In Situ Fluid Formation for Cleaning Oil- or Synthetic-Oil-Based Mud

United States Patent Application 20080110618

What is claimed is: 1. A method of cleaning oil-based mud (OBM) filter cake particles from a hydrocarbon reservoir wellbore comprising: drilling a wellbore in a hydrocarbon reservoir with an OBM; forming a filter cake of OBM particles over at least part of the wellbore; contacting the OBM and filter cake with at least one surfactant and a polar liquid to form in situ an in-situ fluid selected from the group consisting of a miniemulsion, a nanoemulsion, a microemulsion in equilibrium with excess oil or water or both (Winsor III) and a single phase microemulsion (Winsor IV), and thereby incorporating at least a portion of the oil in the filter cake particles into the in-situ fluid. 2. The method of claim 1 where the at least one surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 3. The method of claim 2 where in the surfactants, the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, amine ethoxylates, diamine ethoxylates, methyl glucoside esters, polyglycerol esters, alkyl ethoxylates, alcohol that have been polypropoxylated and/or ethoxylated; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides, and mixtures thereof, and surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group. 4. The method of claim 1 where the in-situ fluid further comprises brine containing salts selected from the group consisting of inorganic salts, organic salts and combinations thereof. 5. The method of claim 1 where the in-situ fluid is a thermodynamically stable, macroscopically homogeneous mixture of at least three components, where the three components comprise: a polar phase from the polar liquid, a nonpolar phase from the OBM or filter cake and the at least one surfactant. 6. The method of claim 1 where the filter cake particles are selected from the group consisting of calcium carbonate, hematite, ilmenite, magnesium tetroxide, manganous oxide, iron carbonate, magnesium oxide, barium sulfate, and mixtures thereof. 7. The method of claim 1 where the in-situ fluid further comprises an acid selected from the group consisting of mineral acids and organic acids. 8. The method of claim 7 further comprising generating the acid in situ.

9. A method of cleaning oil-based mud (OBM) filter cake particles from a hydrocarbon reservoir wellbore comprising: drilling a wellbore in a hydrocarbon reservoir with an OBM; forming a filter cake of OBM particles over at least part of the wellbore; pumping into the wellbore a gravel pack carrier brine comprising: sized gravel, at least one surfactant, and a polar liquid; placing a gravel pack into the wellbore; contacting the OBM and filter cake with the gravel pack carrier brine to form in situ an in-situ fluid selected from the group consisting of a miniemulsion, a nanoemulsion, a microemulsion, and a single phase microemulsion, and thereby incorporating at least a portion of the oil from the OBM into the in-situ fluid by solubilization without circulating the well; changing the wettability of the filter cake particles from oil-wet to water-wet allowing the in-situ fluid to contact the filter cake for a period of time as a soak solution; and removing a majority of the filter cake particles. 10. The method of claim 9 where the at least one surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 11. The method of claim 10 where in the surfactants, the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, amine ethoxylates, diamine ethoxylates, methyl glucoside esters, polyglycerol esters, alkyl ethoxylates, alcohol that have been polypropoxylated and/or ethoxylated; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides, and mixtures thereof, and surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group. 12. The method of claim 9 where the in-situ fluid further comprises brine containing salts selected from the group consisting of inorganic salts, organic salts and combinations thereof. 13. The method of claim 9 where the in-situ fluid is a thermodynamically stable, macroscopically homogeneous mixture. 14. The method claim 9 where the filter cake particles are selected from the group consisting of calcium carbonate, hematite, ilmenite, magnesium tetroxide, manganous oxide, iron carbonate, magnesium oxide, barium sulfate, and mixtures thereof. 15. The method of claim 9 where the in-situ fluid further comprises an acid selected from the group consisting of mineral acids and organic acids. 16. The method of claim 15 further comprising generating the acid in situ. 17. A method of cleaning oil-based mud (OBM) filter cake particles from a hydrocarbon reservoir wellbore comprising: drilling a wellbore in a hydrocarbon reservoir with an OBM; forming a filter cake of

OBM particles over at least part of the wellbore; contacting the OBM and filter cake with at least one surfactant and a brine to form in situ an in-situ fluid selected from the group consisting of a miniemulsion, a nanoemulsion, a microemulsion in equilibrium with excess oil or water or both (Winsor III) and a single phase microemulsion (Winsor IV), and thereby incorporating at least a portion of the oil in the filter cake particles into the in-situ fluid, where the in-situ fluid is a thermodynamically stable, macroscopically homogeneous mixture of at least three components, where the three components comprise: brine, a nonpolar phase from the OBM or filter cake and the at least one surfactant, and where the filter cake particles are selected from the group consisting of calcium carbonate, hematite, ilmenite, magnesium tetroxide, manganous oxide, iron carbonate, magnesium oxide, barium sulfate, and mixtures thereof. 18. The method of claim 17 where the at least one surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 19. The method of claim 18 where in the surfactants, the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, amine ethoxylates, diamine ethoxylates, methyl glucoside esters, polyglycerol esters, alkyl ethoxylates, alcohol that have been polypropoxylated and/or ethoxylated; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides, and mixtures thereof, and surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group. 20. The method of claim 17 where the in-situ fluid further comprises an acid selected from the group consisting of mineral acids and organic acids.

