Oilfield chemicals with attached spin probes
Detecting a spin probe in an oilfield fluid may indicate or determine the amount of the particular chemicals within an oilfield fluid. The detection of the spin probe may also indicate at least one property of the oilfield fluid, such as but not limited to pH, dielectric constant, rotational freedom of the spin probe, at least one chemical, the concentration of at least one chemical, residue of at least one chemical in the fluid, the speciation of coupled chemistry between the spin probe and the chemical, and combinations thereof. In one non-limiting embodiment, the spin probe may be attached to at least one chemical. The oilfield fluid may be or include, but is not limited to, a drilling fluid, a completion fluid, a production fluid, a servicing fluid, and combinations thereof.
1. A method comprising:
detecting at least one spin probe within its microenvironment of an oilfield fluid, wherein the presence of the at least one spin probe indicates the presence of at least one chemical, pH of the microenvironment, dielectric constant of the microenvironment, rotational freedom of the at least one spin probe, the concentration of the at least one chemical, residue of the at least one chemical in the fluid, the speciation of the coupled chemistry between the at least one spin probe and the at least one chemical, the placement origin of the at least one chemical, secondary phenomena of the microenvironment, and combinations thereof; wherein the oilfield fluid is selected from the group consisting of a drilling fluid, a completion fluid, a production fluid, a servicing fluid, and combinations thereof; wherein the concentration of the at least one spin probe within the oilfield fluid ranges from about 10 ppm to about 50,000 ppm; and
where the at least one spin probe was added to the oilfield fluid prior to detecting the at least one spin probe, and wherein the at least one spin probe is attached to the at least one chemical wherein the attachment of the at least one spin probe to the at least one chemical is a covalent attachment via a reaction selected from the group consisting of esterification, nucleophilic addition, substitution, elimination, rearrangement, and combinations thereof.
2. The method of claim 1 , wherein the at least one chemical is selected from the group consisting of an oil-based chemical, a water-based chemical, and combinations thereof.
3. The method of claim 1 , wherein the at least one spin probe is selected from the group consisting of [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl](TEMPO); [2,2,5,5-tetramethylpyrrolidin-1-yloxyl] (Proxyl); [2,2,5,5-tetramethyl-3-oxazolidinoxy] (Doxo); [2,2,5,5tetramethyl-1-dihydropyrrolinoxy](Proxo); [2,2,3,4,5,5-hexamethyl-imidazoline-1yloxyl] (Imidazo); [2,5-dihydro-3-(hydroxymethyl)-2,2,5,5-tetramethyl-1H-pyrrol-1-yloxy]; [5-(Diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide] (DEPMPO); [5-(Diisopropoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide]; [2-Diisopropylphosphono-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide] (DIPPMPO); [5-tert-Butoxycarbonyl-5-methyl-1-pyrroline-N-oxide] (BMPO); [5,5-Dimethyl-1-pyrroline-N-oxide] (DMPO); [2-Ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide] (EMPO); [4-Hydroxy-5,5-dimethyl-2-trifluoromethylpyrroline-1-oxide] (FDMPO); [bis-(2,2,5,5-Tetramethyl-3-imidazoline-1-oxyl-4-yl) disulfide, biradical] (RSSR); [4-(Dimethylamino)-2-ethyl-5,5-dimethyl-2-pyridine-4-yl-2,5-dihydro-1H-imidazol-1-oxyl] (DEDPI); [(1-Oxyl-2,2,5,5-tetramethylpyrroline-3-methyl)] methanethiosulfonate (MTSSL); [2-n-Heptyl-4-hydroxyquinoline N-oxide] (HQNO); [N-t-Butyl-α-phenylnitrone] (PBN); [N-(Dithiocarbamoyl)-N-methyl-D-glucamine (MGD. Na.H2O)]; Diethyldithiocarbamate; [2-(4-Carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide. potassium salt] (Carboxy-PTIO.K); transition metal ions, lanthanides metal ions, rare earth metals, salts and complexes thereof; and combinations thereof.
4. The method of claim 1 , wherein the amount of the at least one chemical in the oilfield fluid ranges from about 10 ppm to about 20,000 ppm.
5. The method of claim 1 , wherein the at least one chemical is selected from the group consisting of asphaltene inhibitors, paraffin inhibitors, scale inhibitors, corrosion inhibitors, biocides, low dose hydrate inhibitors, oxygen scavengers, hydrogen sulfide scavengers, demulsifiers, reverse emulsion breakers, water clarifiers, drag reducers, foamers, defoamers, fracturing fluid additives, water flooding additives, carbon dioxide flooding additives, and combinations thereof, and combinations thereof.
6. A method for probing an oilfield fluid for at least one spin probe attached to at least one chemical, wherein the method comprises:
adding the at least one spin probe attached to the at least one chemical to the oilfield fluid; wherein the attachment of the at least one spin probe to the at least one chemical is a covalent attachment via a reaction selected from the group consisting of esterification, nucleophilic addition, substitution, elimination, rearrangement, and combinations thereof;
detecting the at least one spin probe attached to the at least one chemical within an oilfield fluid selected from the group consisting of a drilling fluid, a completion fluid, a production fluid, a servicing fluid, and combinations thereof; and wherein the at least one chemical is selected from the group consisting of an oil-based chemical, a water-based chemical, and combinations thereof; and
wherein the detecting the at least one spin probe within its microenvironment indicates the at least one chemical, pH of the microenvironment, dielectric constant of the microenvironment, rotational freedom of the spin probe, the concentration of the at least one chemical, residue of at least one chemical in the oilfield fluid, the speciation of the coupled chemistry between the spin probe and the chemical, the placement origin of the at least one chemical, secondary phenomena of the microenvironment, and combinations thereof.
