Method of using high molecular weight demulsifiers
View Patent ↗Homopolymers and copolymers of an esterified reaction product of an epoxidized mono-hydroxyl alcohol and a free radical polymerizable monomer are highly effective demulsifying agents. The molecular weight of the polymer is between from about 10,000 to about 500,000. The epoxidized mono-hydroxyl alcohol is preferably a reaction product of a C 6 –C 30 linear or branched alcohol and an alkylene oxide. The alkylene oxide is preferably either ethylene oxide, propylene oxide or butylenes oxide or a mixture thereof. The free radical polymerizable monomer is preferably a vinyl aromatic compound or an acrylic or methacrylic based monomer. The polymer preferably comprises a micellar assembly. Such polymers are highly effective in demulsifying crude oils having API gravities of from 8 to 28 or a crude oil having a viscosity between from about 3 to about 10,000 CPS @ at 25° C.
1. A method of demulsifying a petroleum water-in-oil emulsion wherein the petroleum is a crude oil having an API gravity of from 8 to 28 which comprises:
(A.) introducing into the emulsion a demulsifying effective amount of a liquid comprising a micellar assembly of a bomb- or copolymer of an esterified reaction product of
an epoxidized mono-hydroxyl alcohol; and
a free radical polymerizable monomer
wherein the weight average molecular weight of the homo- or copolymer is between from about 10,000 to about 500,000 Daltons; and
(B.) resolving or separating the oil-in-water emulsion by diffusion.
2. The method of claim 1 , wherein the epoxidized mono-hydroxyl alcohol is a reaction product of an alkylene oxide and a C 6 –C 60 linear or branched chain alcohol.
3. The method of claim 1 , wherein the weight ratio of epoxidized mono-hydroxyl alcohol and free radical polymerizable monomer is between from about 3:1 to about 8:1.
4. The method of claim 1 , wherein the free radical polymerizable monomer is an acrylic or methacrylic based monomer.
5. The method of claim 4 , wherein the homopolymers or copolymer is formed by mixing a second free radical polymerizable monomer with the ester formed from the epoxidized mono-hydroxyl alcohol and the acrylic or methacrylic based monomer, and further wherein the second free radical polymerizable monomer is of the structural formula:
(CX 2 ═CX) a -Ar(-Z-) b
wherein each X is the same or different and is hydrogen, alkyl, aryl or halogen; Ar is at least one aryl ring; and Z is a substituent on any position of the aryl ring(s) and is alkyl, alkoxy, aryl, aryloxy, halogen, haloalkyl, haloaryl, alkylaryl, arylalkyl, alkanoyl, and oxyalkanoyl; a is 1 or 2; and b is 0 to 9.
6. A method of demulsifying a crude oil having a viscosity between from about 3 to about 100 CPS @ 25° C. which comprises introducing to the crude oil a demulsifying effective amount of a homo- or copolymer of an esterified reaction product of:
(A.) an epoxidized mono-hydroxyl alcohol; and
(B.) a free radical polymerizable monomer
wherein the weight average molecular weight of the homo- or copolymer is between from about 10,000 to about 500,000; and
further wherein the epoxidized mono-hydroxyl alcohol is the product of an alkylene oxide and a C 6 –C 60 linear or branched chain alcohol.
7. The method of claim 6 , wherein the homo- or copolymer comprises a micellar assembly.
8. The method of claim 6 , wherein the weight ratio of epoxidized mono-hydroxyl alcohol and free radical polymerizable monomer is between from about 3:1 to about 8:1.
9. The method of claim 6 , wherein the free radical polymerizable monomer is an acrylic or methacrylic based monomer.
10. The method of claim 9 , wherein the homopolymer or copolymer is formed by mixing a second free radical polymerizable monomer with the ester formed from the epoxidized mono-hydroxyl alcohol and the acrylic or methacrylic based monomer, and further wherein the second free radical polymerizable monomer is of the structural formula:
(CX 2 ═CX) a -Ar(-Z-) b
wherein each X is the same or different and is hydrogen, alkyl, aryl or halogen; Ar is at least one aryl ring; and Z is a substituent on any position of the aryl ring(s) and is alkyl, alkoxy, aryl, aryloxy, halogen, haloalkyl, haloaryl, alkylaryl, arylalkyl, alkanoyl, and oxyalkanoyl; a is 1 or 2; and b is 0 to 9.
