Processes for regenerating dispersions of ligand stabilized, palladium and platinum (II) halide-complexes used in carbonylation and hydroformylation catalysts

Claim 2

A process for the regeneration of dispersions of spent ligand-stabilized palladium(II) or platinum(II) halide catalysts in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) and trihalogermanate(II), the spent catalysts being obtained from the carbonylation or hydroformylation of olefins, said ligand-stabilized groups being selected from the group consisting of P(C 6 H 5 ) 3 , P(p-CH 3 .C 6 H 4 ) 3 , P(C 6 H 5 ) 3 CH 2 Cl, As(C 6 H 5 ) 3 , S(C 6 H 5 ) 2 , P(OC 6 H 5 ) 3 , P(n-C 4 H 9 ) 3 , (C 6 H 5 ) 2 AsCH 2 CH 2 As(C 6 H 5 ) 2 , the process consisting essentially of: a. contacting each part by weight of said dispersions to be regenerated with from 0.1 part by weight to 10 3 part by weight of mineral acid consisting of mixtures of hydrochloric acid, having a specific gravity of from 1.00 to 1.20 at 20° C, and nitric acid having a specific gravity of from 1.00 to 1.51 at 20° C, said acids being in volume ratios ranging from 0.01 to 100 parts by volume of hydrochloric acid for each part by volume of nitric acid; b. evaporating said mixture of solid catalyst plus acid to dryness at 50°-110° C; c. adding additional stabilizing ligand in the ratio of 1-10 mole of ligand per mile of palladium or platinum present in said spent dispersions, d. refluxing the mixture from (c) with excess organic solvent mixture, removing excess solvent and drying the dispersion to a solid in a vacuum.

Claim 3

A process for regenerating dispersions of spent ligand-stabilized palladium(II) and platinum(II) halide complexes in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) or trihalogermanate(II) by ligand-stabilized palladium(II) and platinum(II), said ligand-stabilized catalyst being obtained from the carbonylation or hydroformylation of olefins, said ligand-stabilized dispersion to be regenerated selected from the group consisting of: [(C.sub.2 H.sub.5).sub.4 N][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PdCl.sub.2 [P(p-CH.sub.3.C.sub.6 H.sub.4).sub.3 ].sub.2 [clCH.sub.2 (C.sub.6 H.sub.5).sub.3 P][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(n-C.sub.4 H.sub.9).sub.4 N][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][geCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PdCl.sub.2 [P(p-CH.sub.3 O.C.sub.6 H.sub.4).sub.3 ].sub.2 and [(C.sub.7 H.sub.15).sub.4 N][GeCl.sub.3 ]--PdCl.sub.2 [As(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [As(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [S(C.sub.6 H.sub.5).sub.2 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [P(OC.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [P(n-C.sub.4 H.sub.9).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [(C.sub.6 H.sub.5).sub.2 AsCH.sub.2 CH.sub.2 As(C.sub.6 H.sub.5).sub.2 ] [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [O-Phenanthroline] and [(C.sub.2 H.sub.5).sub.4 N][SnCl.sub.3 ]--PtCl.sub.2, [(C.sub.6 H.sub.5).sub.4 As][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 by the process consisting essentially of: a. contacting each part by weight of said dispersions to be regenerated with from 0.1 part by weight to 10 3 part by weight of mineral acid concisting of mixtures of hydrochloric acid, having a specific gravity of from 1.00 to 1.20 at 20° C, and nitric acid having a specific gravity of from 1.00 to 1.51 at 20° C, said acids being in volume ratios ranging from 0.01 to 100 parts by volume of hydrochloric acid for each part by volume of nitric acid; b. evaporating said mixture of solid catalyst plus acid to dryness at 50°-110° C; c. adding additional stabilized ligand corresponding to the original ligand contained in the dispersion of spent catalyst prior to the catalyst's use in the aforementioned hydroformylation, hydrogenation and carbonylation reactions, said ligand's ratio of 1-10 moles of ligand per mole of palladium or platinum present in the spent dispersion; d. refluxing the mixture from (c) with excess organic solvent mixture, removing excess solvent and drying the dispersion to a solid in a vacuum.

