Union Carbide Chemicals & Plastics Technology Corporation

Union Carbide Corporation

Union Carbide Chemicals and Plastics Company, Inc.

Davy Mckee (london) Limited

Union Carbide Chemicals & Technology LLC

David Robert Bryant

Ernst Billig

Anthony G Abatjoglou

John Michael Maher

James Clair Nicholson

John Robert Briggs

David James Miller

Thomas Carl Eisenschmid

John N Argyropoulos

Diane Lee Packett

Ailene Gardner Phillips

Jeffrey Scott Kanel

Donald Lee Morrison

Tak W Leung

Richard W Wegman

Brian Michael Roesch

Michael Leo Tulchinsky

Paul Foley

Kurt Damar Olson

Rex E Murray

Richard A Galley

Max Min Lee

James E Babin

James Russell Nelson

Kenneth Elwood Stockman

David James Schreck

Anthony J Papa

Wellington E Walker

Anil Sakharam Guram

John E Logsdon

Ronald R Peterson

Earle S Brown

Donald Leroy Bunning

Jackie D Jamerson

Bernard L Shaw

Kenneth L Hoy

Wei-Jun Peng

Erik Bruce Tjaden

Arnold M Harrison

Morteza Mokhtarzadeh

Barry Brent Fish

Jay Fingeret Miller

Nancy E Kinkade

Ernesto Vera-Castaneda

John Braithwaite

Elaine Susan Brigham

Donald J Weintritt, Jr

James C Nicholson

Rachel Hilda Zanapalidou

Bernard Leslie Shaw

Michael Carl Becker

Anthony George Abatjoglou

Johnathan Eugene Holladay

Eric Bruce Tjaden

John M Mather

Craig Alan Beasley

Diane A Montevideo

Michael David Warholic

Arthur Roy Doumaux, Jr

An improved hydroformylation process involving reacting one or more reactants, such as an olefin, with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst, to produce a reaction product fluid comprising one or more products, preferably aldehydes; wherein said process is conducted in a region of the hydroformylation rate curve that is negative or inverse order in carbon monoxide, which is sufficient to prevent and/or lessen deactivation of the hydroformylation catalyst; and wherein total pressure is controlled at a predetermined target value and/or vent flow rate is controlled at a predetermined target value, by adjusting a flow of a carbon-monoxide containing inlet gas, so as to prevent and/or lessen cycling of process parameters, e.g., reaction rate, total pressure, vent flow rate, and/or temperature.

Stabilization of a hydroformylation process

A novel organophosphorus composition and synthesis thereof, the composition being characterized by one phosphite moiety, one phosoxophite moiety, and a plurality of sterically bulky substituents. The novel composition finds utility as a ligand in Group VIII transition metal phosoxophite complex catalysts and complex catalyst precursors that are used in carbonylation processes, preferably, hydroformylation processes. Additionally, there is disclosed a novel method of preparing a phosphoromonochloridite composition that finds utility as a precursor to the novel phosoxophite composition.

Phosoxophite ligands and use thereof in carbonylation processes

This invention relates to a process for producing one or more organic acids in high purity which process comprises (i) oxidizing in a liquid oxidation reactor one or more organic liquids with essentially pure oxygen or oxygen-enriched air containing at least about 50% oxygen, at a temperature sufficiently stable to prevent cycling of reaction rate, to produce a crude reaction product fluid, and (ii) refining said crude reaction product fluid to give said one or more organic acids in high purity. The oxidation temperature is preferably controlled to within about &plusmn;3&deg; C. of a target temperature. The organic acids described herein is useful in a variety of applications, such as intermediates in the manufacture of chemical compounds, pharmaceutical manufacture and the like.

Preparation of organic acids

This invention relates to a process for separating one or more organophosphorus ligand degradation products, one or more reaction byproducts and one or more products from a continuously generated reaction product fluid comprising one or more unreacted reactants, a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more organophosphorus ligand degradation products, said one or more reaction byproducts, said one or more products, one or more polar solvents and one or more nonpolar solvents by phase separation wherein (i) the selectivity of the polar phase for the organophosphorus ligand with respect to the one or more products is expressed by a partition coefficient ratio Ef1 which is a value greater than about 2.5, (ii) the selectivity of the polar phase for the organophosphorus ligand with respect to the one or more organophosphorus ligand degradation products is expressed by a partition coefficient ratio Ef2 which is a value greater than about 2.5, and (iii) the selectivity of the polar phase for the organophosphorus ligand with respect to the one or more reaction byproducts is expressed by a partition coefficient ratio Ef,which is a value greater than about 2.5.

