Methods of treating flowback water from a subterranean formation penetrated by a well bore are provided, comprising: (a) providing remediated flowback water having a ferrous iron (Fe+2) ion concentration of less than about 100 milligrams of ferrous iron ion per liter of flowback water, a barium ion
Methods of treating flowback water from a subterranean formation penetrated by a well bore are provided, comprising: (a) providing remediated flowback water having a ferrous iron (Fe+2) ion concentration of less than about 100 milligrams of ferrous iron ion per liter of flowback water, a barium ion (Ba+2) concentration of less than about 500 milligrams of barium ion per liter of flowback water, and a calcium ion (Ca+) concentration of at least about 1,000 milligrams of calcium ion per liter of remediated flowback water; and (b) treating the flowback water with: (i) at least one friction reducing agent; and (ii) at least one scale formation inhibiting agent and/or at least one iron precipitation control agent to provide treated flowback water which can be reused as fracturing fluid in a well drilling operation.
대표청구항▼
1. A method of treating flowback water from a subterranean formation penetrated by a well bore, comprising: (1) providing flowback water having a ferrous iron (Fe+2) ion concentration of less than about 100 milligrams of ferrous iron ion per liter of flowback water, a barium ion (Ba+2) concentration
1. A method of treating flowback water from a subterranean formation penetrated by a well bore, comprising: (1) providing flowback water having a ferrous iron (Fe+2) ion concentration of less than about 100 milligrams of ferrous iron ion per liter of flowback water, a barium ion (Ba+2) concentration of less than about 500 milligrams of barium ion per liter of flowback water, and a calcium ion (Ca+) concentration of at least about 1,000 milligrams of calcium ion per liter of flowback water;(2) treating the flowback water with a fluid treatment system comprising: (a) at least one friction reducing agent comprising a water-in-oil emulsion composition comprising: 5% to 99% by weight of a water-in-oil emulsion polymer comprising at least one polyacrylamide comprising one or more repeat units according to Formula I: wherein each occurrence of R1 is independently selected from H, methyl and ethyl; n is an integer from 10 to 10,000,000; Z is selected from —O—and —NR2—; and each occurrence of R2 is independently selected from the group consisting of H, C1-C22 linear, branched or cyclic alkyl, aryl, alkaryl, aralkyl or alkenyl group,—R3—NR22,—R3—N+R23 X, and —R3—SO3Y, wherein R2 is as previously defined; R3 is a divalent linking group selected from the group consisting of C1-C22 linear, branched or cyclic alkylene, arylene, alkarylene, aralkylene or alkenylene, poly(ethyleneoxide) and poly(propyleneoxide); Y is H or an alkali metal ion; and X is a halide or methylsulfate, wherein the polyacrylamide has a molecular weight of 1,000,000 to 50,000,000 grams per mole;(ii) 0.1% to 10% by weight of one or more inorganic microparticles;(iii) 0.5% to 90% by weight of a carrier solvent; and(iv) 0 to 90% by weight of a fluidizing agent;(b) at least one scale formation inhibiting agent selected from the group consisting of water-soluble polycarboxylates, phosphonates, metal salts, sulfonates, and mixtures thereof,and (c) at least one iron control agent comprising (1) at least one carboxylic acid functional group and (2) at least one sulfur-containing group selected from the group consisting of sulfonyl functional groups, sulfonate functional groups, and mixtures thereof, wherein the material (a) has a weight average molecular weight ranging from about 500 to about 30,000 grams per mole, to provide treated flowback water; and(3) introducing the treated flowback water into a subterranean formation as an aqueous fracturing fluid for hydraulic fracturing of the formation. 2. The method according to claim 1, wherein the treated flowback water is reused as a fracturing fluid. 3. The method according to claim 1, wherein the subterranean formation is a Marcellus Shale formation. 4. The method according to claim 1, wherein the flowback water has a ferrous iron (Fe+2) ion concentration of less than about 50 milligrams of ferrous iron ion per liter of flowback water. 5. The method according to claim 1, wherein the flowback water has a barium ion (Ba++2) concentration of less than about 100 milligrams of barium ion per liter of flowback water. 