Granted Patent B2

US 8,507,565 · App. 13/159,770 · Granted Aug 13, 2013

Abstract

Claims (128)

1. A method for separating emulsions of oil and water, the method comprising incorporating a demulsifying-effective amount of at least one polyorganosiloxane demulsifier into an emulsion comprising an oil phase and an aqueous phase, the polyorganosiloxane demulsifier having a molecular structure comprising a polysiloxane backbone of at least two siloxane units covalently bound to (i) one or more pendant alkylene oxide groups comprising one or more alkylene oxide units independently having 1 to 6 carbon atoms, and (ii) one or more pendant groups having the formula (C r H 2r )B wherein r equals 0 to 30 and B is an aryl radical; and (iii) one or more pendant alkyl groups having at least 4 and up to 40 carbon atoms.

2. The method of claim 1 , wherein the polyorganosiloxane has the formula:

M 1 a M 2 b M 3 c M 4 d D 1 e D 2 f D 3 g D 4 h T 1 i T 2 j T 3 k T 4 l Q m

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

M 2 =R 4 R 5 R 6 SiO 1/2

M 3 =R 7 R 8 R 9 SiO 1/2

M 4 =R 10 R 11 R 12 SiO 2/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

T 1 =R 21 SiO 3/2

T 2 =R 22 SiO 3/2

T 3 =R 23 SiO 3/2

T 4 =R 24 SiO 3/2

Q=SiO 4/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 18 , R 21 are alkyl groups having from 1 to 12 carbon atoms; R 4 , R 15 , R 22 are (C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R 26 , n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 7 , R 17 , R 23 are branched, linear or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; R 10 , R 19 , R 24 are aryl groups having the general formula (C r H 2r )B wherein r equals 0-30 and B is an aryl radical; R 11 , R 12 , R 20 are aryl groups having the general formula (C r H 2r )B, wherein r equals 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl groups having from 1 to 12 carbon atoms, wherein the subscripts a, b, c, d, e, f, g, h, i, j, k, l, m are zero or positive integers for molecules subject to the following limitations: 3≦a+b+c+d+e+f+g+h+i+j+k+l+m≦500, b+f+j≧1, c+g+k>0, d+h+l≧1, and (a+b+c+d) equals 2+i+j+k+l+2m.

3. The method of claim 2 , wherein R 1 is CH 3 , OH or OCH 3 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 , R 21 are CH 3 , R 20 is an aryl having the formula (C r H 2r )B and R 11 , R 12 are either CH 3 or an aryl having the formula (C r H 2r )B, with the proviso if the polysiloxane contains diphenyl R 19 and R 20 are C 6 H 5 .

4. The method of claim 2 , wherein R 1 is CH 3 , OH or OCH 3 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 , R 21 are CH 3 , and R 11 , R 12 , R 20 are CH 3 .

5. The method of claim 1 , wherein the polyorganosiloxane has the formula:

M 1 a M 2 b M 3 c M 4 d D 1 e D 2 f D 3 g D 4 h

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

M 2 =R 4 R 5 R 6 SiO 1/2

M 3 =R 7 R 8 R 9 SiO 1/2

M 4 =R 10 R 11 R 12 SiO 2/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 are alkyl groups having from 1 to 12 carbon atoms; R 4 , and R 15 , are (C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R 26 ; n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 7 and R 17 are linear, branched or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; R 10 and R 19 are aryl groups having the general formula (C r H 2r )B wherein r equals 0-30 and B is an aryl radical; R 11 , R 12 , R 20 are aryl groups having the general formula (C r H 2r )B, wherein r equals 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl groups having from 1 to 12 carbon atoms, 3≦a+b+c+d+e+f+g+h≦500, b+f≧1, c+g>0, d+h≧1, and a plus b plus c plus d equals 2.

6. The method of claim 1 , wherein polyorganosiloxane has the formula:

M 1 a D 1 e D 2 f D 3 g D 4 h T 1 i T 2 j T 3 k T 4 l Q m

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

T 1 =R 21 SiO 3/2

T 2 =R 22 SiO 3/2

T 3 =R 23 SiO 3/2

T 4 =R 24 SiO 3/2

Q=SiO 4/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 13 , R 14 , R 16 , R 18 , R 21 are alkyl groups having from 1 to 12 carbon atoms; R 15 , R 22 are (C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R 26 , n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 17 and R 23 are linear, branched or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; R 19 and R 24 are aryl groups having the general formula (C r H 2r )B wherein r equals 0-30 and B is an aryl radical; R 20 is an aryl group having the general formula (C r H 2r )B, wherein r equals 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl groups having from 1 to 12 carbon atoms, i+j+k+l+m>0; a=2+i+j+k+l+2m; a+e+f+g+h+i+j+k+l+m≦500, f+j≧1, g+k>0, h+l≧1.