Separation processes

This invention relates to a process for separating one or more organophosphorus ligand degradation products, one or more reaction byproducts and one or more formylester products from a reaction product fluid comprising one or more unreacted unsaturated ester reactants, a metal-organophoshorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more organophosphorus ligand degradation products, said one or more reaction byproducts, said one or more products, a nonpolar solvent and a polar solvent by phase separation wherein (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more products is expressed by a partition coefficient ratio Ef1 which is a value greater than about 2.5 (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more organophosphorus ligand degradation products is expressed by a partition coefficient ratio Ef2 which is a value greater than about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more reaction byproducts is expressed by a partition coefficient ratio Ef3 which is a value greater than about 2.5.

Metal-ligand complex catalyzed processes

This invention relates to a process for separating one or more products from a reaction product fluid comprising a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more products, one or more nonpolar reaction solvents and one or more polar reaction solvents, in which said reaction product fluid exhibits phase behavior depicted by FIG.,, wherein said process comprises (1) supplying said reaction product fluid from a reaction zone to a separation zone, (2) controlling concentration of said one or more nonpolar reaction solvents and said one or more polar reaction solvents, temperature and pressure in said separation zone sufficient to obtain by phase separation two immiscible liquid phases depicted by regions,and,of FIG.,comprising a polar phase and a nonpolar phase and to prevent or minimize formation of three immiscible liquid phases depicted by region,of FIG.,and one homogeneous liquid phase depicted by regions,and,of FIG.,, and (3) recovering said polar phase from said nonpolar phase or said nonpolar phase from said polar phase.

This invention relates to a process for separating one or more organophosphorus ligand degradation products, one or more reaction byproducts and one or more products from a continuously generated reaction product fluid comprising one or more unreacted reactants, a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more organophosphorus ligand degradation products, said one or more reaction byproducts, said one or more products, one or more nonpolar solvents and one or more polar solvents by phase separation wherein (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more products is expressed by a partition coefficient ratio Ef1which is a value greater than about 2.5, (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more organophosphorus ligand degradation products is expressed by a partition coefficient ratio Ef2 which is a value greater than about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more reaction byproducts is expressed by a partition coefficient ratio Ef3 which is a value greater than about 2.5.

This invention relates to a process for separating one or more organophosphorus ligand degradation products, one or more reaction byproducts and one or more formylester products from a reaction product fluid comprising one or more unreacted unsaturated ester reactants, a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more organophosphorus ligand degradation products, said one or more reaction byproducts, said one or more products, a polar solvent and a nonpolar solvent by phase separation wherein(i) the selectivity of the polar phase for the organophosphorus ligand with respect to the one or more products is expressed by a partition coefficient ratio Ef1 which is a value greater than about 2.5, (ii) the selectivity of the polar phase for the organophosphorus ligand with respect to the one or more organophosphorus ligand degradation products is expressed by a partition coefficient ratio Ef2 which is a value greater than about 2.5, and (iii) the selectivity of the polar phase for the organophosphorus ligand with respect to the one or more reaction byproducts is expressed by a partition coefficient ratio Ef3 which is a value greater than about 2.5.

This invention relates to a process for separating one or more products from a reaction product fluid comprising a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more products, one or more nonpolar reaction solvents and one or more polar reaction solvents, wherein said process comprises (1) subjecting said reaction product fluid to fractional countercurrent extraction with at least two immiscible extraction solvents, said at least two immiscible extraction solvents comprising at least one nonpolar extraction solvent and at least one polar extraction solvent, to obtain a nonpolar phase comprising said metal-organophosphorus ligand complex catalyst, said optionally free organophosphorus ligand, said one or more nonpolar reaction solvents and said at least one nonpolar extraction solvent and a polar phase comprising said one or more products, said one or more polar reaction solvents and said at least one polar extraction solvent, and (2) recovering said polar phase from said nonpolar phase; wherein (i) the organophosphorus ligand has a partition coefficient Kp1 defined herein between the nonpolar phase and the polar phase of greater than about 5, and (ii) the one or more products have a partition coefficient Kp2 defined herein between the nonpolar phase and the polar phase of less than about 2.0.