IN SITU MICROEMULSIONS USED AS SPACER FLUIDS

United States Patent Application 20080274918
What is claimed is: 1. A method of removing at least a portion of oil-based mud or synthetic-based mud (O/SBM) from a wellbore comprising: drilling a wellbore in a hydrocarbon reservoir with an O/SBM; pumping a fluid pill into the wellbore, where the fluid pill comprises: at least one surfactant; at least one viscosifier; and water or brine; forming an emulsion in situ in the wellbore; and contacting the O/SBM and removing at least a portion of the O/SBM from the wellbore. 2. The method of claim 1 where the at least one surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 3. The method of claim 2 where: the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, alcohol ethoxylates, and polyglycol esters; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; and the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides, and mixtures thereof. 4. The method of claim 1 where the water in the fluid pill comprises brine selected from the group consisting of halide brines, formate brines and mixtures thereof. 5. The method of claim 1 where the in situ emulsion is a macroscopically homogeneous mixture of at least four components, where the four components comprise a polar phase from the water or brine, a nonpolar phase from the O/SBM, the at least one viscosifier and the at least one surfactant. 6. The method of claim 1 further comprising pumping a cement slurry into the wellbore subsequent to forming the emulsion in situ. 7. The method claim 1 where the emulsion is selected from the group consisting of miniemulsions, microemulsions, nanoemulsions, and single phase emulsions. 8. The method of claim 1 where the fluid pill is a first fluid pill that is a drive weighted spacer comprising: at least one weighting agent; the at least one surfactant; the at least one viscosifer; and the water or brine; and the method further comprises pumping a second fluid pill into the wellbore subsequent to the first fluid pill, where the second fluid pill comprises: at least one surfactant; and water or brine. 9. A method of removing at least a portion of oil-based mud or synthetic-based mud (O/SBM) from a

wellbore comprising: drilling a wellbore in a hydrocarbon reservoir with an O/SBM; pumping a first fluid pill into the wellbore, where the first fluid pill is a drive weighted spacer comprising: at least one weighting agent; at least one surfactant; at least one viscosifer; and water or brine; pumping a second fluid pill into the wellbore subsequent to the first fluid pill, where the second fluid pill comprises: at least one surfactant; and water or brine; forming a single phase microemulsion (SPME) in situ in the wellbore; and contacting the O/SBM and substantially removing at least a portion of the O/SBM from the wellbore. 10. The method of claim 9 where the at least one surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 11. The method of claim 10 where: the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, alcohol ethoxylates, and polyglycol esters; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; and the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides, and mixtures thereof. 12. The method of claim 9 where the water in the first and/or second fluid pill comprises brine. 13. The method of claim 9 where the in situ SPME is a macroscopically homogeneous mixture of at least four components, where the four components comprise a polar phase from the water or brine, a nonpolar phase from the O/SBM, the at least one viscosifier and the at least one surfactant. 14. The method claim 9 where the first fluid pill and/or second fluid pill further comprises an alkoxylated alcohol co-surfactant. 15. The method of claim 9 further comprising pumping a cement slurry into the wellbore subsequent to forming the emulsion in situ. 16. A thermodynamically stable, single phase microemulsion (SPME) comprising a polar phase, a nonpolar phase, a polyglycerol ester surfactant and at least one viscosifier. 17. The SPME of claim 16 where the polar phase is water or brine. 18. The SPME of claim 16 where the polar phase is brine selected from the group consisting of halide brines and formate brines. 19. The SPME of claim 16 where the nonpolar phase is selected from the group consisting of oil-based mud, synthetic-based mud, residual oily debris, and combinations thereof. 20. The SPME of claim 16 further comprising a second surfactant selected from the group consisting of:

nonionic surfactants selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, alcohol ethoxylates, and mixtures thereof; anionic surfactants selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates and mixtures thereof; and cationic surfactants selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides, and mixtures thereof. 21. The SPME of claim 20 where the second surfactant is an alkoxylated alcohol.

Single Phase Microemulsions and In Situ Microemulsions for Cleaning Formation Damage

Abstract:

Single phase microemulsions (SPMEs) and in situ-formed microemulsions may be used to clean up and remove non-polar materials from reservoir production zones of oil and gas wells. This clean up occurs by solubilization of the non-polar material into the microemulsion when the treatment fluid contacts the non-polar material. An in situ microemulsion may be formed when one or more surfactant and a polar phase (e.g. water or brine), and eventually some small amount of organic phase, contacts the reservoir formation and solubilizes the non-polar material encountered in the porous media. The microemulsions are effective for removing the formation damage caused by non-polar materials which include, but are not necessarily limited to oil-based mud, synthetic-based mud, paraffins, asphaltenes, emulsions, slugs, and combinations thereof.

