Synergistic formulations of functionalized copolymers and ionic liquids for dehydrated and desalted of medium, heavy and extra heavy crude oils

Patent metadata

Field	Value
Publication number	US-9587182-B2
Application number	US-201213449007-A
Country	US
Kind code	B2
Filing date	Apr 17, 2012
Priority date	Apr 18, 2011
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The present invention is related to formulations including one or more block copolymers with low polydispersity and bifunctionalized with amines, and an ionic liquid. A method of demulsifying, dehydrating, and desalting crude oils having API gravity ranging between 8 to 30 admixes the formulation with the crude oil in an amount effective to demulsify, dehydrate and/or desalt the crude oils.

First claim

What is claimed is:

1. A method of demulsifying, dehydrating and desalting light, medium, heavy and extra-heavy crude oils having an API gravity of 8 to 30° API comprising the step of
combining the crude oil and a formulation in an amount of 5 to 3000 ppm based on the amount of crude oil effective for demulsifying the crude oil and forming a mixture, said formulation comprising a mixture of (a) a poly(ethyleneoxide) poly(propyleneoxide) poly(ethyleneoxide) copolymer having a molecular weight of 400 to 4400 Daltons and a polydispersity of 1.02 to 1.5 and bifunctionalized with an amine, and a synergistic amount of (b) an ionic liquid having a cation selected from the group consisting of 1,5-dicarboxy-pentane-2-ammonium, pyridinium, isoquinolinium, imidazolium, ammonium and ammonium carboxymethane, and an anion selected from the group consisting of R 5 COO − , Cl − , Br − , [BF 4 ] − , [PF 6 ] − , [SbF 6 ] − , [R 6 SO 4 ] − , [OTs] − , [OMs] 31 , where R 5 is an alkyl, cycloalkyl, benzyl, alkenyl, aromatic, or allyl-functionalized chain having 1 and 18 carbon atoms; and R 6 is methyl or ethyl, and
mixing the resulting mixture for a time sufficient to demulsify, dehydrate and desalt the crude oil.

2. The method of claim 1 , wherein said amine is selected from the group consisting of a C-5 or C-6 heterocyclic amine having an oxygen or nitrogen heteroatom, and an acyclic group substituted with an aliphatic or aromatic group.

3. The method of claim 1 , wherein said block copolymer and ionic liquid are present in an amount of 1 to 50% by weight based on the total weight of the formulation and where said formulation further contains a solvent having a boiling point of 30° C. to 200° C.

4. The method of claim 3 , wherein said solvent is selected from the group consisting of dichloromethane, chloroform, benzene, toluene, xylenes, jet fuel, naphtha and linear and branched C 1 to C 8 alcohols.

5. The method of claim 1 , wherein said poly(ethyleneoxide) poly(propyleneoxide) poly(ethyleneoxide) copolymer and said ionic liquid are mixed with said crude oil in an amount of 50 to 1500 ppm based on the amount of the crude oil.

6. The method of claim 1 , wherein said poly(ethyleneoxide) poly(propyleneoxide) poly(ethyleneoxide) copolymer and said ionic liquid are mixed with said crude oil in an amount of 100 to 1000 ppm based on the amount of the crude oil.

7. The method of claim 1 , wherein said copolymer has a molecular weight of 1000-4000.

8. The method of claim 1 , wherein said copolymer has a molecular weight of 400-800.

9. The method of claim 1 , wherein said copolymer and said ionic liquid are present in substantially equal amounts in said formulation.

10. The method of claim 1 , wherein said copolymer and ionic liquid are added in an amount of 50-1500 ppm.

11. The method of claim 1 , wherein said copolymer and ionic liquid are added in an amount of 200-500 ppm.

12. A method of desalting light, medium, heavy and extra-heavy crude oils having an API gravity of 8 to 30° API comprising the step of
combining a formulation to crude oil in need of desalting in an amount of 5 to 3000 ppm based on the amount of crude oil effective for desalting the crude oil and forming a mixture, said formulation comprising a mixture of (a) a poly(ethyleneoxide) poly(propyleneoxide) poly(ethyleneoxide) copolymer having a molecular weight of 400 to 4400 Daltons and a polydispersity of 1.02 to 1.5 and bifunctionalized with an amine, and a synergistic amount of (b) an ionic liquid having a cation selected from the group consisting of 1,5-dicarb oxy-p entane-2-ammonium, pyridinium, isoquinolinium, imidazolium, ammonium and ammonium carboxymethane, and an anion selected from the group consisting of R 5 COO − , Cl − , Br − , [BF 4 ] − , [PF 6 ] − , [SbF 6 ] − , [R 6 SO 4 ] − , [OTs] − , [OMs] − , where R 5 is an alkyl, cycloalkyl, benzyl, alkenyl, aromatic, or allyl-functionalized chain having 1 and 18 carbon atoms; and R 6 is methyl or ethyl, and
mixing the resulting mixture for a time sufficient to desalt the crude oil.