11. The method of claim 6 , wherein the weight average molecular weight of the homo- or copolymer is between from about 50,000 to about 100,000 Daltons.
12. The method of claim 4 , wherein the free radical polymerizable monomer is methyl acrylate, methyl methacrylate, benzyl methacrylate or dimethylaminoethyl methacrylate.
13. The method of claim 1 , wherein the weight average molecular weight of the homo- or copolymer is between from about 50,000 to about 100,000 Daltons.
14. The method of claim 1 , wherein the alkylene oxide is ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
15. The method of claim 2 , wherein the mono-hydroxyl alcohol is a saturated or unsaturated C 6 –C 30 linear or branched alcohol.
16. The method of claim 2 , wherein the alkylene oxide is ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
17. The method of claim 9 , wherein the free radical polymerizable monomer is methyl acrylate, methyl methacrylate, benzyl methacrylate, or dimethylaminoethyl methacrylate.
18. A method of demulsifying a petroleum water-in-oil emulsion of a crude oil which comprises adding to the emulsion a demulsifying effective amount of a micellar assembly consisting essentially of a homo- or copolymer of an esterified reaction product comprising an epoxidized mono-hydroxyl alcohol and a free radical polymerizable monomer.
19. The method of claim 18 , wherein the weight average molecular weight of the homo- or copolymer is between from about 10,000 to about 500,000.
20. The method of claim 18 , wherein the epoxidized mono-hydroxyl alcohol is a reaction product of an alkylene oxide and a C 6 –C 60 linear or branched chain alcohol.
21. The method of claim 18 , wherein the free radical polymerizable monomer is an acrylic or methacrylic based monomer.
22. The method of claim 21 , wherein the homopolymer or copolymer is formed by mixing a second free radical polymerizable monomer with the ester formed from the epoxidized mono-hydroxyl alcohol and the acrylic or methacrylic based monomer, and further wherein the second free radical polymerizable monomer is of the structural formula:
(CX 2 ═CX) a -Ar(-Z-) b
wherein each X is the same or different and is hydrogen; alkyl, aryl or halogen; Ar is at least one aryl ring; and Z is a substituent on any position of the aryl ring(s) and is alkyl, alkoxy, aryl, aryloxy, halogen, haloalkyl, haloaryl, alkylaryl, arylalkyl, alkanoyl, and oxyalkanoyl; a is 1 or 2; and b is 0 to 9.
23. The method of claim 18 , wherein the crude oil has a viscosity between from about 3 to about 100 CPS @25° C.
24. The method of claim 19 , wherein the weight average molecular weight of the homo- or copolymer is between from about 50,000 to about 100,000 Daltons.
25. The method of claim 21 , wherein the free radical polymerizable monomer is methyl acrylate, methyl methacrylate, benzyl methacrylate or dimethylaminoethyl methacrylate.
26. The method of claim 18 , wherein the alkylene oxide is ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
27. The method of claim 20 , wherein the epoxidized mono-hydroxyl alcohol is a reaction product of an alkylene oxide and a C 6 –C 30 liner or branched chain alcohol.
28. The method of claim 1 , wherein the micellar assembly comprises aggregates that are 0.5 microns or greater in diameter.
29. The method of claim 1 , wherein the homo- or copolymer has a viscosity between from about 500 to about 1,500 CPS @ 25° C.
30. The method of claim 6 , wherein the homo- or copolymer has a viscosity between from about 500 to about 1,500 CPS @ 25° C.
31. A method of demulsifying a petroleum water-in-oil emulsion which comprises:
(A.) introducing into the emulsion a demulsifying effective amount of a liquid comprising a micellar assembly of a homo- or copolymer of an esterified reaction product of
an epoxidized mono-hydroxyl alcohol; and
a free radical polymerizable monomer; and
(B.) resolving or separating the oil-in-water emulsion by diffusion.