Claims:
1. A method of removing at least a portion of non-polar material from a subterranean reservoir containing non-polar material, the method comprising:pumping a cleaning fluid into the subterranean reservoir to contact the cleaning fluid with the non-polar material, where the cleaning fluid comprises components selected from the group consisting of:a single-phase microemulsion (SPME), which comprises:at least one surfactant;at least one non-polar fluid; andat least one polar fluid; andin situ emulsion-forming components comprising:at least one surfactant; andat least one polar fluid;incorporating at least part of the non-polar material into an emulsion selected from the group consisting of the SPME and an emulsion formed in situ in the subterranean reservoir; andremoving the emulsion incorporating the non-polar material from the subterranean reservoir. 2. The method of claim 1 where the at least one surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, extended surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 3. The method of claim 2 where in the surfactants:the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, polyglycol esters, and alcohol ethoxylates;the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; andthe cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamines, extended surfactants with propoxylated or ethoxylated spacer arms, and mixtures thereof. 4. The method of claim 1 where the at least one polar fluid further comprises brine. 5. The method of claim 1 where the in situ emulsion-forming components further comprise a non-polar fluid and/or a fluid of intermediate polarity. 6. The method of claim 1 where the SPME or the in situ-formed emulsion is a thermodynamically stable, macroscopically homogeneous mixture of at least three components, where the three components are: a polar phase from the polar fluid, a non-polar phase from the

non-polar fluid and/or the non-polar material, and the at least one surfactant. 7. The method of claim 1 where the cleaning fluid further comprises a component selected from the group consisting of acids, oxidizing agents, water-soluble enzymes, barite dissolvers, precursors to these components, and combinations thereof. 8. The method of claim 1 where the surfactant in the cleaning fluid is an ionic surfactant and the cleaning fluid further comprises a co-surfactant. 9. The method of claim 8 where the co-surfactant is a surface active substance selected from the group consisting of mono or poly-alcohols, low molecular weight organic acids or amines, polyethylene glycol, low ethoxylation solvents and mixtures thereof. 10. A method of removing at least a portion of non-polar material from a subterranean reservoir containing non-polar material, the method comprising:pumping a cleaning fluid into the subterranean reservoir to contact the cleaning fluid with the non-polar material, where the cleaning fluid comprises components selected from the group consisting of:a single-phase microemulsion (SPME), which comprises:at least one surfactant;at least one non-polar fluid; andat least one polar brine; andin situ emulsion-forming components comprising:at least one surfactant; andat least one polar brine;incorporating at least part of the non-polar material into an emulsion selected from the group consisting of the SPME and an emulsion formed in situ in the subterranean reservoir; andremoving the emulsion incorporating the non-polar material from the subterranean reservoir,where the SPME or the in situ-formed emulsion is a thermodynamically stable, macroscopically homogeneous mixture of at least three components; and where the three components are: a polar phase from the polar fluid, a non-polar phase from the non-polar fluid and/or the non-polar material, and the at least one surfactant. 11. The method of claim 10 where the at least one surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, extended surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 12. The method of claim 11 where in the surfactants:the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, polyglycol esters, and alcohol ethoxylates;the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; andthe cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamines, extended surfactants with propoxylated or ethoxylated spacer arms, and mixtures thereof. 13. The method of claim 10 where the cleaning fluid further comprises a component selected from the group consisting of acids, oxidizing agents, water-soluble enzymes, barite dissolvers, precursors to these components, and combinations thereof.

14. The method of claim 10 where the in situ emulsion-forming components further comprise a non-polar fluid and/or a fluid of intermediate polarity. 15. The method of claim 10 where the surfactant in the cleaning fluid is an ionic surfactant and the cleaning fluid further comprises a co-surfactant. 16. The method of claim 15 where the co-surfactant is a surface active substance selected from the group consisting of mono or poly-alcohols, low molecular weight organic acids or amines, polyethylene glycol, low ethoxylation solvents and mixtures thereof. 17. The method of claim 10 where the non-polar material is selected from the group consisting of oil-based mud, synthetic-based mud, paraffins, aromatic hydrocarbons, asphaltenes, emulsions, slugs, and combinations thereof. 18. A method of removing at least a portion of non-polar material from a subterranean reservoir that contains non-polar material, the method comprising:pumping a cleaning fluid into the subterranean reservoir to contact the cleaning fluid with the non-polar material, where the cleaning fluid comprises components selected from the group consisting of:a single-phase microemulsion (SPME), which comprises:at least one surfactant;at least one non-polar fluid; andat least one polar brine; andin situ emulsion-forming components comprising:at least one surfactant; andat least one polar brine;where the at least one surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, extended surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof; andwhere the non-polar material is selected from the group consisting of oil-based mud, synthetic-based mud, paraffins, aromatic hydrocarbons, asphaltenes, emulsions, slugs, and combinations thereof;incorporating at least part of the non-polar material into an emulsion selected from the group consisting of the SPME and an emulsion formed in situ in the subterranean reservoir; andremoving the emulsion incorporating the non-polar material from the subterranean reservoir. 19. The method of claim 18 where the in situ emulsion-forming components further comprise a non-polar fluid and/or a fluid of intermediate polarity. 20. The method of claim 18 where the surfactant in the cleaning fluid is an ionic surfactant and the cleaning fluid further comprises a co-surfactant.