6. The method according to claim 1, wherein the flowback water has a Total Dissolved Solids (TDS) content of greater than about 10,000 milligrams of dissolved solids per liter of flowback water. 7. The method according to claim 1, wherein the at least one friction reducing agent further comprises at least one additional friction reducing agent selected from the group consisting of guar gums, other polyacrylamide(s) different from polyacrylamide of (i), hydratable cellulosic materials, viscoelastic surfactants, and mixtures thereof. 8. The method according to claim 7, wherein the hydratable cellulosic material is selected from the group consisting of cellulose, methyl cellulose, hydroxyethyl cellulose, grafted hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, carboxymethylhydroxyethyl cellulose and mixtures thereof. 9. The method according to claim 1, wherein the scale formation inhibiting agent comprises at least one water-soluble polycarboxylate comprising a polymer derived from at least one carboxylic acid functional, ethylenically unsaturated material selected from the group consisting of acrylic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, fumaric acid, phosphinocarboxylic acid, maleic acid or anhydride, itaconic acid, α-halo acrylic acid, β-carboxyethyl acrylic acid and mixtures thereof. 10. The method according to claim 1, wherein the scale formation inhibiting agent comprises at least one water-soluble phosphonated selected from the group consisting of hydroxyphosphono acetic acid (HPA), diethylenetriamine-penta(methylenephosphonic acid), hexamethylenediaminetetra(methylenephosphonic acid), 2-phosphono-1,2,4-tricarboxybutane, amino tri(methylene phosphonic acid), hydroxyethylidene diphosphonic acid, phosphonosuccinic acid, benzene phosphonic acid, 2-aminoethyl phosphonic acid, polyamino phosphonates, and salts thereof where they exist. 11. The method according to claim 1, wherein the scale formation inhibiting agent comprises at least one water-soluble phosphonate polyether selected from the group consisting of polyamino methylene phosphonates. 12. The method according to claim 1, wherein the scale formation inhibiting agent comprises at least one water-soluble metal salt selected from the group consisting of water-soluble salts of zinc, molybdenum, chromate, sodium silicate and mixtures thereof. 13. The method according to claim 1, wherein the scale formation inhibiting agent comprises at least one water-soluble sulfonate comprising a polymer derived from at least one monomer selected from the group consisting of 2-acrylamido-2 -methylpropylsulfonic acid, 2-methacrylamido-2-methylpropylsulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, sulfo alkyl acrylate or methacrylate, allyl or methallyl sulfonic acid, sulfonic acid acrylate, 3-methacrylamido-2-hydroxy propyl sulfonic acid, their salts and mixtures thereof. 14. The method according to claim 1, wherein the scale formation inhibiting agent comprises at least one water-soluble phosphonate and at least one water-soluble polycarboxylate. 15. The method according to claim 1, wherein the scale formation inhibiting agent comprises at least one water-soluble phosphonate, at least one water-soluble polycarboxylate and at least one material (a 1) comprising (1) at least one carboxylic acid functional group and (2) at least one sulfur-containing group selected from the group consisting of sulfonyl functional groups, sulfonate functional groups and mixtures thereof. 16. The method according to claim 15, wherein the scale formation inhibiting agent comprises 2-phosphono-1,2,4-tricarboxybutane, polyacrylic acid and a reaction product prepared from acrylic acid and 2-acrylamido-2-methylpropyl sulfonic acid. 17. The method according to claim 1, wherein the at least one iron control agent comprises at least one sulfonyl functional group. 18. The method according to claim 1, wherein the at least one iron control agent comprises at least one sulfonate functional group. 19. The method according to claim 1, wherein the at least one iron control agent comprises (i) at least one sulfonated styrene moiety: and (ii) at least one moiety derived from maleic anhydride: wherein each M is independently selected from NH 4, H, Na, or K. 20. The method according to claim 1, further comprising treating the flowback water with at least one surfactant. 