摘要:
An industrial preparation of aldehydes and/or alcohols from olefins of more than 3 carbon atoms by a catalytic hydroformylation of the olefin reactant at a pressure of from 50 to 1000 bar and a temperature of from 50 to 180.degree. C. in the presence of an uncomplexed rhodium catalyst homogeneously dissolved in the reaction medium. The catalytic activity of the rhodium is maintained, first by extracting it from the initially discharged reaction mixture by means of an aqueous solution of a nitrogen-containing complexing agent such as sulfonated or carboxylated pyridines, quinolines or the like. In a recycle of the complexed rhodium to be reused in the hydroformylation reaction, the aqueous rhodium-containing extract is fed to a precarbonylation stage where it subjected to a required precarbonylation in the presence of an essentially water-insoluble organic liquid and in the presence of carbon monoxide, synthesis gas or another gas mixture containing carbon monoxide at from 50 to 1000 bar and from 50 to 180.degree. C. The mixture discharged from this precarbonylation stage is then separated into an organic phase containing the main part of the rhodium and an aqueous phase containing the complexing agent. The resulting rhodium-containing organic phase with the regenerated catalyst is then fed into the hydroformylation stage to complete its recycle.
摘要:
A process for the preparation of aldehydes or aldehydes and alcohols by hydroformylation of olefins containing more than 3 carbon atoms comprising a hydroformylation stage, in which the olefin is hydroformylated under a pressure of from 50 to 1000 bar and at a temperature of from 50.degree. to 180.degree. C. using a rhodium catalyst that is dissolved in a homogeneous reaction medium and by extraction of the rhodium catalyst, in whicha) the hydroformylation is carried out in the presence of a rhodium complex, which exhibits, as ligand, a polydentate, organic nitrogen compound that is free from phosphorus and capable of forming complexes with Group VIII metals, which additionally contains at least one tertiary nitrogen radical that is capable of being protonized by a weak acid,b) the effluent of the hydroformylation stage is subjected to extraction with an aqueous solution of a distillable acid optionally following separation or partial separation of aldehydes and alcohols,(c) the aqueous acid extract is subjected to thermal treatment in the presence of an organic solvent or solvent mixture, which is inert under the hydroformylation conditions, with distillation of the aqueous acid, by means of which treatment the complex is deprotonized and transferred to the organic phase, and(d) the organic phase containing the catalyst complex is recycled to the hydroformylation stage.
摘要:
Aldehydes with a higher number of carbon atoms and high selection are prepared by reacting olefins, in particular from petrochemical refinery products, by a hydroformylation with aldol condensation using a mixed catalyst of rhodium-carbonyl-phosphines and Mannich catalyst.
摘要:
Phosphorus-containing calixarenes of the general formula I ##STR1## and a process for their preparation are described. Additionally, a process for the preparation of aldehydes by the hydroformylation of C.sub.3 -C.sub.20 -olefins by means of rhodium or ruthenium carbonyl complexes, in which the phosphorus-containing calixarenes of the formula I are used as ligands, is described.
摘要:
Aldehydes or aldehydes and alcohols are prepared by hydroformylation of olefins of more than 3 carbon atoms by a process comprising the stage of hydroformylation by means of a rhodium catalyst homogeneously dissolved in the reaction medium, the separation of the rhodium catalyst from the discharge from the hydroformylation reaction and the recycling of the rhodium separated from the hydroformylation discharge to the hydroformylation stage, wherein the rhodium catalyst is extracted from the hydroformylation discharge into the aqueous phase by means of an aqueous solution of a water-soluble, phosphorus-containing complexing agent selected from the group consisting of the mono- or polysulfonated mono- and oligophosphines and/or from the group consisting of the mono- or polycarboxylated mono- or oligophosphines or the mono- or polysulfonated oligophosphites and the aldehyde or the aldehyde and the alcohol are isolated from the extracted hydroformylation discharge, the aqueous rhodium-containing extract is fed to a precarbonylation stage and is subjected to a precarbonylation in the precarbonylation stage in the presence of an essentially water-insoluble, organic liquid and in the presence of carbon monoxide or of a carbon monoxide-containing gas mixture.
