably ethylene dichloride). The feed stream may contain other components, but will contain at least 60% chloral and less than 40% water. Preferably, the feed stream is substantially free of components other than choral and water. Water is removed from the overhead product of the azeotropic and EDC separation distillations periodically or continuously throughout the process. The azeotropic agent is preferably separated from the anhydrous chloral product. This separation may be performed in the azeotropic distillation column or in a separate distillation column.

Abstract: In a process for producing acetic anhydride and acetic acid by reacting methanol and methyl acetate, optionally together with dimethyl ether, with carbon monoxide, acetic anhydride and acetic acid are effectively produced with the use of a sequence of production facilities by carrying out separation of low-boiling point fraction mainly consisting of methyl iodide, methyl acetate and dimethyl ether with the use of at least two distillation zones, separating catalyst drops entrained from the vapor-liquid separation zone in at least one distillation zone and further by controlling the pressurization of the vapor-liquid separation zone and the above distillation zones under 5 bar to a pressure greater than atmospheric pressure.

Abstract: Disclosed is a process for the removal of crotonaldehyde impurity from cyclopropanecarboxaldehyde by the selective, catalytic hydrogenation of crotonaldehyde to butyraldehyde followed by distillation of the butyraldehyde from the cyclopropanecarboxaldehyde.

Abstract: A propylene stream which contains propane as an impurity is contacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst thereby producing a product stream containing butyraldehyde and/or n-butyl alcohol, unreacted propylene and propane. A gas mixture containing propylene and propane is separated from the product stream and subjected to adsorption at a temperature of 0.degree. to 250.degree. C. in a bed of adsorbent which selectively adsorbs propylene, thereby adsorbing substantially all of the propylene from the gas mixture. The propylene is desorbed from the adsorbent and recycled to the reaction zone. The process is operated on a low per pass conversion with recycle of unreacted propylene. In the system of the invention the propylene adsorption unit may be upstream or downstream of the hydroformylation reactor.

Abstract: A method for starting a preformer reactor disposed within a hydroformylation system which comprises an oxo reactor, a stripper reactor and a preformer reactor, wherein the bottoms from the stripper reactor comprise at least a water soluble cobaltous salt and wherein the overhead from the stripper reactor comprises entrained volatile cobalt compounds, wherein at least a portion of the entrained volatile cobalt compounds from the stripper reactor are recycled to the preformer reactor to act an initiator in the conversion of the cobaltous salt to cobalt carbonyl.

Abstract: A process for producing dichloroacetaldehyde hydrate together with chloral from acetaldehyde or para-aldehyde. The process comprises a step of chlorinating acetaldehyde or para-aldehyde to obtain a chlorinated solution containing dichloroacetaldehyde as a major component, a step of distilling this chlorinated solution to obtain a distillate having a boiling point of 90.degree.-100.degree. C. and containing 50% or more of dichloroacetaldehyde, a step of adding water to this distillate, crystallizing dichloroacetaldehyde hydrate, and separating the crystals, and a step of chlorinating the remaining aldehyde components into chloral. The process enables dichloroacetaldehyde hydrate to be separated at a high purity and the raw materials to be utilized efficiently.

Abstract: A method for removing cobalt values from the crude product of a cobalt-catalyzed hydroformylation reaction by the application of an airless cobalt demetalling step upstream of the stripping step of a Cobalt Flash hydroformylation catalyst recovery process for C.sub.4 to C.sub.14 olefins, whereby no oxygen is required to oxidize cobalt carbonyls to their cobaltous form. This airless demetalling step may also be used downstream of the stripping step in the case of C.sub.7 to C.sub.20 olefins to remove carbonyls from a water soluble cobaltous salt and carbon carbonyl stream which is taken as bottoms from the stripper reactor.

Abstract: Carbonaceous preformer catalysts used to convert cobalt salts to hydrido cobalt carbonyl for use in the oxonation of olefins are activated or regenerated by treatment with an aqueous cobalt salt solution in the presence of a light alcohol having from about 4 to 7 carbon atoms and syn gas prior to exposure to or processing with any other organic stream at a temperature of about 120.degree. C. to 190.degree. C. and a pressure of about 13 MPa to 32 MPa for about 2 to 50 hours.