21. The method according to claim 20, wherein the at least one surfactant is selected from the group consisting of alkanolamides, polyoxyethylene derivatives of sorbitan esters, sorbitan monooleate, sorbitan monostearate, C6-C22 linear or branched alkyl ethoxylates having 1 to 30 oxyethylene units, C6-C22 linear or branched alkyl propoxylates having 1 to 30 oxypropylene units, C6-C22 linear or branched alkyl ethoxylatespropoxylates having 1 to 30 combined oxyethylene and propoxylate units, alkylaryl ethoxylates containing a C6-C22 aryl group and having 1 to 30 oxyethylene units, hexadecyl sodium phthalate, cetyl sodium phthalate, stearyl sodium phthalate, ethylene oxide condensates of fatty acid amides, alpha olefin sulfonates, ether sulfates, ether sulfonates, alkoxylated alcohol surfactants, sulfosuccinates, and mixtures thereof. 22. The method according to claim 1, further comprising treating the flowback water with at least one biocide. 23. The method according to claim 1, wherein the flowback water is remediated flowback water. 24. The method according to claim 23, further comprising pretreating raw flowback water to remove a portion of at least one contaminant selected from the group consisting of TDS, iron ions, iron-containing compounds, barium ions, barium-containing compounds, strontium ions, strontium-containing compounds, calcium ions and calcium-containing compounds to provide the remediated flowback water. 25. The method according to claim 24, further comprising diluting the pretreated flowback water with fresh water having a TDS of less than about 100 milligrams of dissolved solids per liter of fresh water to provide the remediated flowback water. 26. The method according to claim 1, wherein the at least one iron control agent is a reaction product or salt thereof, wherein the reaction product is prepared from reactants comprising: (a) at least one ethylenically unsaturated, carboxylic acid functional material or anhydride thereof; and(b) at least one ethylenically unsaturated, sulfur-containing material, wherein the ethylenically unsaturated sulfur-containing material comprises at least one sulfur-containing group selected from the group consisting of sulfonyl functional groups or sulfonate functional groups. 27. The method according to claim 26, wherein the at least one ethylenically unsaturated, carboxylic acid functional material or anhydride thereof comprises about 10 to about 90 weight percent of the reactants, on a basis of total weight of the reactants. 28. The method according to claim 26, wherein the weight ratio of ethylenically unsaturated, carboxylic acid functional material or anhydride thereof to ethylenically unsaturated, sulfonyl functional or sulfonate functional material ranges from about 1:20 to about 20:1. 29. The method according to claim 26, wherein the ethylenically unsaturated, carboxylic acid functional material or salt thereof has acrylic or vinyl functionality. 30. The method according to claim 26, wherein the ethylenically unsaturated, carboxylic acid functional material is selected from the group consisting of acrylic acid, methacrylic acid, α-halo acrylic acid, maleic acid, itaconic acid, vinyl acetic acid, allyl acetic acid, fumaric acid, β-carboxyethyl acrylic acid, salts thereof, and mixtures thereof. 31. The method according to claim 26, wherein ethylenically unsaturated, carboxylic acid functional anhydride is maleic anhydride. 32. The method according to claim 26, wherein the ethylenically unsaturated, sulfur-containing material has vinyl functionality, acrylic functionality, acrylamido functionality, acrylamido alkyl functionality or acrylamido aryl functionality. 33. The method according to claim 26, wherein the ethylenically unsaturated, sulfur-containing material is selected from the group consisting of 2-acrylamido-2-methylpropyl sulfonic acid; allyl-2-hydroxypropyl sulfonic acid ether; allyl-2-hydroxypropyl sulfonate ether; sulfomethylacrylamide; 2-propene-1-sulfonic acid, 2-methyl; 2-methacrylamido-2-methylpropyl sulfonic acid; styrene sulfonic acid; vinyl sulfonic acid; sulfoalkyl acrylate; sulfoalkyl methacrylate; sulfoalkyl acrylamide; ally sulfonic acid; methallyl sulfonic acid; para methallyloxy benzene sulfonic acid; allyl-2-hydroxypropyl sulfonic acid; 3-methacrylamido-2-hydroxypropyl sulfonic acid; sulfonic acid acrylate; sulfonated phenolmethacrylic ether; salts thereof and mixtures thereof. 34. The method according to claim 26, wherein the iron control agent is prepared from acrylic acid and 2-acrylamido-2-methylpropyl sulfonic acid. 35. The method according to claim 34, wherein the iron control agent is prepared from about 25 to about 95 mole percent of acrylic acid and about 5 to about 75 mole percent of 2-acrylamido-2-methylpropyl sulfonic acid. 36. The method according to claim 26, wherein the at least one ethylenically unsaturated, sulfur-containing material comprises about 5 to about 95 weight percent of the reactants, on a basis of total weight of the reactants. 