13. The method of claim 12 , wherein said copolymer has a molecular weight of 1000-4000.

14. The method of claim 12 , wherein said copolymer has a molecular weight of 400-800.

15. The method of claim 12 , wherein said copolymer and said ionic liquid are present in substantially equal amounts in said formulation.

16. The method of claim 12 , wherein said copolymer and ionic liquid are added in an amount of 50-1500 ppm.

17. The method of claim 12 , wherein said copolymer and ionic liquid are added in an amount of 200-500 ppm.

18. A method of demulsifying, dehydrating and desalting light, medium, heavy and extra-heavy crude oils having an API gravity of 8 to 30° API comprising the step of
combining the crude oil and a formulation in an amount of 5 to 3000 ppm based on the amount of crude oil effective for demulsifying the crude oil and forming a mixture, said formulation comprising a mixture of (a) a poly(ethyleneoxide) poly(propyleneoxide) poly(ethyleneoxide) copolymer having the formula

where:
w and y numbers are in the range of 10 to 60;
R 1 and R 2 radicals are independently represented by the groups
—H; —CH 2 (CH 2 ) A B; —CEGJ; —CH 2 CHLM; —CH 2 (CH 2 ) Q M;

where: A is a number between 1 and 11, B is H;
E, G and J are independently a radical selected from the group consisting of: —H, methyl, ethyl, n-propyl, iso-propyl, sec-butyl, iso-butyl, tent-butyl, n-butyl, phenyl, cyclohexyl and cyclopentyl;
L is a radical represented by methyl and ethyl, and M is a hydroxyl group;
Q is a number between 1 and 5; T is a radical selected from the group consisting of: —H, methyl, ethyl, n-propyl, iso-propyl, sec-butyl, iso-butyl, tent-butyl, n-butyl, phenyl, cyclohexyl, cyclopentyl, NO 2 , Cl, F and Br; or

where
w and y are as defined in Formula 5a;
U is a number between 1 and 2;
X is oxygen or nitrogen, when X is nitrogen then V is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, n-butyl, phenyl, cyclohexyl, cyclopentyl, and benzyl;
Z is a mono- or di-substitution and is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, n-butyl, phenyl, cyclohexyl, cyclopentyl, benzyl and hydroxyl; and
a synergistic amount of (b) an ionic liquid having a cation selected from the group consisting of 1,5-dicarboxy-pentane-2-ammonium, pyridinium, isoquinolinium, imidazolium, ammonium and ammonium carboxymethane, and an anion selected from the group consisting of R 5 COO − , Cl − , Br − , [BF 4 ] 31 , [PF 6 ] − , [SbF 6 ] − , [R 6 SO 4 ] 31 , [OTs] − , [OMs] − , where R 5 is an alkyl, cycloalkyl, benzyl, alkenyl, aromatic, or allyl-functionalized chain having 1 and 18 carbon atoms; and R 6 is methyl or ethyl, and
mixing the resulting mixture for a time sufficient to demulsify, dehydrate and desalt the crude oil.

19. The method of claim 18 , wherein said ionic liquid is selected from the group consisting of triethylammonium methanesulfonate, ethyltrihexylammonium bromide, 1,5-dicarboxy-pentane-2-ammonium methanesulfonate, meth

Assignees

• Flores Oropeza Eugenio Alejandro
• Castro Sotelo Laura Verónica
• López Ortega Alfonso
• Hernández Cortez José Gonzalo
• Alvarez Ramírez Fernando
• Estrada Martínez Arquímedes
• Vázquez Moreno Flavio Salvador
• Mexicano Inst Petrol

Inventors

• Flores Oropeza Eugenio Alejandro
• Castro Sotelo Laura Verónica
• López Ortega Alfonso
• Hernández Cortez José Gonzalo
• Alvarez Ramírez Fernando
• Estrada Martínez Arquímedes
• Vázquez Moreno Flavio Salvador

Classifications

• C08G65/2624

  containing aliphatic amine groups · CPC title

• C10G33/04 Primary

  with chemical means · CPC title

• C10G29/20

  Organic compounds not containing metal atoms · CPC title

• C08G65/263

  containing heterocyclic amine groups · CPC title

• C10G2300/1033

  Oil well production fluids · CPC title