Mesophase Fluids with Extended Chain Surfactants for Downhole Treatments

United States Patent Application 20090183877
What is claimed is: 1. A method of treating non-polar material in a wellbore and/or subterranean reservoir containing nonpolar material, the method comprising: introducing a mesophase fluid into the wellbore and/or subterranean reservoir to contact the mesophase fluid with the non-polar material, where the mesophase

fluid comprises components selected from the group consisting of: a pre-formed mesophase fluid which comprises: at least one extended chain surfactant; at least one non-polar fluid; and at least one polar fluid; and in situ mesophase fluid-forming components comprising: at least one extended chain surfactant; and at least one polar fluid. 2. The method of claim 1 where the extended chain surfactant is selected from the group consisting of extended surfactants with a propoxylated spacer arm having from 2 to 20 propoxy moieties and an ethoxylated spacer arm having from 0 to 20 ethoxy moieties. 3. The method of claim 2 where the extended chain surfactant has a lipophilic moiety selected from the group consisting of linear or branched, saturated or unsaturated hydrocarbon chains having from 8 to 50 carbon atoms. 4. The method of claim 2 where the extended chain surfactant has a hydrophilic polar head selected from the group consisting of polyoxyethylene, sulfate, ethoxysulfate, carboxylate, ethoxy-carboxylate, C6 sugar, xylitol, di-xylitol, ethoxy-xylitol, carboxylate and xytol, carboxylate and glucose. 5. The method of claim 2 where the extended chain surfactant has a lipophilic spacer arm and a hydrophilic polar head, where the extended chain surfactant does not precipitate in the mesophase fluid. 6. The method of claim 1 where the extended chain surfactant is present in a concentration from about 0.1% w/w to about 20% w/w. 7. The method of claim 1 where the in situ mesophase fluid-forming components further comprise a nonpolar fluid and/or a fluid of intermediate polarity. 8. The method of claim 1 where the mesophase fluid further comprises at least one additional surfactant selected from the group consisting of a non-extended chain surfactant, a co-surfactant, and combinations thereof. 9. The method of claim 8 where the co-surfactant is a surface active substance selected from the group consisting of mono or poly-alcohols, low molecular weight organic acids or amines, polyethylene glycol, low ethoxylation solvents and mixtures thereof. 10. The method of claim 1 further comprising a procedure selected from the group consisting of: removing at least a portion of non-polar material from a subterranean reservoir containing the non-polar material by incorporating at least part of the non-polar material into a mesophase fluid selected from the group consisting of the pre-formed mesophase fluid and the mesophase fluid formed in situ in the subterranean reservoir, and removing the mesophase fluid incorporating the non-polar material from the subterranean reservoir; introducing the mesophase fluid into the subterranean reservoir as a fluid pill, where the fluid pill is selected from the group consisting of a water-wetting pill, a drive-weighted spacer, and combinations thereof; releasing a stuck drill string; and combinations thereof. 11. A method of treating non-polar material in a wellbore and/or subterranean reservoir containing non-

polar material, the method comprising: introducing a mesophase fluid into the wellbore and/or subterranean reservoir to contact the mesophase fluid with the non-polar material, where the mesophase fluid comprises components selected from the group consisting of: a pre-formed mesophase fluid which comprises: at least one extended chain surfactant; at least one non-polar fluid; and at least one polar fluid; and in situ mesophase fluid-forming components comprising: at least one extended chain surfactant; and at least one polar fluid. where the extended chain surfactant is present in a concentration from about 0.1% w/w to about 20% w/w, and where the extended chain surfactant is selected from the group consisting of extended surfactants with spacer arms having from 2 to 20 propoxy moieties, from 0 to 20 ethoxy moieties, and combinations thereof. 12. The method of claim 11 where the extended chain surfactant has a lipophilic moiety selected from the group consisting of linear or branched, saturated or unsaturated hydrocarbon chains having from 8 to 50 carbon atoms. 13. The method of claim 11 where the extended chain surfactant has a hydrophilic polar head selected from the group consisting of polyoxyethylene, sulfate, ethoxysulfate, carboxylate, ethoxy-carboxylate, C6 sugar, xylitol, di-xylitol, ethoxy-xylitol, carboxylate and xytol, carboxylate, and glucose. 14. The method of claim 11 where the extended chain surfactant has a lipophilic spacer arm and a hydrophilic polar head, where the extended chain surfactant does not precipitate in the mesophase fluid. 15. The method of claim 11 where the in situ mesophase fluid-forming components further comprise a non-polar fluid and/or a fluid of intermediate polarity. 16. The method of claim 11 where the mesophase fluid further comprises at least one additional surfactant selected from the group consisting of a non-extended chain surfactant, a co-surfactant, and combinations thereof. 17. The method of claim 16 where the co-surfactant is a surface active substance selected from the group consisting of mono or poly-alcohols, low molecular weight organic acids or amines, polyethylene glycol, low ethoxylation solvents and mixtures thereof. 18. A method of treating non-polar material in a wellbore and/or subterranean reservoir containing nonpolar material, the method comprising: introducing a mesophase fluid into the wellbore and/or subterranean reservoir to contact the mesophase fluid with the non-polar material, where the mesophase fluid comprises components selected from the group consisting of: a pre-formed mesophase fluid, which comprises: at least one extended chain surfactant; at least one non-polar fluid; and brine; and in situ mesophase fluid-forming components comprising: at least one extended chain surfactant; and brine; where the extended chain surfactant has a lipophilic spacer arm and a hydrophilic polar head, where the extended chain surfactant does not precipitate in the mesophase cleaning fluid. 19. The method of claim 18 where the extended chain surfactant is selected from the group consisting of extended surfactants with propoxylated and/or ethoxylated spacer arms.

