Union Carbide Chemicals & Plastics Technology Corporation

Dow Technology Investments LLC

Basf Se Corporation

Dow Global Technolgoies LLC

Union Carbide Chemicals & Technology LLC

Thomas Carl Eisenschmid

Michael A Brammer

John Robert Briggs

Glenn A Miller

Kurt Damar Olson

Diane Lee Packett

David Robert Bryant

Anil Sakharam Guram

Erik Bruce Tjaden

John Michael Maher

James Clair Nicholson

Rick B Watson

Michael C Becker

Tak W Leung

Ernst Billig

George R Phillips

Jeffrey Scott Sawrey

Irvin B Cox

Ronald R Peterson

David James Schreck

Jens Rudolph

Ailene Gardner Phillips

Morteza Mokhtarzadeh

Edward Adrian Lord

Elaine Susan Brigham

Donald L Campbell, Jr

Hans-Rüdiger Reeh

David A Wilson

Cynthia L Rand

Aaron W Sanders

Anthony G Abatjoglou

Brian W Kolthammer

Rainer Papp

Donald Lee Morrison

Marinus A Bigi

Martin Smidt

Amarnath Singh

Pierre Thomas Varineau

Cloid Russell Smith, Iii

Donald Leroy Bunning

Adrian Lord

Kara S Weber

Kirk R Thompson

Hans-Günter Thelen

Donald L Campbell

Robert Kirk Thompson

William N Felsted, Ii

Anthony G Abatjoglon

Arthur Roy Doumaux, Jr

Michael Allen Brammer

Johnathan Eugene Holladay

Robert Hetterley

Michael John Bainbridge

Eric Bruce Tjaden

Maximilian Walter

Ludwig Herk

Daine Lee Packett

Hans-Rudiger Reeh

Ludwig Heck

William N Felsted Ii

Molly I-Chin Busby

The present invention generally relates to processes for the recovery of rhodium from a catalyst purge stream from a C6 or higher olefin hydroformylation process. In one embodiment, the process comprises (a) treating a catalyst-containing liquid purge stream from the hydroformylation process, wherein the catalyst comprises a precious metal and an organophosphorous ligand, with an oxidant in the presence of a separate liquid aqueous phase comprising a halide-free acid at a sufficient temperature to effect oxidation of a majority of the contained organophosphorous ligand, wherein the halide-free acid is a C1-C6 organic acid or phosphorous acid; (b) recovering the aqueous phase; (c) contacting the aqueous phase with a separate organic phase by mixing the two phases under a syngas atmosphere, wherein the separate organic phase comprises water-insoluble, hydrolysable organophosphorous ligand and recycled olefin from a hydroformylation process; and (d) separating the organic phase to be recycled back to a hydroformylation process.

Processes for recovery of rhodium from a hydroformylation process

Disclosed herein are methods to rejuvenate a deactivated hydroformylation catalyst solution wherein the solution comprises rhodium, polydentate phosphine ligands, and polydentate phosphine ligand degradation products. In one embodiment, such methods comprise adding a peroxide to the deactivated hydroformylation catalyst solution.

Methods to rejuvenate a deactivated hydroformylation catalyst solution

The catalyst solution used in a hydroformylation process is prepared for storage by first reducing its acid concentration and/or water content, and then storing the solution under a blanket of syngas and/or an inert gas. Alternatively, or in addition to, the catalyst solution can be stored with an aqueous buffer comprising materials that will neutralize and/or absorb the acid species within the catalyst solution.

Methods to store transition metal organophosphorous ligand based catalysts

A hydroformylation process wherein a water-soluble amine is contacted with the reaction fluid, liquid from the reactor is sent to an extraction zone, and a neutralized phosphorus acidic compound is at least partially removed from the extraction zone.

Hydroformylation process

Catalytic metal loss when using a hydroformylation catalyst comprising an organophosphite ligand is ameliorated by adding CO to a strip gas vaporizer.

A multi-reaction train hydroformylation process wherein a common product-catalyst separation zone is employed.

A heterocyclic nitrogen stabilizing agent is employed to reduce the rate of catalyst deactivation in a hydroformylation process.

Hetereocyclic agent as catalytic stabilizing agent in a hydroformylation process

A hydroformylation process that tolerates a high level of methanol in the feed.