Abstract: A catalyst for use in hydroformylation of olefins which comprises a Group VIII noble metal complexed with a phosphine ligand having at least one alkyl or aryl group bonded thereto, such as tris-4-propylphenyl phosphines and tris-4-octylphenyl phosphines. These and other triphenylphosphine catalysts can be separated from a crude reaction product of a noble metal-catalyzed hydroformylation reaction by contacting the crude reaction product with a dense polymeric, nonpolar membrane, preferably nonpolar polyolefin membranes.

Abstract: A process for the preparation of aldehydes by hydroformylation of olefins having more than 7 carbon atoms, comprising hydroformylation by means of a rhodium catalyst dissolved homogeneously in the reaction medium, removal of the rhodium catalyst from the hydroformylation reaction product, and recycling of the rhodium separated off from the hydroformylation product into the hydroformylation step, in which the rhodium catalyst is extracted from the hydroformylation product into the aqueous phase by means of an aqueous solution of a nitrogen-containing complexing agent from the group comprising of sulfonated pyridines, sulfonated quinolines, substituted or unsubstituted, sulfonated or sulfonated substituent-carrying 2,2'-bipyridines, 1,10-phenanthrolines, 2,2'-biquinolines, 2,2',6',2"-terpyridines and porphines, and/or from the group comprising of carboxylated pyridines, carboxylated quinolines, substituted or unsubstituted, carboxylated or carboxylated substituent-carrying 2,2'-bipyridines, 1,10-phenanthrolines

Abstract: A process for isolating 4-hydroxybutanal and 3-hydroxy-2-methylpropanal from aqueous mixtures of the isomers is disclosed. Reaction of the aqueous mixture with a hydroxy compound in the presence of an acidic catalyst and a nonpolar organic solvent gives a product aqueous solution of 3-hydroxy-2-methylpropanal and an organic solution containing a 2-oxytetrahydrofuran derived from 4-hydroxybutanal. The 4-hydroxybutanal can be regenerated by acidic hydrolysis of the 2-oxytetrahydrofuran.

Abstract: An apparatus for removing cobalt values from the crude product of a cobalt-catalyzed hydroformylation reaction wherein an overhead stripper-reactor reflux product is recycled to a location on the stripper-reactor which is capable of forming a stripping zone in the upper portion of the stripper-reactor and a reaction zone in the lower portion of the stripper-reactor.

Abstract: A process for producing acrolein which comprises bringing a reaction gas resulting from a catalytic oxidation of propylene into contact in a cooling tower with a condensate which is being circulated through the cooling tower and a circulating part, thereby to cool and separate the reaction gas and discharge an effluent gas from the cooling tower, the condensate in a bottom part of the cooling tower having a temperature of from 35.degree. to 50.degree. C., the effluent gas discharged from the cooling tower having a temperature of from 35.degree. to 55.degree. C.

Abstract: A method for separating a noble metal catalyst from a crude reaction product of a noble metal-catalyzed hydroformylation reaction which comprises: (a) contacting the crude reaction product under perstraction conditions with a membrane capable of allowing a substantial portion of unreacted olefin feed and hydroformylation reaction product to pass therethrough as permeate while retaining a substantial portion of the catalyst as retentate; (b) removing the permeate by sweeping it away from the membrane by means of a sweep stream which is the same as the olefin feed used in the hydroformylation reaction; and (c) retaining the catalyst as retentate.

Abstract: An improved allyl alcohol hydroformylation process and catalyst are disclosed. The process uses a catalyst system comprising a Group VIII metal carbonyl complex catalyst, a trisubstituted phosphine, a neutral Group VIII(a) metal complex cocatalyst, and optionally, a diphosphinoalkane. The process uniquely gives an enhanced linear:branched aldehyde product ratio.

Abstract: A process for separating and recovering rhodium from oxo synthesis products comprising extracting under pressure an oxo synthesis product containing rhodium with an aqueous solution of a complexing organic phosphine to obtain a solution of a water-soluble phosphine substituted rhodium carbonyl compound.