20. The method of claim 18 where the spacer arms contain alkoxy moieties selected from the group consisting of from 2 to 20 propoxy moieties, from 0 to 20 ethoxy moieties, and combinations thereof. 21. The method of claim 18 where the extended chain surfactant is present in a concentration from about 0.1% w/w to about 20% w/w. 22. The method of claim 18 where the extended chain surfactant has a lipophilic moiety selected from the group consisting of linear or branched, saturated or unsaturated hydrocarbon chains having from 8 to 50 carbon atoms. 23. The method of claim 18 where the extended chain surfactant has a hydrophilic polar head selected from the group consisting of polyoxyethylene, sulfate, ethoxysulfate, carboxylate, ethoxy-carboxylate, C6 sugar, xylitol, di-xylitol, ethoxy-xylitol, carboxylate and xytol, carboxylate, and glucose. 24. The method of claim 18 where the in situ mesophase fluid-forming components further comprise a non-polar fluid and/or a fluid of intermediate polarity. 25. The method of claim 18 where the mesophase fluid further comprises at least one additional surfactant selected from the group consisting of a non-extended chain surfactant, a co-surfactant, and combinations thereof. 26. The method of claim 25 where the co-surfactant is a surface active substance selected from the group consisting of mono or poly-alcohols, low molecular weight organic acids or amines, polyethylene glycol, low ethoxylation solvents and mixtures thereof.

METHOD FOR CHANGING THE WETTABILITY OF ROCK FORMATIONS

United States Patent Application 20090325826
What is claimed is: 1. A method of changing the wettability of a rock formation previously contacted with an oil-based mud (OBM), the method comprising: pumping a water-wetting pill into the rock formation, where the waterwetting pill is selected from the group consisting of: a composition selected from the group consisting of a miniemulsion, a nanoemulsion, an emulsion, and a microemulsion, which composition comprises: at least one surfactant; at least one non-polar fluid; and at least one polar fluid; and in situ emulsion-forming components comprising: at least one surfactant; and at least one polar fluid; thereby contacting the rock formation with the composition and or the in situ-formed emulsion, where in at least the case of the in situ emulsion-forming components, at least some of the first non-polar fluid is incorporated into the in situformed emulsion; changing the wettability of at least part of the rock formation to water-wet; and subsequently pumping a second pill into the rock formation where the subsequent pill comprises water. 2. The method of claim 1 where the second pill is selected from the group consisting of fluid loss pills,

crosslink pills, reservoir rock cleaning pills, horizontal healing pills and combinations thereof. 3. The method of claim 1 where the at least one surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, fluorocarbon surfactants, silicon surfactants, cleavable, gemini surfactants, and extended surfactants containing a nonionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 4. The method of claim 3 where in the surfactants: the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, polyglycol esters, and alcohol ethoxylates; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides; and the extended chain surfactants comprise propoxylated and/or ethoxylated spacer arms, and mixtures thereof. 5. The method of claim 1 where at least one polar fluid further comprises brine. 6. The method of claim 1 where the in situ emulsion-forming components further comprise a fluid selected from the group consisting of a non-polar fluid, a fluid of intermediate polarity and mixtures thereof. 7. The method of claim 1 where the compositions and/or the in situ-formed emulsion is a thermodynamically stable, macroscopically homogeneous mixture of at least three components, where the three components comprise a polar phase from the polar fluid, a non-polar phase at least partially from the first non-polar fluid of the OBM, and the at least one surfactant. 8. The method of claim 1 where the surfactant in the water-wetting pill is an ionic surfactant and the water-wetting pill further comprises a co-surfactant. 9. The method of claim 8 where the co-surfactant is a surface active substance selected from the group consisting of mono or poly-alcohols, low molecular weight organic acids or amines, polyethylene glycol, low ethoxylation solvents and mixtures thereof. 10. The method of claim 1 where the water wetting pill further comprises an acid. 11. A method of changing the wettability of a rock formation previously contacted with an oil-based mud (OBM), the method comprising: pumping a water-wetting pill into the rock formation, where the waterwetting pill is selected from the group consisting of: a single-phase microemulsion (SPME), which comprises: at least one surfactant; at least one non-polar fluid; and at least one polar brine fluid; and in situ emulsion-forming components comprising: at least one surfactant; and at least one polar brine fluid; thereby contacting the rock formation with the SPME and/or the in situ-formed emulsion, where the SPME and/or the in situ-formed emulsion is a thermodynamically stable, macroscopically homogeneous

