Use of zeta potential modifiers to decrease the residual oil saturation

1. A method for increasing production comprising:

pumping, into an oil producing reservoir or formation, a surface coating composition under conditions sufficient to partially coat surfaces and particles of the producing reservoir or formation with the composition, where the composition comprises an amine component, an amine/phosphate ester reaction product component and optionally a solvent component, where the amine component comprises a mixture of nitrogen containing heterocyclic compounds, where the coating is substantially permanent or permanent, where the coating modifies surface properties of the surfaces and particles of the producing reservoir or formation to decrease residual oil saturation in the producing reservoir or formation by decreasing the capillary pressure at low oil saturation and changing a wettability of the surfaces and/or particles that is more water wetting.

2. The method of claim 1 , wherein the amine/phosphate ester reaction product component comprises a reaction product between an amine or a mixture of amines and a phosphate compound or a mixture of phosphate compounds.

3. The method of claim 2 , wherein the amines comprise any amine that is capable of reacting with a suitable phosphate compound.

4. The method of claim 3 , wherein the amines comprise amines of the general formula R 1 , R 2 NH or mixtures or combinations thereof, where R 1 and R 2 are independently a hydrogen atom or a carbyl group having between about between about 1 and 40 carbon atoms and the required hydrogen atoms to satisfy the valence and where one or more of the carbon atoms can be replaced by one or more hetero atoms selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur and mixture or combinations thereof and where one or more of the hydrogen atoms can be replaced by one or more single valence atoms selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures or combinations thereof.

5. The method of claim 4 , wherein the amines are selected from the group consisting of aniline and alkyl anilines or mixtures of alkyl anilines, pyridines and alkyl pyridines or mixtures of alkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkyl pyrroles, piperidine and alkyl piperidines or mixtures of alkyl piperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkyl pyrrolidines, indole and alkyl indoles or mixtures of alkyl indoles, imidazole and alkyl imidazole or mixtures of alkyl imidazoles, quinoline and alkyl quinoline or mixtures of alkyl quinolines, isoquinoline and alkyl isoquinoline or mixtures of alkyl isoquinolines, pyrazine and alkyl pyrazine or mixtures of alkyl pyrazines, quinoxaline and alkyl quinoxaline or mixtures of alkyl quinoxalines, acridine and alkyl acridine or mixtures of alkyl acridines, pyrimidine and alkyl pyrimidine or mixtures of alkyl pyrimidines, quinazoline and alkyl quinazoline or mixtures of alkyl quinazolines, and mixtures or combinations thereof.

6. The method of claim 2 , wherein the phosphate compounds comprise any phosphate compound capable of reacting with an amine to form phosphate ester.

7. The method of claim 6 , wherein the phosphate compounds comprise phosphate esters of the general formula P(O)(OR 3 )(OR 4 )(OR 5 ), phosphoric acid, polyphosphoric acid, or mixture or combinations thereof, where R 3 , R 4 , and R 5 are independently a hydrogen atom or a carbyl group having between about between about 1 and 40 carbon atoms and the required hydrogen atoms to satisfy the valence and where one or more of the carbon atoms can be replaced by one or more hetero atoms selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur or mixture or combinations thereof and where one or more of the hydrogen atoms can be replaced by one or more single valence atoms selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures or combinations thereof.

8. The method of claim 6 , wherein the phosphate compounds comprise phosphate esters include, without limitation, phosphate ester of alkanols having the general formula P(O)(OH) x (OR 6 ) y where x+y=3 and R 6 is independently a hydrogen atom or a carbyl group having between about 1 and 40 carbon atoms and the required hydrogen atoms to satisfy the valence and where one or more of the carbon atoms can be replaced by one or more hetero atoms selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur and mixture or combinations thereof and where one or more of the hydrogen atoms can be replaced by one or more single valence atoms selected from the group consisting of fluorine, chlorine, bromine, iodine or mixtures or combinations thereof.