Claim 4

A process for regenerating dispersions of spent ligand-stabilized palladium(II) and platinum(II) halide complexes in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) or trihalogermanate(II) by ligand-stabilized palladium(II) and platinum(II), said ligand-stabilized catalyst being obtained from the carbonylation or hydroformylation of olefins, said ligand-stabilized dispersion to be regenerated selected from the group consisting of: [(C.sub.2 H.sub.5).sub.4 N][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PdCl.sub.2 [P(p-CH.sub.3.C.sub.6 H.sub.4).sub.3 ].sub.2 [clCH.sub.2 (C.sub.6 H.sub.5).sub.3 P][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(n-C.sub.4 H.sub.9).sub.4 N][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][geCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PdCl.sub.2 [P(p-CH.sub.3 O.C.sub.6 H.sub.4).sub.3 ].sub.2 and [(C.sub.7 H.sub.15).sub.4 N][GeCl.sub.3 ]--PdCl.sub.2 [As(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [As(C.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [S(C.sub.6 H.sub.5).sub.2 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [P(OC.sub.6 H.sub.5).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [P(n-C.sub.4 H.sub.9).sub.3 ].sub.2 [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [(C.sub.6 H.sub.5).sub.2 AsCH.sub.2 CH.sub.2 As(C.sub.6 H.sub.5).sub.2 ] [(c.sub.2 h.sub.5).sub.4 n][snCl.sub.3 ]--PtCl.sub.2 [O-Phenanthroline] and [(C.sub.2 H.sub.5).sub.4 N][SnCl.sub.3 ]--PtCl.sub.2, [(C.sub.6 H.sub.5).sub.4 As][SnCl.sub.3 ]--PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 by the process consisting essentially of: a. contacting each part by weight of said dispersions to be regenerated with from 0.1 part by weight to 10 3 part by weight of mineral acid concisting of mixtures of hydrochloric acid, having a specific gravity of from 1.00 to 1.20 at 20° C, and nitric acid having a specific gravity of from 1.00 to 1.51 at 20° C, said acids being in volume ratios ranging from 0.01 to 100 parts by volume of hydrochloric acid for each part by volume of nitric acid; b. evaporating said mixture of solid catalyst plus acid to dryness at 50°-110° C; c. adding additional stabilized ligand corresponding to the original ligand contained in the dispersion of spent catalyst prior to the catalyst's use in the aforementioned hydroformylation, hydrogenation and carbonylation reactions, said ligand's ratio of 1-10 moles of ligand per mole of palladium or platinum present in the spent dispersion; d. refluxing the mixture from (c) with excess organic solvent mixture, removing excess solvent and drying the dispersion to a solid in a vacuum.

Claim 5

A process for regenerating dispersions of [(C 2 H 5 ) 4 N][SnCl 3 ]--PdCl 2 [P(C 6 H 5 ) 3 ] 2 catalyst spent in carbonylating olefins, the process consisting essentially of: a. contacting each part by weight of said dispersions to be regenerated with from 0.1 part by weight to 10 3 part by weight of mineral acid consisting of mixtures of hydrochloric acid, having a specific gravity of from 1.00 to 1.20 at 20° C, and nitric acid having a specific gravity of from 1.00 to 1.51 at 20° C, said acids being in volume ratios ranging from 0.01 to 100 parts by volume of hydrochloric acid for each part by volume of nitric acid; b. evaporating said mixture of solid catalyst plus acid to dryness at 50°-110° C; c. adding additional P(C 6 H 5 ) 3 ligand in the ratio of 1-10 mole of ligand per mole of palladium or platinum present in said spent dispersions; d. refluxing the mixture from (c) with excess organic solvent mixture, removing excess solvent and drying the dispersion to a solid in a vacuum.

Claim 6

A process for regenerating dispersions of [(C 2 H 5 ) 4 N][SnCl 3 ]--PdCl 2 [P(C 6 H 5 ) 3 ] 2 catalyst spent in carbonylating olefins, the process consisting essentially of: a. contacting each part by weight of said dispersions to be regenerated with from 0.1 part by weight to 10 3 part by weight of mineral acid consisting of mixtures of hydrochloric acid, having a specific gravity of from 1.00 to 1.20 at 20° C, and nitric acid having a specific gravity of from 1.00 to 1.51 at 20° C, said acids being in volume ratios ranging from 0.01 to 100 parts by volume of hydrochloric acid for each part by volume of nitric acid; b. evaporating said mixture of solid catalyst plus acid to dryness at 50°-110° C; c. adding additional P(C 6 H 5 ) 3 ligand in the ratio of 1-10 mole of ligand per mole of palladium or platinum present in said spent dispersions; d. refluxing the mixture from (c) with excess organic solvent mixture, removing excess solvent and drying the dispersion to a solid in a vacuum.