This invention relates in part to processes for producing one or more substituted or unsubstituted epsilon caprolactams, e.g., epsilon caprolactam, which comprise (a) converting one or more substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanal, optionally in the presence of a catalyst or a catalyst and promoter, to one or more substituted or unsubstituted hydroxyamides, e.g. 6-hydroxycaproamide, and/or one or more substituted or unsubstituted epsilon caprolactam precursors, e.g., 6-aminocaproamide, epsilon caprolactone, epsilon caprolactone oligomers and esters of 6-hydroxycaproic acid and mixtures thereof, and (b) converting said one or more substituted or unsubstituted hydroxyamides and/or said one or more substituted or unsubstituted epsilon caprolactam precursors, optionally in the presence of a catalyst or a catalyst and promoter, to said one or more substituted or unsubstituted epsilon caprolactams; wherein the amount of byproducts resulting from reduction and/or reductive amination of said one or more substituted or unsubstituted hydroxyaldehydes, e.g., 1,6-hexanediol, aminohexanol, and the like, is no greater than about 10 weight percent, preferably no greater than about 5 weight percent, and more preferably no greater than about 1 weight percent, of the total of said one or more substituted or unsubstituted hydroxyamides and/or one or more substituted or unsubstituted epsilon caprolactam precursors. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted epsilon caprolactams as principal product(s) of reaction.

Processes for producing epsilon caprolactams

This invention relates to a process for separating one or more products from a reaction product fluid comprising a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more products, one or more polar reaction solvents and one or more nonpolar reaction solvents, wherein said process comprises (1) subjecting said reaction product fluid to fractional countercurrent extraction with at least two immiscible extraction solvents, said at least two immiscible extraction solvents comprising at least one polar extraction solvent and at least one nonpolar extraction solvent, to obtain a polar phase comprising said metal-organophosphorus ligand complex catalyst, said optionally free organophosphorus ligand, said one or more polar reaction solvents and said at least one polar extraction solvent and a nonpolar phase comprising said one or more products, said one or more nonpolar reaction solvents and said at least one nonpolar extraction solvent, and (2) recovering said nonpolar phase from said polar phase; wherein (i) the organophosphorus ligand has a partition coefficient Kp1 defined herein between the polar phase and the nonpolar phase of greater than about 5, and (ii) the one or more products have a partition coefficient Kp2 defined herein between the polar phase and the nonpolar phase of less than about 2.0.

This invention relates to a process for separating one or more cyclic products from a reaction product fluid comprising one or more cyclic reactants, a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, a non-polar solvent and said one or more cyclic products, wherein said process comprises: (1) reacting said one or more cyclic reactants in the presence of said metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and non-polar solvent to form a multiphase reaction product fluid; and (2) separating said multiphase reaction product fluid to obtain a non-polar phase comprising said one or more cyclic reactants, metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and non-polar solvent and a polar phase comprising said one or more cyclic products.

This invention relates in part to processes for producing one or more substituted or unsubstituted 1,6-hexanediols which comprise subjecting one or more substituted or unsubstituted penten-1-ols to reductive hydroformylation in the presence of a reductive hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce said one or more substituted or unsubstituted 1,6-hexanediols. The substituted and unsubstituted 1,6-hexanediols produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactone. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted 1,6-hexanediols as principal product(s) of reaction.

Processes for producing 1,6-hexanediols

This invention relates to a method of stabilizing a metal-organophosphorus ligand complex catalyst against deactivation in a process which comprises reacting one or more reactants in the presence of a metal-organophosphorus ligand complex catalyst and optionally free organophosphorus ligand to produce a reaction product fluid comprising one or more products, and in which at least a portion of said process is conducted under separation conditions sufficient to effect at least some deactivation of the metal-organophosphorus ligand complex catalyst, which method comprises conducting the portion of said process that occurs under separation conditions in the presence of one or more alkadienes sufficient to prevent and/or lessen deactivation of the metal-organophosphorus ligand complex catalyst.

This invention relates to a process for separating one or more products from a reaction product fluid comprising a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, a nonpolar solvent and said one or more products, wherein said process comprises (1) mixing said reaction product fluid with a polar solvent to obtain by phase separation a non-polar phase comprising said metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and said nonpolar solvent and a polar phase comprising said one or more products and polar solvent, and (2) recovering said polar phase from said nonpolar phase; wherein said organophosphorus ligand has a partition coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and said one or more products have a partition coefficient between the polar solvent and the nonpolar solvent of greater than about 0.5.

Growing community of inventors

South Charleston, WV, United States of America

David Robert Bryant