37. The method according to claim 26, wherein the reactants further comprise at least one ethylenically unsaturated material that is chemically different from (1) the at least one ethylenically, unsaturated, carboxylic acid functional material or anhydride thereof; and (2) the at least one ethylenically unsaturated, sulfur-containing material. 38. The method according to claim 37, wherein the at least one ethylenically unsaturated material comprises up to about 60 weight percent of the reactants, on a basis of total weight of the reactants. 39. The method according to claim 26, wherein the reactants further comprise at least one monomer selected from the group consisting of acrylamides, vinyl esters, vinyl acetates and mixtures thereof, the monomer being different from the ethylenically unsaturated, carboxylic acid functional material or anhydride thereof and the at least one ethylenically unsaturated, sulfur-containing material. 40. The method according to claim 39, wherein the monomer is selected from the group consisting of tert-butyl acrylamide; 2-propenoic acid, 2-methyl-, methyl ester; and mixtures thereof. 41. The method according to claim 26, wherein the reactants further comprise at least one ethylenically unsaturated polyalkylene oxide. 42. The method according to claim 41, wherein the ethylenically unsaturated polyalkylene oxide is selected from the group consisting of allyl polyethylene glycol, methallyl polyethylene glycol, polyethylene glycol acrylate, polyethylene glycol methacrylate, methoxy allyl polyethylene oxide, alkoxyallyl polyethylene oxide, allyl polypropylene glycol, methallyl polypropylene glycol, polypropylene glycol acrylate, polypropylene glycol methacrylate, methoxy allyl polypropylene oxide, alkoxyallyl polypropylene oxide, and mixtures thereof. 43. A method of treating flowback water from a subterranean formation penetrated by a well bore for reuse as a fracturing fluid, comprising: (a) providing flowback water having a ferrous iron (Fe+2) ion concentration of less than about 100 milligrams of ferrous iron ion per liter of flowback water, a barium ion (Ba +2) concentration of less than about 500 milligrams of barium ion per liter of flowback water, and a calcium ion (Ca+) concentration of at least about 1,000 milligrams of calcium ion per liter of flowback water; and(b) treating the flowback water with a fluid treatment system comprising: (i) at least one friction reducing agent comprising a water-in-oil emulsion composition comprising: (1) 5 % to 99% by weight of a water-in-oil emulsion polymer comprising one or more repeat units according to Formula I: wherein each occurrence of R1 is independently selected from H, methyl and ethyl; n is an integer from 10 to 10,000,000 ; Z is selected from —O —and —NR2—; and each occurrence of R2 is independently selected from the group consisting of H, C1-C22 linear, branched or cyclic alkyl, aryl, alkaryl, aralkyl or alkenyl group,—R3—NR22—R3—N+R23 X, and —R3—SO3 Y, wherein R2 is as previously defined; R3 is a divalent linking group selected from the group consisting of C1-C22 linear, branched or cyclic alkylene, arylene, alkarylene, aralkylene or alkenylene, poly(ethyleneoxide) and poly(propyleneoxide); Y is H or an alkali metal ion; and X is a halide or methylsulfate, wherein the polyacrylamide has a molecular weight of 1,000,000 to 50,000,000grams per mole;(2) 0.1 % to 10 % by weight of one or more inorganic microparticles;(3) 0.5% to 90 % by weight of a carrier solvent; and(4) 0 to 90 % by weight of a fluidizing agent.; and(ii) at least one scale formation inhibiting agent comprising 2-phosphono-1,2,4-tricarboxybutane, polyacrylic acid and a reaction product prepared from acrylic acid and 2-acrylamido-2-methylpropyl sulfonic acid, and(iii) at least one iron control agent comprising () at least one carboxylic acid functional group and (2) at least one sulfur-containing group selected from the group consisting of sulfonyl functional groups, sulfonate functional groups, and mixtures thereof, wherein the material (a) has a weight average molecular weight ranging from about 500 to about 1,000,000 grams per mole to provide a treated flowback water; and(3) introducing the treated flowback water into a subterranean formation as an aqueous fracturing fluid for hydraulic fracturing of the formation.
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