Abstract: This invention provides a process for producing crystalline hydroxyacetaldehyde precipitated from a complex mixture of products provided by the pyrolysis of a carbohydrate-containing feedstock. The method includes distilling a first condensate under reduced pressure to give a second condensate which is enriched in hydroxyacetaldehyde; combining the second condensate with a solvent to give a homogeneous solution; precipitating hydroxyacetaldehyde from the solution; and separating the precipitated hydroxyacetaldehyde from the solution.Aqueous solutions of hydroxyacetaldehyde are useful for browning foodstuffs and for producing flavors by contacting the hydroxyacetaldehyde with ammonia or amines.In addition, hydroxyacetaldehyde may be used to make an artificial tanning product containing a suitable topical vehicle and an amount of hydroxyacetaldehyde suitable to impart a brown color to skin.

Abstract: A method for removing cobalt values from the crude product of a cobalt-catalyzed hydroformylation reaction which utilizes the same equipment in two different operating sequences to accommodate olefinic feedstocks having a wide range of carbon numbers. Olefinic feedstocks having a carbon number in the range C.sub.4 -C.sub.14, more preferably C.sub.5 -C.sub.7, can be decobalted by the application of an acid-air cobalt demetalling step upstream of the stripping step of a Cobalt Flash hydroformylation catalyst recovery process; whereas C.sub.7 to C.sub.20 olefinic feedstocks, more preferably C.sub.8 -C.sub.14, can be decobalted by application of the acid-air cobalt demetalling step downstream of the stripping step.

Abstract: A method for removing cobalt values from the crude product of a cobalt-catalyzed hydroformylation reaction wherein an overhead stripper-reactor reflux product is recycled to a location on the stripper-reactor which is capable of forming a stripping zone in the upper portion of the stripper-reactor and a reaction zone in the lower portion of the stripper-reactor.

Abstract: The present invention provides a process for producing 2-ethylhexanol having a reduced concentration of 2-ethyl-4-methyl pentanol. It may be practiced in its most basic form as a distillation. It may also be practiced as part of a multi-stage continuous process. In either form it begins with a feed stream comprising n-butyraldehyde containing as a contaminant, isobutyraldehyde, complexes of isobutyraldehyde, oligomers of isobutyraldehyde and mixtures thereof, to which is added or introduced, an amount of water effective to hydrolyze the oligomeric contaminants to the monomeric form of isobutyraldehyde during distillation. The water containing aldehyde mixture is introduced to a distillation zone with a residence time and at a temperature sufficient to hydrolyze the oligomeric contaminants to and then distill substantially all of the isobutyraldehyde overhead.

Abstract: A process for recovering a Group VIII metal from an organic solution is disclosed. The organic solution is contacted with an acidic ion exchange resin that has sulfonic acid active groups. The invention provides an effective and economical way to recover valuable transition metals from dilute organic solutions.

Abstract: This invention relates to a process for separating an aldehyde that contains at least seven carbon atoms and that is free of alpha substituents from a solution containing the aldehyde and a non-polar organic liquid which process comprises contacting the solution with water under conditions such that a solid hydrate of the aldehyde forms and separating the solid hydrate from the solution. This invention also relates to novel hydrates so produced.

Abstract: A process for improving the catalytic activity of a partially deactivated solubilized rhodium - tertiary organophosphine complex hydroformylation catalyst.

Abstract: Process for the separation and recovery of aldehyde product from a non-aqueous hydroformylation reaction product composition comprising the aldehyde product, a rhodium-ionically charged phosphorus ligand complex, a free ionically charged phosphorus ligand and an organic solubilizing agent for said complex and said free ligand via phase separation using added water or both added water and an added non-polar hydrocarbon compounds.

Abstract: Disclosed is a continuous process for the manufacture of 2-ethyl-2-(hydroxymethyl)hexanal wherein 2-ethylhexanal, formaldehyde and a tertiary amine are continuously fed to a reaction zone and crude product comprising an aqueous phase and an organic phase containing 2-ethyl-2-(hydroxymethyl)hexanal and 2-ethylhexanal is continuously removed from the reaction zone. Also disclosed are processes for (1) the azeotropic distillation of the organic phase of the crude product whereby unreacted 2-ethylhexanal is recovered and (2) the catalytic hydrogenation of the refined, organic phase of the crude product to produce 2-butyl-2-ethyl-1,3-propanediol.

