Patent EA-001502-B1 (EA)
Title: Improved metal-ligand complex catalyzed processes
Inventor: BILLIG ERNST
IPC: C07C45/50
Filed: 1996-12-05
Abstract: 1. A hydroformylation process which comprises reacting one or more reactants in the presence of a metal-organopolyphosphite ligand complex catalyst to produce a reaction product fluid comprising one or more products, wherein said process is conducted at a free organopolyphosphite ligand concentration of from 0 to about 8 grams per liter of reaction product fluid; and treating at least a portion of said reaction product fluid which also contains phosphorus acidic compounds formed during said process with an acid removal substance sufficient to remove at least some amount of the phosphorus acidic compounds from said reaction product fluid. 2. A process according claim 1, which is conducted at a reaction zone and/or separator zone residence time sufficient to prevent and/or lessen hydrolytic degradation of the organopolyphosphite ligand and deactivation of the metal-organopolyphosphite ligand complex catalyst. 3. A process according claim 1, wherein phosphorus acidic compounds are removed from reaction product fluid formed during said process, by (a) withdrawing from reaction zone or separation zone at least a portion of a reaction product fluid derived from said process and which also contains phosphorus acidic compounds formed during said process, (b) treating in at least one acid removal zone at least a portion of the withdrawn reaction product fluid from stage (a) with an acid removal substance sufficient to remove at least some amount of the phosphorus acidic compounds from said reaction product fluid, and (c) returning the treated reaction product fluid to said at least one reaction zone or said at least one separation zone. 4. The process of any preceding claim wherein the free organopolyphosphite ligand concentration is from about 0.1 moles or less to about 4 moles of organopolyphosphite ligand per mole of metal. 5. The process of any preceding claim wherein the free organopolyphosphite ligand concentration is such that said process can be operated below the threshold for autocatalytic hydrolysis of the organopolyphosphite ligand. 6. The process of any preceding claim wherein said metal-organopolyphosphite ligand complex catalyst is homogeneous or heterogeneous. 7. The process of any claims from 1 to 5 wherein said reaction product fluid contains a homogeneous or heterogeneous metal-organopolyphosphite ligand complex catalyst or at least a portion of said reaction product fluid contacts a fixed heterogeneous metal-organopolyphosphite ligand complex catalyst during said processes. 8. The process of any preceding claim wherein said metal-organopolyphosphite ligand complex catalyst comprises rhodium complexed with an organopolyphosphite ligand represented by the formula:   wherein X represents a substituted or unsubstituted _n_-valent organic bridging radical containing from 2 to 40 carbon atoms, each R<1> is the same or different and represents a divalent organic radical containing from 4 to 40 carbon atoms, each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, wherein _a_ and _b_ can be the same or different and each have a value of 0 to 6, with the proviso that the sum of _a_+_b_ is 2 to 6 and _n_ equals _a_+_b_. 9. The process of claims 1-7 wherein said metal-organopolyphosphite ligand complex catalyst comprises rhodium complexed with an organopolyphosphite ligand having the formula selected from:   wherein X represents a substituted or unsubstituted divalent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R<1> is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, and each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms. 10. The process of claims 1-7 wherein said metal-organopolyphosphite ligand complex catalyst comprises rhodium complexed with an organopolyphosphite ligand having the formula selected from:   wherein X represents a substituted or unsubstituted divalent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, R<1> is a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, each Ar is the same or different and represents a substituted or unsubstituted aryl radical, each _y_ is the same or different and is a value of 0 or 1, Q represents a divalent bridging group selected from -C(R<3>)2-, -O-, -S-, -NR<4>-, -Si(R<5>)2- and -CO-, wherein each R<3> is the same or different and represents hydrogen, alkyl radical having from 1 to 12 carbon atoms, phenyl, tolyl, and anisyl, R<4> represents hydrogen or a methyl radical, each R<5> is the same or different and represents hydrogen or a methyl radical, and _m_ is a value of 0 or 1. 11. The process of any preceding claim wherein said free organopolyphosphite ligand is represented by the formula:   wherein X represents a substituted or unsubstituted _n_-valent organic bridging radical containing from 2 to 40 carbon atoms, each R<1> is the same or different and represents a divalent organic radical containing from 4 to 40 carbon atoms, each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, wherein _a_ and _b_ can be the same or different and each have a value of 0 to 6, with the proviso that the sum of _a_+_b_ is 2 to 6 and _n_ equals _a_+_b_. 12. The process of any of claims 1-10 wherein free organopolyphosphite ligand is represented by the formula:   wherein X represents a substituted or unsubstituted divalent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R<1> is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, and each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms. 13. The process of any of claims 1-10 wherein free organopolyphosphite ligand is represented by the formula:   wherein X represents a substituted or unsubstituted divalent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, R<1> is a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R<2> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, each Ar is the same or different and represents a substituted or unsubstituted aryl radical, each _y_ is the same or different and is a value of 0 or 1, Q represents a divalent bridging group selected from -C(R<3>)2-, -O-, -S-, -NR<4>-, -Si(R<5>)2- and -CO-, wherein each R<3> is the same or different and represents hydrogen, alkyl radical having from 1 to 12 carbon atoms, phenyl, tolyl, and anisyl, R<4> represents hydrogen or a methyl radical, each R<5> is the same or different and represents hydrogen or a methyl radical, and _m_ is a value of 0 or 1. 14. The process of any preceding claim wherein reaction product fluid containing phosphorus acidic compounds is treated with an aqueous buffer solution, water, ion exchange resin or a Group 2, 11 or 12 metal oxide, hydroxide, carbonate, bicarbonate or carboxylate. 15. The process of claims 1-13 wherein phosphorus acidic compounds present in the reaction product fluid are scavenged by an organic nitrogen compound that is also present in said reaction product fluid and wherein at least some amount of the phosphorus acidic compound of the conversion products of the reaction between said phosphorus acidic compound and said organic nitrogen compound are also neutralized and removed by the treatment with the aqueous buffer solution, water, ion exchange resin or a Group 2, 11 or 12 metal oxide, hydroxide, carbonate, bicarbonate or carboxylate. 16. The process of claim 15 wherein the organic nitrogen compound is selected from the group consisting of diazole, triazole, diazine and triazine. 17. The process of claim 15 wherein the organic nitrogen compound is benzimidazole or benzotriazole.