A process for stabilizing a phosphite ligand against degradation in a hydroformylation reaction fluid, said process comprising adding an epoxide to the reaction fluid, and further comprising separating one or more phosphorus acidic compounds from the reaction fluid by treating the reaction fluid with an aqueous buffer solution under conditions sufficient to neutralize and remove at least some amount of the phosphorus acidic compounds from the reaction fluid.

Process for stabilizing a phosphite ligand against degradation

The extraction process for removing metal salts from an organic hydroformylation reaction fluid ('HRF') prior to returning the HRF to a reaction zone of a hydroformylation process, the extraction process comprising the step of contacting the HRF with an aqueous buffer solution, is improved by contacting the HRF with water in addition to that present in the aqueous buffer solution, i.e., with added water.

Mitigation of fouling in hydroformylation processes by water addition

Control of an in-series, multiple, e.g., two, reaction zone, hydroformylation process for producing normal (N) and iso (I) aldehydes at a N:I ratio, the process comprising contacting an olefinically unsaturated compound, e.g., propylene, with carbon monoxide, hydrogen and a catalyst comprising (A) a transition metal, e.g., rhodium, (B) an organobisphosphite, and (C) an organomonophosphite ligand, the contacting conducted in first and subsequent reaction zones and at hydroformylation conditions comprising an olefinically unsaturated compound partial pressure in each zone, the control exercised by decreasing the olefinically unsaturated compound partial pressure in the first reaction zone to decrease the N:I ratio or increasing the olefinically unsaturated compound partial pressure in the first reaction zone to increase the N:I ratio.

Controlling the normal:ISO aldehyde ratio in a mixed ligand hydroformylation process by controlling the olefin partial pressure

A method of controlling an in-series, multiple, e.g., two, reaction zone, hydroformylation process for producing normal (N) and iso (I) aldehydes at a N:I ratio, the process comprising contacting an olefinically unsaturated compound with synthesis gas and a catalyst comprising (A) a transition metal, e.g., rhodium, (B) an organobisphosphite ligand, and (C) an organomonophosphite ligand, the contacting conducted in first and subsequent reaction zone(s) and at hydroformylation conditions comprising a transition metal concentration in each zone, the method comprising decreasing the transition metal concentration in the first reaction zone to decrease the N:I ratio or increasing the transition metal concentration in the first reaction zone to increase the N:I ratio.

Controlling the normal:ISO aldehyde ratio in a mixed ligand hydroformylation process

A method of controlling a hydroformylation process for producing normal (N) and iso (I) aldehydes at a N:I ratio, the process comprising contacting an olefinically unsaturated compound, e.g., propylene, with synthesis gas and a catalyst comprising a transition metal, e.g., rhodium, and an organopolyphosphite and an organomonophosphite ligand, the contacting conducted at hydroformylation conditions comprising a synthesis gas partial pressure, the method comprising increasing the synthesis gas partial pressure in the first reaction zone to decrease the N:I ratio or decreasing the synthesis gas partial pressure in the first reaction zone to increase the N:I ratio.

Controlling the normal:iso aldehyde ratio in a mixed ligand hydroformylation process by controlling the syngas partial pressure

A process of controlling heavies in a recycle catalyst stream, particularly, for use in a continuous hydroformylation process of converting an olefin with synthesis gas in the presence of a hydroformylation catalyst to form an aldehyde product stream with subsequent separation of the catalyst for recycle to the hydroformylation step. Heavies are controlled, and preferably reduced, by means of feeding a recycle gas stream, taken as a portion of an over-head stream from a condenser, back to a vaporizer wherein the aldehyde product stream is separated.

Process of controlling heavies in a recycle catalyst stream

Novel mixtures of long-chain (C10-C20) olefins are functionalized by conversion to aldehydes using an OXO process, or to sulfates, sulfonates, sulfones, sulfides, or sulfoxides by direct sulfonation. The aldehydes may then be hydrogenated to form alcohols, or aminated to form amines or amides. The olefins starting mixture may be acquired as a byproduct of the tetramerization of ethylene in the presence of certain chromium-containing tetramerization catalysts. The functionalized mixtures, and derivatives prepared therefrom such as alkoxylates prepared from the alcohols, may be useful as surfactants that may offer improved performance in many applications, while their preparation based on a byproduct mixture reduces their cost and also reduces waste-handling issues for this non-targeted stream.

Functionalized long-chain olefin mixtures and uses therefor

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Cross Lanes, WV, United States of America

Thomas Carl Eisenschmid