High temperature hydroformylation in the presence of triarylphosphine rhodium carbonyl hydride complex catalyst systems

A homogeneous liquid phase hydroformylation process which comprises selectively reacting a dissolved C.sub.2 -C.sub.40 1-n-olefin with CO and H.sub.2 at temperatures between about 120.degree. and 200.degree. C. and at a total pressure of 100 to 1500 psia to selectively produce n-aldehydes in the presence of a tris-triarylphosphine rhodium carbonyl hydride complex catalyst free from halogen on the rhodium wherein the homogeneous reaction medium comprises oxygenated solvents comprising mainly straight chain and mono-branched monohydric alcohols and aliphatic mono carboxylic acid alkyl esters and aldehyde acetals thereof, and branched aldehydes derived via aldol condensation and excess triarylphosphine ligand as a catalyst stabilizer modifier having a minimum of 1 mole per kg. phosphorus equivalent based on said reaction medium wherein the daily loss of catalyst activity is below 0.5%.

A concurrent homogeneous isomerization, hydroformylation process comprising isomerizing an internal linear olefin to a terminal C.sub.4 -C.sub.40 1-n-olefin and hydroformylating the 1-olefin component resulting from the isomerization in the presence of a tris-triarylphosphine rhodium carbonyl hydride complex catalyst free from halogen on the rhodium wherein the homogeneous reaction medium comprises oxygenated solvents comprising mainly straight chain and mono-branched monohydric alcohols and monocarboxylic acid alkyl esters and aldehyde acetals thereof and branched aldehydes derived via aldol condensation and excess triarylphosphine ligand as a catalyst modifier stabilizer having a minimum of 1 mole per kg. phosphorus equivalent based on said reaction medium and wherein the CO partial pressure is below 100 psia.

A continuous homogeneous liquid phase hydroformylation process which comprises reacting a dissolved C.sub.2 to C.sub.12 olefinic feed with CO and H.sub.2 at temperatures between about 120.degree. and 200.degree. C. and at a total pressure in the range of 100 to 1500 psia to selectively produce aldehydes in the presence of tris-triarylphosphine rhodium monocarbonyl hydride and bis-diarylphosphine rhodium dicarbonyl hydride complex catalyst free from halogen on the rhodium wherein homogeneous reaction medium comprise oxygenated solvents comprising mainly straight chain and monobranched monohydric alcohols and aliphatic monocarboxylic acid alkyl esters and aldehyde acetals thereof and branched aldehydes derived via aldol condensation and excess triarylphosphine ligand as a catalyst modifier stabilizer having a minimum of 1 mole per kg. phosphorus equivalent based on said reaction medium wherein the daily loss of catalyst activity is below 0.5% and continuously removing the products and unreacted reactants in the gas phase.

A continuous homogeneous liquid phase hydroformylation process comprising reacting a C.sub.4 to C.sub.12 n-1 olefinic feed with CO and H.sub.2 at temperatures between about 120.degree. and 200.degree. C. and at a total pressure of 100 to 1000 psia to selectively produce n-aldehydes in the presence of a tris-triarylphosphine rhodium carbonyl hydride complex catalyst free from halogen on the rhodium wherein said reaction medium comprises oxygenated solvents comprising mainly monohydric alcohols and mono carboxylic acid esters and acetals thereof and branched aldehydes and excess triaryl phosphine ligand as catalyst stabilizer modifier having 1 mole per kg. phosphorus equivalent based on said oxygenated solvent, continuously removing the products and unreacted reactants from said medium during the reaction in the gas phase, and recirculating H.sub.2 and CO in the substantial absence of product aldehyde.

A continuous homogeneous liquid phase hydroformylation process which comprises reacting a dissolved butene-1 feed with CO and H.sub.2 at temperatures between about 120.degree. and 160.degree. C., a total pressure in the range of 100 to 700 psia to selectively produce n-valeraldehyde in the presence of tris-triphenylphosphine rhodium carbonyl hydride complex catalyst free from halogen on the rhodium wherein the homogeneous reaction medium comprises oxygenated solvents containing amyl alcohol, amyl propylheptanoate, valeraldehyde diamyl acetal, propylheptanal, propylheptanol, and excess triarylphosphine ligand having a minimum of 1 mole per kg. phosphorus equivalent based on said reaction medium and wherein the daily loss of catalyst activity is below 0.5%, continuously introducing reactants into the liquid reaction medium, continuously removing aldehyde products and unreacted reactants in the gas phase, separating the products by condensation and recirculating H.sub.2 and CO in the substantial absence of aldehyde product.

A continuous homogeneous liquid phase hydroformylation process comprising reacting a C.sub.4 to C.sub.12 linear internal olefinic feed with CO and H.sub.2 at temperatures between about 120.degree. and 200.degree. C. and at a CO partial pressure above 100 psi and a total pressure not exceeding 1500 psia to selectively produce aldehydes in the presence of a bis-triarylphosphine rhodium dicarbonyl hydride complex catalyst free from halogen on the rhodium wherein the homogeneous reaction medium comprises oxygenated solvents comprising mainly straight chain and mono-branched monohydric alcohols and aliphatic monocarboxylic acid alkyl esters and aldehyde acetals and branched aldehydes which oxygenated solvents are derived via aldol condensation in said reaction medium and excess triarylphosphine ligand as catalyst stabilizer modifier having a minimum of 1 mole phosphorus equivalent per kg. of reaction medium and continuously removing the products and unreacted reactants in the gas phase.

A continuous homogeneous liquid phase hydroformylation process which comprises reacting a C.sub.4 to C.sub.12 olefinic feed comprising one or more unsymmetrically disubstituted ethylene reactants with CO and H.sub.2 at temperatures between about 120.degree. and 200.degree. C. and at a CO partial pressure in excess of 100 psia and a total pressure not exceeding 1500 psia to selectively produce terminal aldehydes in the presence of a bis-triarylphosphine rhodium dicarbonyl hydride complexed catalyst free from halogen on the rhodium wherein the homogeneous reaction medium comprises lower boiling oxygenated solvents comprising mainly straight chain and mono-branched monohydric alcohols and aliphatic mono-carboxylic acid alkyl esters and aldehyde acetals and branched aldehydes which oxygenated solvents are derived via aldol condensation in said reaction medium and excess triarylphosphine ligand as a catalyst stabilizer modifier having a minimum of 1 mole phosphorus equivalent per kg. of reaction medium.