mixture of at least three components, where the three components comprise a polar phase from the polar fluid, a non-polar phase at least partially from the first non-polar fluid of the OBM, and the at least one surfactant; changing the wettability of at least part of the rock formation to water-wet; and subsequently pumping a second pill into the rock formation where the subsequent pill comprises water. 12. The method of claim 11 where the second pill is selected from the group consisting of fluid loss pills, crosslink pills, horizontal healer pills, reservoir rock cleaning pills and combinations thereof. 13. The method of claim 11 where the at least one surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, fluorocarbon surfactants, silicon surfactants, cleavable, gemini surfactants, and extended surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 14. The method of claim 13 where in the surfactants: the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, polyglycol esters, and alcohol ethoxylates; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides; and the extended chain surfactants comprise propoxylated and/or ethoxylated spacer arms, and mixtures thereof. 15. The method of claim 11 where the in situ emulsion-forming components further comprise a fluid selected from the group consisting of a non-polar fluid, a fluid of intermediate polarity and mixtures thereof. 16. The method of claim 11 where the surfactant in the water-wetting pill is an ionic surfactant and the water-wetting pill further comprises a co-surfactant. 17. The method of claim 16 where the co-surfactant is a surface active substance selected from the group consisting of mono or poly-alcohols, low molecular weight organic acids or amines, polyethylene glycol, low ethoxylation solvents and mixtures thereof. 18. A method of changing the wettability of a rock formation previously contacted with an oil-based mud (OBM), the method comprising: pumping a water-wetting pill into the rock formation, where the waterwetting pill is selected from the group consisting of: a composition selected from the group consisting of a miniemulsion, a nanoemulsion, an emulsion, and a microemulsion, which composition comprises: at least one surfactant; at least one non-polar fluid; and at least one polar fluid; and in situ emulsion-forming components comprising: at least one surfactant; and at least one polar fluid; thereby contacting the rock formation with the composition and or the in situ-formed emulsion, where in at least the case of the in situ emulsion-forming components, at least some of the first non-polar fluid is incorporated into the in situformed emulsion; changing the wettability of at least part of the rock formation to water-wet; and

subsequently pumping a second pill into the rock formation where the subsequent pill comprises water, the second pill being selected from the group consisting of fluid loss pills, crosslink pills, reservoir rock cleaning pills, horizontal healing pills and combinations thereof; where the at least one surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, fluorocarbon surfactants, silicon surfactants, cleavable, gemini surfactants, and extended surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, and mixtures thereof. 19. The method of claim 18 where in the surfactants: the nonionic surfactants are selected from the group consisting of alkyl polyglycosides, sorbitan esters, methyl glucoside esters, polyglycol esters, and alcohol ethoxylates; the anionic surfactants are selected from the group consisting of alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates; the cationic surfactants are selected from the group consisting of arginine methyl esters, alkanolamines, and alkylenediamides; and the extended chain surfactants comprise propoxylated and/or ethoxylated spacer arms, and mixtures thereof. 20. The method of claim 18 where the in situ emulsion-forming components further comprise a fluid selected from the group consisting of a non-polar fluid, a fluid of intermediate polarity and mixtures thereof. 21. The method of claim 18 where the surfactant in the water-wetting pill is an ionic surfactant and the water-wetting pill further comprises a co-surfactant.

NANOEMULSIONS
United States Patent Application 20100137168
What is claimed is: 1. A nanoemulsion composition comprising: (1) a continuous phase, (2) a discontinuous phase with a mean droplet size of less than 1000 nm, (3) a surfactant, and (4) a solid weighting agent; wherein, one of the phases (1) and (2) is a non-polar based phase and the other of these is a polar based phase. 2. The nanoemulsion composition of claim 1, wherein the mean droplet size of the discontinuous phase is less than 400 nm, the non-polar based phase is an oil phase and the polar based phase is an aqueous phase. 3. The nanoemulsion composition of claim 2, wherein the solid weighting agent is selected from the group consisting of barium sulfate, calcium carbonate, hematite, ilmenite, siderite, manganese tetraoxide and combinations thereof. 4. The nanoemulsion composition of claim 2, wherein the aqueous phase comprises water and a dissolved salt, the dissolved salt being different from the material chosen for the surfactant (3) and for the solid weighting agent (4). 5. The nanoemulsion composition of claim 4, wherein the dissolved salt in the aqueous phase is selected from the group consisting of: a chloride of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a bromide of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a sulfate of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a phosphate of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a formate of sodium, potassium, cesium or other cation; an ammonium salt; and combinations thereof. 6. The nanoemulsion composition of claim 2, further comprising a cosurfactant, where the co-surfactant is different from the material chosen for the surfactant (3) and for the solid weighting agent (4) and is selected from the group consisting of a mono-alcohol, a poly-alcohol, an organic acid, a salt of an organic acid, an amine, a polyethylene glycol, an ethoxylated solvent and combinations thereof. 7. The nanoemulsion composition of claim 1, wherein the surfactant (3) is selected from the group consisting of an anionic surfactant selected from the group consisting of alkali metal alkyl sulfates, alkyl ether sulfonates, alkyl sulfonates, alkylaryl sulfonates, linear and branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated sulfates, alcohol polyethoxylated sulfates, alcohol polypropoxylated polyethoxylated sulfates, alkyl disulfonates, alkylaryl disulfonates, alkyl disulfates, alkyl sulfosuccinates, alkyl ether sulfates, linear and branched ether sulfates, alkali metal carboxylates, fatty acid carboxylates, and phosphate esters; a nonionic surfactant selected from the group consisting of amides, diamides, polyglycol esters, alkyl polyglycosides, sorbitan esters, methyl glucoside esters and alcohol ethoxylates; a cationic surfactant selected from the group consisting of arginine methyl esters, alkanolamines and alkylenediamines; a surfactant containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, wherein the non-ionic spacer-arm central extension results from a process selected