7. The method of claim 6 , further comprising detecting an amount of the at least one spin probe within the oilfield fluid, wherein the amount of the at least one spin probe ranges from about 10 ppm to about 50,000 ppm.
8. The method of claim 6 , wherein the at least one spin probe is selected from the group consisting of [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] (TEMPO); [2,2,5,5-tetramethylpyrrolidin-1-yloxyl] (Proxyl); [2,2,5,5-tetramethyl-3-oxazolidinoxy] (Doxo); [2,2,5,5tetramethyl-1-dihydropyrrolinoxy] (Proxo); [2,2,3,4,5,5-hexamethyl-imidazoline-1yloxyl] (Imidazo); [2,5-dihydro-3-(hydroxymethyl)-2,2,5,5-tetramethyl-1H-pyrrol-1-yloxy]; [5-(Diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide] (DEPMPO); [5-(Diisopropoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide]; [2-Diisopropylphosphono-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide] (DIPPMPO); [5-tert-Butoxycarbonyl-5-methyl-1-pyrroline-N-oxide] (BMPO); [5,5-Dimethyl-1-pyrroline-N-oxide] (DMPO); [2-Ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide] (EMPO); [4-Hydroxy-5,5-dimethyl-2-trifluoromethylpyrroline-1-oxide] (FDMPO); [bis-(2,2,5,5-Tetramethyl-3-imidazoline-1-oxyl-4-yl) disulfide, biradical] (RSSR); [4-(Dimethylamino)-2-ethyl-5,5-dimethyl-2-pyridine-4-yl-2,5-dihydro-1H-imidazol-1-oxyl] (DEDPI); [(1-Oxyl-2,2,5,5-tetramethylpyrroline-3-methyl)] methanethiosulfonate (MTSSL); [2-n-Heptyl-4-hydroxyquinoline N-oxide] (HQNO); [N-t-Butyl-α-phenylnitrone] (PBN); [N-(Dithiocarbamoyl)-N-methyl-D-glucamine (MGD.Na.H2O)]; Diethyldithiocarbamate; [2-(4-Carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide. potassium salt] (Carboxy-PTIO.K); transition metal ions, lanthanides metal ions, rare earth metals, salts and complexes thereof; and combinations thereof.
9. The method of claim 6 , wherein the at least one spin probe has a g value ranging from about 1.4 to about 3.0.
10. A method comprising: detecting at least one spin probe within its microenvironment of an oilfield fluid, wherein the presence of the at least one spin probe indicates the presence of at least one chemical, pH of the microenvironment, dielectric constant of the microenvironment, rotational freedom of the at least one spin probe, the concentration of the at least one chemical, residue of the at least one chemical in the fluid, the speciation of the coupled chemistry between the at least one spin probe and the at least one chemical, the placement origin of the at least one chemical, secondary phenomena of the microenvironment, and combinations thereof; wherein the oilfield fluid is selected from the group consisting of a drilling fluid, a completion fluid, a production fluid, a servicing fluid, and combinations thereof; wherein the at least one spin probe is selected from the group consisting of [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] (TEMPO); [2,2,5,5-tetramethylpyrrolidin-1-yloxyl] (Proxyl); [2,2,5,5-tetramethyl-3-oxazolidinoxy] (Doxo); [2,2,5,5tetramethyl-1-dihydropyrrolinoxy] (Proxo); [2,2,3,4,5,5-hexamethyl-imidazoline-1yloxyl] (Imidazo); [2,5-dihydro-3-(hydroxymethyl)-2,2,5,5-tetramethyl-1H-pyrrol-1-yloxy]; [5-(Diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide] (DEPMPO); [5-(Diisopropoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide]; [2-Diisopropylphosphono-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide] (DIPPMPO); [5-tert-Butoxycarbonyl-5-methyl-1-pyrroline-N-oxide](BMPO); [5,5-Dimethyl-1-pyrroline-N-oxide] (DMPO); [2-Ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide] (EMPO); [4-Hydroxy-5,5-dimethyl-2-trifluoromethylpyrroline-1-oxide] (FDMPO); [bis-(2,2,5,5-Tetramethyl-3-imidazoline-1-oxyl-4-yl) disulfide, biradical] (RSSR); [4-(Dimethylamino)-2-ethyl-5,5-dimethyl-2-pyridine-4-yl-2,5-dihydro-1H-imidazol-1-oxyl] (DEDPI); [(1-Oxyl-2,2,5,5-tetramethylpyrroline-3-methyl)]methanethiosulfonate (MTSSL); [2-n-Heptyl-4-hydroxyquinoline N-oxide](HQNO); [N-t-Butyl-α-phenylnitrone] (PBN); [N-(Dithiocarbamoyl)-N-methyl-D-glucamine (MGD.Na.H 2 O)]; Diethyldithiocarbamate; [2-(4-Carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide. potassium salt] (Carboxy-PTIO.K); transition metal ions, lanthanides metal ions, rare earth metals, salts and complexes thereof; and combinations thereof.