9. The method of claim 1 , wherein the nitrogen containing heterocyclic compounds are selected from the group consisting ofpyridines and alkyl pyridines or mixtures of alkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkyl pyrroles, piperidine and alkyl piperidines or mixtures of alkyl piperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkyl pyrrolidines, indole and alkyl indoles or mixtures of alkyl indoles, imidazole and alkyl imidazole or mixtures of alkyl imidazoles, quinoline and alkyl quinoline or mixtures of alkyl quinolines, isoquinoline and alkyl isoquinoline or mixtures of alkyl isoquinolines, pyrazine and alkyl pyrazine or mixtures of alkyl pyrazines, quinoxaline and alkyl quinoxaline or mixtures of alkyl quinoxalines, acridine and alkyl acridine or mixtures of alkyl acridines, pyrimidine and alkyl pyrimidine or mixtures of alkyl pyrimidines, quinazoline and alkyl quinazoline or mixtures of alkyl quinazolines, and mixtures or combinations thereof.

10. The method of claim 9 , wherein the amine component comprises alkyl pyridines.

11. The method of claim 1 , wherein the solvent component comprises lower alcohols having between 1 and about 4 carbon atoms, glycols, acetates, other oxygen containing solvents and mixtures and combinations thereof

12. The method of claim 1 , wherein the pumping step is performed prior to, during or after a fracturing operation.

13. The method of claim 1 , wherein the pumping step is performed intermittently during the producing life of the producing reservoir or formation.

14. The method of claim 1 , wherein the nitrogen containing heterocycles are selected from the group consisting of alkyl pyridines or mixtures of alkyl pyridines, alkyl pyrroles or mixtures of alkyl pyrroles, alkyl piperidines or mixtures of alkyl piperidines, alkyl pyrrolidines or mixtures of alkyl pyrrolidines, alkyl indoles or mixtures of alkyl indoles, alkyl imidazole or mixtures of alkyl imidazoles, alkyl quinoline or mixtures of alkyl quinolines, alkyl isoquinoline or mixtures of alkyl isoquinolines, alkyl pyrazine or mixtures of alkyl pyrazines, alkyl quinoxaline or mixtures of alkyl quinoxalines, alkyl acridine or mixtures of alkyl acridines, alkyl pyrimidine or mixtures of alkyl pyrimidines, alkyl quinazoline or mixtures of alkyl quinazolines, and mixtures or combinations thereof.

15. A method for increasing production comprising:

injecting, into an oil producing reservoir or formation, a coating composition under conditions sufficient to form a substantially permanent or permanent coating on surfaces and particles of the producing reservoir or formation, where the composition comprises an amine component, an amine/phosphate ester reaction product component and optionally a solvent component, where the amine component comprises a mixture of nitrogen containing heterocyclic compounds, where the coating modifies surface properties of the surfaces and particles of the producing reservoir or formation to decrease residual oil saturation in the producing formations by decreasing the capillary pressure at low oil saturation and changing a wettability of the surfaces and/or particles that is more water wetting.

16. The method of claim 15 , wherein the amine/phosphate ester reaction product component comprises a reaction product between an amine or a mixture of amine and a phosphate compound or a mixture of phosphate compounds.

17. The method of claim 16 , wherein the amines comprise any amine that is capable of reacting with a suitable phosphate compound.

18. The method of claim 17 , wherein the amines comprise amines of the general formula R 1 , R 2 NH or mixtures or combinations thereof, where R 1 and R 2 are independently a hydrogen atom or a carbyl group having between about between about 1 and 40 carbon atoms and the required hydrogen atoms to satisfy the valence and where one or more of the carbon atoms can be replaced by one or more hetero atoms selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur and mixture or combinations thereof and where one or more of the hydrogen atoms can be replaced by one or more single valence atoms selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures or combinations thereof.

19. The method of claim 18 , wherein the amines are selected from the group consisting of aniline and alkyl anilines or mixtures of alkyl anilines, pyridines and alkyl pyridines or mixtures of alkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkyl pyrroles, piperidine and alkyl piperidines or mixtures of alkyl piperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkyl pyrrolidines, indole and alkyl indoles or mixtures of alkyl indoles, imidazole and alkyl imidazole or mixtures of alkyl imidazoles, quinoline and alkyl quinoline or mixtures of alkyl quinolines, isoquinoline and alkyl isoquinoline or mixtures of alkyl isoquinolines, pyrazine and alkyl pyrazine or mixtures of alkyl pyrazines, quinoxaline and alkyl quinoxaline or mixtures of alkyl quinoxalines, acridine and alkyl acridine or mixtures of alkyl acridines, pyrimidine and alkyl pyrimidine or mixtures of alkyl pyrimidines, quinazoline and alkyl quinazoline or mixtures of alkyl quinazolines, and mixtures or combinations thereof.