摘要:
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, 2,2'-biquinolines, 2,2',6',2"-terpyridines and porphines, and the aqueous, rhodium-containing extract is recycled into the hydroformylation step.
摘要:
A process for the preparation of aldehydes or aldehydes and alcohols by hydroformylation of olefins containing more than 3 carbon atoms, comprising a hydroformylation stage, in which the olefin is hydroformylated under a pressure of form 50 to 1000 bar and at a temperature of from 50° to 180° C. by means of a rhodium catalyst dissolved in a homogenous reaction medium and a catalyst recovery stage comprising extraction of the rhodium catalyst with an aqueous solution of chelating agent, isolation of alcohols and/or aldehyde from the extracted hydroformylation product steam, precarbonylation of the aqueous rhodium-containing extract in the presence of carbon monoxide, synthesis gas as, or a gas mixture containing carbon monoxide under a pressure of from 50 to 1000 bar and at a temperature of from 50° to 180° C., separation of the effluent of the precarbonylation stage into an organic phase containing the major portion of the rhodium and an aqueous phase containing the chelating agent and recycling of the organic phase to the hydroformylation stage, where the rhodium catalyst is extracted from the effluent of the hydroformylation stage using an aqueous solution of a sulfonic acid group-free, water-soluble polymer capable of chelating rhodium.
摘要:
Manufacture of 6-aminocapronitrile or 6-aminocapronitrile/hexamethylene diamine mixtures, involving a) the reaction of at least one pentennitrile, selected from the group consisting of 2,3 and 4-pentennitrile with carbon monoxide and hydrogen in the presence of catalysts, which contain at least one element of the eighth subgroup as active components, obtaining a hydrogenation formylating discharge (I), b) the optional separation of carbon monoxide, hydrogen and the catalyst from the hydrogenation formylating discharge (I), obtaining a hydrogenation formylating discharge (II), c) the separation of 5-formyl valeronitrile from the hydrogenation formylating discharge (I) or (II), d) the reaction of separated 5-formyl valeronitrile with ammonia and hydrogen in the presence of hydrogenating catalysts, selected from the group consisting of rhenium, copper and its compounds as well as metals and metallic compounds of the eighth group, obtaining a hydrogenation discharge, and e) obtaining 6-aminocapronitrile and if necessary hexamethylene diamine.
摘要:
A process for the preparation of n-butyraldehyde and/or n-butanol, wherein a) 1,3-butadiene is caused to react with an alcohol of the formula I ROH I, to form a mixture of adducts of the formulas II ##STR1## and III ##STR2## b) the adduct III is isomerized to the adduct II, c) the adduct II is isomerized in the presence of a homogeneous or heterogeneous transition metal element catalyst to form the enol ether of the formula IV ##STR3## and d) n-butyraldehyde and/or n-butanol is/are produced from this ether IV by the reaction thereof with hydrogen and water or water only in the presence of a homogeneous or heterogeneous catalyst.
摘要:
A process for the preparation of n-butyraldehyde and/or n-butanol, in whicha) 1,3-butadiene is caused to react with an amine of the formula IR.sup.1 R.sup.2 NH, I in which R.sup.1 and R.sup.2 independently denote hydrogen, optionally substituted aliphatic or cycloaliphatic radicals, or aryl or aralkyl radicals or are linked to form a bridging member which can contain hetero atoms, at elevated temperature and under superatmospheric pressure in the presence of a compound of a Group VIIIb element and in the presence of an alkali metal amide or a basic metal oxide to form a mixture of the adducts of the formulas II ##STR1## and III ##STR2## b) the adduct III is isomerized to the adduct II, c) the adduct II is isomerized in the presence of a homogeneous or heterogeneous transition metal element catalyst in the liquid phase or in the presence of a heterogeneous catalyst containing a transition metal element in the gaseous phase to form the enamine of the formula IV ##STR3## and d) n-butyraldehyde and/or n-butanol is/are produced from this enamine.