7. The method of claim 1 , wherein the polyorganosiloxane has the formula:

M 1 D 1 e D 2 f D 3 g D 4 h M 1 a

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 13 , R 14 , R 16 , R 18 are alkyl groups having from 1 to 12 carbon atoms; R 15 is (C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R 26 , n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 17 is a linear, branched or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; and R 19 is an aryl group having the general formula (C r H 2r )B wherein r equals 0-30 and B is an aryl radical; R 20 is an aryl group having the general formula (C r H 2r )B, wherein r equal 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl groups having from 1 to 12 carbon atoms, 1≦e+f+g+h≦498, f≧1, g>0 and h≧1.

8. The method of claim 7 , wherein R 1 is CH 3 , OH or OCH 3 ; R 2 , R 3 , R 13 , R 14 , R 16 , R 18 are CH 3 , R 20 is an aryl having the formula (C r H 2r )B, with the proviso if the polyorganosiloxane contains diphenyl R 19 and R 20 are C 6 H 5 .

9. The method of claim 7 , wherein R 1 is CH 3 , OH or OCH 3 ; R 2 , R 3 , R 13 , R 14 , R 16 , R 18 are CH 3 ; and R 20 is CH 3 .

10. The method of claim 1 , wherein the polyorganosiloxane has the structure:

wherein X equals 0 to 498 L equals 1 to 300, K equals 1 to 300, J equals 1 to 300, M equals 0 to 100, N equals 0 to 100, with the proviso that M+N equals 1 to 200, and O equals 2 to 33 and Z is a hydrogen or an alkyl group having from 1 to 12 carbon atoms.

11. The method of claim 1 , further comprising at least one organic demulsifier selected from the group consisting of sulfonic acids, carboxylic acids, thiocarboxylic acids, carboxylic acid esters, phosphinic acids, alkyleneoxide polymers, alkyleneoxide copolymers, alkyleneoxide-functionalized phenolic resins, epoxy resins, amine alkyleneoxides, polyimine alkoxylates, polyester amines, cationic surfactants, bis-amides, silicone-based homopolymers and silicone-based copolymers.

12. The method of claim 1 , wherein the at least one polyorganosiloxane demulsifier is used at a concentration of from 0.1 to 10,000 ppm of the total composition.

13. The method of claim 1 , wherein the at least one polyorganosiloxane demulsifier is used at a concentration of from 0.5 to 1000 ppm of the total composition.

14. The method of claim 1 , wherein the at least one polyorganosiloxane demulsifier is used at a concentration of from 5 to 500 ppm of the total composition.

15. The method of claim 1 , wherein the at least one polyorganosiloxane demulsifier comprises a blend of two or more polyorganosiloxanes.

16. A composition comprising:

a) a demulsifying-effective amount of at least one polyorganosiloxane demulsifier having a molecular structure comprising a polysiloxane backbone of at least two siloxane units covalently bound to (i) one or more pendant alkylene oxide groups comprising one or more alkylene oxide units independently having 1 to 6 carbon atoms, (ii) one or more pendant groups having the formula (C r H 2r )B wherein r equals 0 to 30 and B is an aryl radical; and (iii) one or more pendant alkyl groups having at least 4 and up to 40 carbon atoms;

b) an aqueous phase; and

c) an oil phase.

17. The composition of claim 16 , wherein the polyorganosiloxane has the formula:

M 1 a M 2 b M 3 c M 4 d D 1 e D 2 f D 3 g D 4 h T 1 i T 2 j T 3 k T 4 l Q m

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

M 2 =R 4 R 5 R 6 SiO 1/2

M 3 =R 7 R 8 R 9 SiO 1/2

M 4 =R 10 R 11 R 12 SiO 2/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

T 1 =R 21 SiO 3/2

T 2 =R 22 SiO 3/2

T 3 =R 23 SiO 3/2

T 4 =R 24 SiO 3/2

Q=SiO 4/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 , R 21 are alkyl groups having from 1 to 12 carbon atoms; R 4 , R 15 , R 22 are (C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p (C 4 H 8 O) q —R 26 , n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 7 , R 17 , R 23 are branched, linear or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; R 10 , R 19 , R 24 are aryl groups having the general formula (C r H 2r )B wherein r equals 0-30 and B is an aryl radical; R 11 , R 12 , R 20 are aryl groups having the general formula (C r H 2r )B, wherein r equals 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl group having from 1 to 12 carbon atoms, wherein the subscripts a, b, c, d, e, f, g, h, i, j, k, l, m are zero or positive integers for molecules subject to the following limitations: 3≦a+b+c+d+e+f+g+h+i+j+k+l+m≦500, b+f+j≧1, c+g+k>0, d+h+l≧1, and (a+b+c+d) equals 2+i+j+k+l+2m.

18. The composition of claim 17 , wherein R 1 is CH 3 , OH or OCH 3 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 , R 21 are CH 3 , R 20 is an aryl having the formula (C r H 2r )B and R 11 , R 12 are either CH 3 or an aryl having the formula (C r H 2r )B, with the proviso if the polysiloxane contains diphenyl R 19 and R 20 are C 6 H 5 .

19. The composition of claim 17 , wherein R 1 is CH 3 , OH or OCH 3 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 , R 21 are CH 3 , and R 11 , R 12 , R 20 are CH 3 .