from the group consisting of polypropoxylation, polyethoxylation and both; and dimeric surfactants, gemini surfactants, cleavable surfactants and fluorinated surfactants; and combinations thereof. 8. A method comprising: introducing a nanoemulsion into a wellbore where the nanoemulsion comprises: (1) a continuous phase, (2) a discontinuous phase with a mean droplet size of less than 1000 nm, and (3) a surfactant, wherein, one of the phases (1) and (2) is a non-polar based phase and the other of these is a polar based phase; and a further procedure selected from the group consisting of: drilling a wellbore using a fluid comprising the nanoemulsion; completing a well using a fluid comprising the nanoemulsion; remediating a subterranean formation, other than by acidizing, using a fluid comprising the nanoemulsion; stimulating a subterranean formation using a fluid comprising the nanoemulsion; fracturing a subterranean formation using a fluid comprising the nanoemulsion; and combinations thereof. 9. The method of claim 8 where the nanoemulsion further comprises (4) a solid weighting agent. 10. The method of claim 9, where in the nanoemulsion, the solid weighting agent is selected from the group consisting of barium sulfate, calcium carbonate, hematite, ilmenite, siderite, manganese tetraoxide and combinations thereof. 11. The method of claim 8, where in the nanoemulsion, the mean droplet size of the discontinuous phase is less than 400 nm, the non-polar based phase is an oil phase and the polar based phase is an aqueous phase. 12. The method of claim 11, where in the nanoemulsion, the aqueous phase comprises water and a dissolved salt, the dissolved salt being different from the material chosen for the surfactant (3) and for the solid weighting agent (4). 13. The method of claim 12, wherein the dissolved salt in the aqueous phase is selected from the group consisting of: a chloride of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a bromide of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a sulfate of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a phosphate of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a formate of sodium, potassium, cesium or other cation; an ammonium salt; and combinations thereof. 14. The method of claim 8, where the nanoemulsion further comprises a cosurfactant, where the cosurfactant is different from the material chosen for the surfactant (3) and for the solid weighting agent (4) and is selected from the group consisting of a mono-alcohol, a poly-alcohol, an organic acid, a salt of an organic acid, an amine, a polyethylene glycol, an ethoxylated solvent and combinations thereof. 15. The method of claim 8, where in the nanoemulsion the surfactant (3) is selected from the group consisting of an anionic surfactant selected from the group consisting of alkali metal alkyl sulfates, alkyl ether sulfonates, alkyl sulfonates, alkylaryl sulfonates, linear and branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated sulfates, alcohol polyethoxylated sulfates, alcohol polypropoxylated polyethoxylated sulfates, alkyl disulfonates, alkylaryl disulfonates, alkyl disulfates, alkyl sulfosuccinates, alkyl ether sulfates, linear and branched ether sulfates, alkali metal carboxylates, fatty acid carboxylates

and phosphate esters; a nonionic surfactant selected from the group consisting of amides, diamides, polyglycol esters, alkyl polyglycosides, sorbitan esters, methyl glucoside esters and alcohol ethoxylates; a cationic surfactant selected from the group consisting of arginine methyl esters, alkanolamines and alkylenediamines; a surfactant containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group, wherein the non-ionic spacer-arm central extension results from a process selected from the group consisting of polypropoxylation, polyethoxylation and both; dimeric surfactants, gemini surfactants, cleavable surfactants, fluorinated surfactants; and combinations thereof. 16. The method of claim 9 where the fluid has an improved property selected from the group consisting of reduced friction pressure loss, reduced weighting agent subsidence and both, as compared with an otherwise identical fluid absent the nanoemulsion. 17. A method comprising drilling a wellbore using a drilling fluid comprising a nanoemulsion where the nanoemulsion comprises: (1) a continuous phase, (2) a discontinuous phase with a mean droplet size of less than 400 nm, and (3) a surfactant, (4) a solid weighting agent; wherein, one of the phases (1) and (2) is a non-polar based phase and the other of these is a polar based phase. 18. The method of claim 17, where in the nanoemulsion, the solid weighting agent is selected from the group consisting of barium sulfate, calcium carbonate, hematite, ilmenite, siderite, manganese tetraoxide and combinations thereof. 19. The method of claim 17, where in the nanoemulsion, the polar based phase comprises water and a dissolved salt, the dissolved salt being different from the material chosen for the surfactant (3) and for the solid weighting agent (4). 20. The method of claim 17, where the nanoemulsion further comprises a cosurfactant, where the cosurfactant is different from the material chosen for the surfactant (3) and for the solid weighting agent (4) and is selected from the group consisting of a mono-alcohol, a poly-alcohol, an organic acid, a salt of an organic acid, an amine, a polyethylene glycol, an ethoxylated solvent and combinations thereof. 21. A method of making a nanoemulsion composition comprising: (1) mixing a group of components comprising an oil and a surfactant, (2) adding an aqueous salt solution to the result of (1) with mixing, (3) mixing the result of (2), (4) adding more of the aqueous salt solution to the result of (3) while mixing, and (5) mixing the result of (4). 22. The method of claim 21, wherein the group of components of (1) further comprises a co-surfactant. 23. The method of claim 22, wherein the aqueous salt solution comprises a salt that is selected from the group consisting of: a chloride of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a bromide of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a sulfate of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a phosphate of sodium, potassium, calcium, silver, cobalt, nickel, copper, zinc or iron; a formate of sodium, potassium, cesium or other cation; ammonium chloride, bromide, sulfate, phosphate, formate; an ammonium salt; and combinations thereof; with the proviso that the average weight percentage of the salt in the aqueous salt solution is at