Abstract: Disclosed is an extraction process for the recovery of high-boiling aldehydes produced by the rhodium-catalyzed hydroformylation of olefins in the presence of a hydroformylation solvent. The extraction process involves intimately contacting a hydroformylation product solution comprising (i) a high-boiling aldehyde, (ii) hydroformylation catalyst components comprising rhodium and an organophosphine compound, and (iii) a hydroformylation solvent with an extraction solution comprising a primary alkanol and water to form a 2-phase mixture. The phases are separated to obtain a hydroformylation solvent phase containing catalyst components and an alkanol/water phase containing the high-boiling aldehyde.

Abstract: An improved rhodium catalyzed liquid recycle hydroformylation process, the improvement which comprises selectively separating and recovering phosphorus ligand from the vaporized aldehyde product stream obtained from volatilizing and separating the aldehyde product from the catalyst containing reaction product solution of the hydroformylation process.

Abstract: A method for distilling a crude aldehyde product mixture of branched chain and straight chain aldehyde in a single distillation column to concurrently obtain three separate product streams, i.e. a purified branched chain aldehyde stream and two different purified straight chain aldehyde streams.

Abstract: A process for dimerizing an aromatic halogen compound is disclosed, which comprises the step of: subjecting an aromatic halogen compound having at least one halogen atom bonded to an aromatic nucleus carbon to a dehalogenation-dimerization reaction in the presence of a catalyst, water, a reducing agent, and a halogen acceptor, the catalyst comprising a carrier supported thereon palladium and iron.

Abstract: A method is disclosed for enhancing the purification of citral by fractional distillation by inhibiting the formation of isocitrals from isomerization of citral during the distillation process. The method involves reducing the pH of a mixture containing citral to inhibit the formation of isocitrals from citral upon heating, such as in distillation. Lowering the pH below 7 reduces formation of isocitrals, but a pH of about 4 to 5 is especially preferred. Most preferably, this pH adjustment is accomplished by addition of an acid with a pKa between about 4 and 5.

Abstract: An improved liquid recycle rhodium-catalyzed hydroformylation process wherein the improvement comprises recovering unreacted olefin contained in a vent gas of the process and recycling said unreacted olefin to the hydroformylation reaction medium.

Abstract: A process for the separation of 2-methylalkanals from a mixture thereof with at least one alpha unbranched aldehyde thereof comprising distillation of said mixture in the presence of formaldehyde and an aldolization catalyst whereby the alpha unbranched aldehydes are converted to alpha alkylacrolein and the 2-methylalkanals are recovered in a high purity.

Abstract: Continuous process for hydroformylation of olefins containing, typically, from 6 to 20 carbon atoms to produce the corresponding aldehydes. The rate of formation of high boiling aldehyde condensation products is minimized by use of a high boiling inert solvent whose boiling point, at the pressure prevailing in the product recovery zone, lies intermediate between that of the highest boiling aldehyde product produced in the hydroformylation reaction and that of the ligand, as well as by maintaining the concentration of product aldehyde at or below a predetermined minor amount. In this way the length of a production run can be significantly extended before it becomes necessary to shut down the plant due to accumulation of high boiling aldehyde condensation products.

Abstract: Alkanals having a 2-alkyl branch are obtained from mixtures which contain the alkanals having a 2-alkyl branch in addition to n-alkanals, 3-alkylalkanals and/or further isomers by a process in whicha) the alkanal mixture is reacted with an aqueous formaldehyde solution in the presence of a secondary amine and of a carboxylic acid as a catalyst,b) the aqueous phase containing the catalyst and any unconverted excess formaldehyde is separated off andc) the alkanals having a 2-alkyl branch are isolated by distillation from the condensates of the other alkanals with formaldehyde.

Abstract: An improved process for the rhodium-catalyzed hydroformylation of olefins to aldehydes is described. The improvement provides a means for recovering valuable components in gaseous streams by scrubbing the streams with a stripped or cooled catalyst solution.