20. The composition of claim 16 , wherein the polyorganosiloxane has the formula:

M 1 a M 2 b M 3 c M 4 d D 1 e D 2 f D 3 g D 4 h

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

M 2 =R 4 R 5 R 6 SiO 1/2

M 3 =R 7 R 8 R 9 SiO 1/2

M 4 =R 10 R 11 R 12 SiO 2/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 are alkyl groups having from 1 to 12 carbon atoms; R 4 , and R 15 , are (C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R 26 ; n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 7 and R 17 are linear, branched or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; R 10 and R 19 are aryl groups having the formula (C r H 2r )B wherein r equals 0 to 30 and B is an aryl radical; R 11 , R 12 , R 20 are aryl groups having the general formula (C r H 2r )B, wherein r equals 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl groups having from 1 to 12 carbon atoms, 3≦a+b+c+d+e+f+g+h≦500, b+f≧1, c+g>0, d+h≧1, and a plus b plus c plus d equals 2.

21. The composition of claim 16 , wherein polyorganosiloxane has the formula:

M 1 a D 1 e D 2 f D 3 g D 4 h T 1 i T 2 j T 3 k T 4 l Q m

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

T 1 =R 21 SiO 3/2

T 2 =R 22 SiO 3/2

T 3 =R 23 SiO 3/2

T 4 =R 24 SiO 3/2

Q=SiO 4/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 13 , R 14 , R 16 , R 18 , R 21 are alkyl groups having from 1 to 12 carbon atoms; R 15 , R 22 are (C 2 H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R 26 , n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 17 and R 23 are linear, branched or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; R 19 and R 24 are aryl groups having the general formula (C r H 2r )B wherein r equals 0 to 30 and B is an aryl radical; R 20 is an aryl group having the general formula (C r H 2r )B, wherein r equals 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl groups having from 1 to 12 carbon atoms, i+j+k+l+m>0; a=2+i+j+k+l+2m, 3≦a+e+f+g+h+i+j+k+l+m≦500, f+j≧1, g+k>0, h+l≧1.

22. The composition of claim 16 , wherein the polyorganosiloxane has the formula:

M 1 D 1 e D 2 f D 3 g D 4 h M 1

wherein:

M 1 =R 1 R 2 R 3 SiO 1/2

D 1 =R 13 R 14 SiO 2/2

D 2 =R 15 R 16 SiO 2/2

D 3 =R 17 R 18 SiO 2/2

D 4 =R 19 R 20 SiO 2/2

and, R 1 is an alkyl group having from 1 to 12 carbon atoms, an OH or OR 25 ; R 2 , R 3 , R 13 , R 14 , R 16 , R 18 are alkyl groups having from 1 to 12 carbon atoms; R 15 is (C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R 26 , n equals 0 to 6, o equals 0 to 100, p equals 0 to 100 and q equals 0 to 50, provided o+p+q≧1; R 17 is a linear, branched or cyclic, saturated or unsaturated alkyl groups having from 4 to 36 carbon atoms; and R 19 is an aryl group having the general formula (C r H 2r )B wherein r equals 0-30 and B is an aryl radical; R 20 is an aryl group having the formula (C r H 2r )B, wherein r equal 0 to 30 or an alkyl group having from 1 to 12 carbon atoms; R 25 is an alkyl group with 1 to 12 carbon atoms and R 26 is a hydrogen or an alkyl group having from 1 to 12 carbon atoms, 1≦e+f+g+h≦498, f≧1, g>0 and h≧1.

23. The composition of claim 22 , wherein R 1 is CH 3 , OH or OCH 3 , R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 13 , R 14 , R 16 , R 18 are CH 3 , and R 20 is CH 3 .

24. The composition of claim 22 , wherein R 1 is CH 3 , OH or OCH 3 ; R 2 , R 3 , R 13 , R 14 , R 16 , and R 18 are CH 3 , R 20 is an aryl having the formula (C r H 2r )B, with the proviso if the polysiloxane contains diphenyl R 19 and R 20 are C 6 H 5 .

25. The composition of claim 16 wherein the polyorganosiloxane has the structure:

wherein X equals 0 to 498, L equals 1 to 300, K equals 1 to 300, J equals 1 to 300, M equals 0 to 100, N equals 0 to 100, with the proviso that M+N equals 1 to 200, and O equals 2 to 33 and Z is a hydrogen or an alkyl group having from 1 to 12 carbon atoms.

26. The composition of claim 16 , further comprising at least one organic demulsifier selected from the group consisting of sulfonic acids, carboxylic acids, thiocarboxylic acids, carboxylic acid esters, phosphinic acids, alkyleneoxide polymers, alkyleneoxide copolymers, alkyleneoxide-functionalized phenolic resins, epoxy resins, amine alkyleneoxides, polyimine alkoxylates, polyester amines, cationic surfactants, bis-amides, silicone-based homopolymers and silicone-based copolymers.

27. The composition of claim 16 , wherein the at least one polyorganosiloxane demulsifier is used at a concentration of from 5 to 500 ppm of the total composition.

Assignments (23)