least one-tenth of the weight percentage of this salt in water at 25 C. at maximum solubility. 24. The method of claim 21, further comprising adding a solid weighting agent to the result of (5). 25. The method of claim 21, wherein the adding with mixing of (2) occurs until the viscosity of the composition of (2) reaches a viscosity of at least about 275 cP when measured at a shear rate of 500/s at 25 C.; and the mixing of (3) occurs until the viscosity of the composition of (3) drops below about 20 cP when measured at a shear rate of 500/s at 25 C. 26. The nanoemulsion composition produced by the method of claim 21.

MICROEMULSIONS TO CONVERT OBM FILTER CAKES TO WBM FILTER CAKES HAVING FILTRATION CONTROL
United States Patent Application 20100216671
What is claimed is: 1. A thermodynamically stable, macroscopically homogeneous, single phase microemulsion (SPME) comprising: a polar phase; a nonpolar phase; a surfactant; and a water-soluble filtration control additive selected from the group consisting of solid particulates, polymers and mixtures thereof. 2. The SPME of claim 1 where the surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactant, cationic surfactants and amphoteric surfactants. 3. The SPME of claim 1 further comprising an acid selected from the group of inorganic acids consisting of hydrochloric acid, sulfuric acid, and mixtures thereof, and organic acids consisting of acetic acid, formic acid and salts of these organic acids, and mixtures of one or more of these acids.

4. The SPME of claim 1 further comprising at least one polyamino carboxylic acid or salt thereof, where the concentration of polyamino carboxylic acid or a salt thereof in the microemulsion ranges from 1 to 30 volume %. 5. The SPME of claim 1 where in the filtration control additive, the solid particulates are selected from the group consisting of sized salts, hematite, ilmenite, manganese tetroxide, and mixtures thereof, and where the water-soluble polymers are selected from the group consisting of natural and synthetic polymers and copolymers and mixtures thereof. 6. The SPME of claim 1 where the proportion of filtration control additive in the SPME ranges from about 0.1 to about 10 lb/bbl. 7. The SPME of claim 1 where the nonpolar phase is selected from the group consisting of synthetic base and mineral oils, ester fluids, paraffins, and isomerized olefins. 8. A thermodynamically stable, macroscopically homogeneous, single phase microemulsion (SPME) comprising: a polar phase; a nonpolar phase; a surfactant selected from the group consisting of non-ionic surfactants, anionic surfactant, cationic surfactants and amphoteric surfactants; and from about 0.1 to about 10 lb/bbl, based on the SPME, of a water-soluble filtration control additive selected from the group consisting of solid particulates, polymers and mixtures thereof. 9. The SPME of claim 8 further comprising an acid selected from the group of inorganic acids consisting of hydrochloric acid, sulfuric acid, and mixtures thereof, and organic acids consisting of acetic acid, formic acid and salts of these organic acids, and mixtures of one or more of these acids. 10. The SPME of claim 8 further comprising at least one polyamino carboxylic acid or salt thereof, where the concentration of polyamino carboxylic acid or a salt thereof in the microemulsion ranges from 1 to 30 volume %. 11. The SPME of claim 8 where in the filtration control additive, the solid particulates are selected from the group consisting of sized salts, hematite, ilmenite, manganese tetroxide, and mixtures thereof, and where the water-soluble polymers are selected from the group consisting of natural and synthetic polymers and copolymers and mixtures thereof. 12. The SPME of claim 8 where the nonpolar phase is selected from the group consisting of synthetic base and mineral oils, ester fluids, paraffins, and isomerized olefins. 13. A thermodynamically stable, macroscopically homogeneous, single phase microemulsion (SPME) comprising: a polar phase; a nonpolar phase; a surfactant; and from about 0.1 to about 10 lb/bbl, based on the SPME, of a water-soluble filtration control additive selected from the group consisting of sized salts, hematite, ilmenite, manganese tetroxide, and mixtures thereof, and where the water-soluble polymers are selected from the group consisting of natural and synthetic polymers and copolymers and mixtures thereof.

14. The SPME of claim 13 where the surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactant, cationic surfactants and amphoteric surfactants. 15. The SPME of claim 13 further comprising an acid selected from the group of inorganic acids consisting of hydrochloric acid, sulfuric acid, and mixtures thereof, and organic acids consisting of acetic acid, formic acid and salts of these organic acids, and mixtures of one or more of these acids. 16. The SPME of claim 13 further comprising at least one polyamino carboxylic acid or salt thereof, where the concentration of polyamino carboxylic acid or a salt thereof in the microemulsion ranges from 1 to 30 volume %. 17. The SPME of claim 13 where the nonpolar phase is selected from the group consisting of synthetic base and mineral oils, ester fluids, paraffins, and isomerized olefins.