20. The method of claim 16 , wherein the phosphate compounds comprise any phosphate compound capable of reacting with a amine to form phosphate ester.

21. The method of claim 20 , wherein the phosphate compounds comprise phosphate esters of the general formula P(O)(OR 3 )(OR 4 )(OR 5 ), phosphoric acid, polyphosphoric acid, or mixture or combinations thereof, where R 3 , R 4 , and R 5 are independently a hydrogen atom or a carbyl group having between about 1 and 40 carbon atoms and the required hydrogen atoms to satisfy the valence and where one or more of the carbon atoms can be replaced by one or more hetero atoms selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur and mixture or combinations thereof and where one or more of the hydrogen atoms can be replaced by one or more single valence atoms selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures or combinations thereof.

22. The method of claim 20 , wherein the phosphate compounds comprise phosphate esters include, without limitation, phosphate ester of alkanols having the general formula P(O)(OH) x (OR 6 ) y where x+y=3 and R 6 is independently a hydrogen atom or a carbyl group having between about 1 and 40 carbon atoms and the required hydrogen atoms to satisfy the valence and where one or more of the carbon atoms can be replaced by one or more hetero atoms selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur and mixture or combinations thereof and where one or more of the hydrogen atoms can be replaced by one or more single valence atoms selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures or combinations thereof.

23. The method of claim 15 , wherein nitrogen containing heterocyclic compounds are selected from the group consisting of pyridines and alkyl pyridines or mixtures of alkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkyl pyrroles, piperidine and alkyl piperidines or mixtures of alkyl piperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkyl pyrrolidines, indole and alkyl indoles or mixtures of alkyl indoles, imidazole and alkyl imidazole or mixtures of alkyl imidazoles, quinoline and alkyl quinoline or mixtures of alkyl quinolines, isoquinoline and alkyl isoquinoline or mixtures of alkyl isoquinolines, pyrazine and alkyl pyrazine or mixtures of alkyl pyrazines, quinoxaline and alkyl quinoxaline or mixtures of alkyl quinoxalines, acridine and alkyl acridine or mixtures of alkyl acridines, pyrimidine and alkyl pyrimidine or mixtures of alkyl pyrimidines, quinazoline and alkyl quinazoline or mixtures of alkyl quinazolines, and mixtures or combinations thereof.

24. The method of claim 23 , wherein the amine component comprises alkyl pyridines.

25. The method of claim 15 , wherein the solvent component comprises lower alcohols having between 1 and about 4 carbon atoms, glycols, acetates, other oxygen containing solvents and mixtures and combinations thereof

26. The method of claim 15 , wherein the injecting step is performed prior to, during or after a fracturing operation.

27. The method of claim 15 , wherein the injecting step is performed intermittently during the producing life of the producing reservoir or formation.

28. The method of claim 15 , wherein the nitrogen containing heterocycles are selected from the group consisting of alkyl pyridines or mixtures of alkyl pyridines, alkyl pyrroles or mixtures of alkyl pyrroles, alkyl piperidines or mixtures of alkyl piperidines, alkyl pyrrolidines or mixtures of alkyl pyrrolidines, alkyl indoles or mixtures of alkyl indoles, alkyl imidazole or mixtures of alkyl imidazoles, alkyl quinoline or mixtures of alkyl quinolines, alkyl isoquinoline or mixtures of alkyl isoquinolines, alkyl pyrazine or mixtures of alkyl pyrazines, alkyl quinoxaline or mixtures of alkyl quinoxalines, alkyl acridine or mixtures of alkyl acridines, alkyl pyrimidine or mixtures of alkyl pyrimidines, alkyl quinazoline or mixtures of alkyl quinazolines, and mixtures or combinations thereof.