US20100307757A1 - Aqueous solution for controlling bacteria in the water used for fracturing - Google Patents
Aqueous solution for controlling bacteria in the water used for fracturing Download PDFInfo
- Publication number
- US20100307757A1 US20100307757A1 US12/793,479 US79347910A US2010307757A1 US 20100307757 A1 US20100307757 A1 US 20100307757A1 US 79347910 A US79347910 A US 79347910A US 2010307757 A1 US2010307757 A1 US 2010307757A1
- Authority
- US
- United States
- Prior art keywords
- fluid
- subterranean formation
- sodium hypochlorite
- acid
- equipment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 99
- 241000894006 Bacteria Species 0.000 title description 26
- 239000007864 aqueous solution Substances 0.000 title description 2
- 239000012530 fluid Substances 0.000 claims abstract description 134
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 58
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 36
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000001632 sodium acetate Substances 0.000 claims abstract description 34
- 235000017454 sodium diacetate Nutrition 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000872 buffer Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000011282 treatment Methods 0.000 claims abstract description 21
- 244000005700 microbiome Species 0.000 claims abstract description 19
- 230000002829 reductive effect Effects 0.000 claims abstract description 7
- 230000003247 decreasing effect Effects 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 116
- 230000000694 effects Effects 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 238000005553 drilling Methods 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 63
- 239000000654 additive Substances 0.000 description 29
- 239000003638 chemical reducing agent Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000005755 formation reaction Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 17
- 230000001580 bacterial effect Effects 0.000 description 16
- 239000000523 sample Substances 0.000 description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 15
- 229910052801 chlorine Inorganic materials 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- 239000003139 biocide Substances 0.000 description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000003115 biocidal effect Effects 0.000 description 9
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- -1 quat amines Chemical class 0.000 description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000002147 killing effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 208000010392 Bone Fractures Diseases 0.000 description 3
- 206010017076 Fracture Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 229940093915 gynecological organic acid Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 241001148470 aerobic bacillus Species 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- 239000004318 erythorbic acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000954 titration curve Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 238000004457 water analysis Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- GCGWQXSXIREHCF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;zirconium Chemical compound [Zr].OCCN(CCO)CCO GCGWQXSXIREHCF-UHFFFAOYSA-N 0.000 description 1
- PAITUROHVRNCEN-UHFFFAOYSA-J 2-hydroxyacetate;zirconium(4+) Chemical compound [Zr+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O PAITUROHVRNCEN-UHFFFAOYSA-J 0.000 description 1
- LYPJRFIBDHNQLY-UHFFFAOYSA-J 2-hydroxypropanoate;zirconium(4+) Chemical compound [Zr+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O LYPJRFIBDHNQLY-UHFFFAOYSA-J 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- ZCGHEBMEQXMRQL-UHFFFAOYSA-N benzyl 2-carbamoylpyrrolidine-1-carboxylate Chemical compound NC(=O)C1CCCN1C(=O)OCC1=CC=CC=C1 ZCGHEBMEQXMRQL-UHFFFAOYSA-N 0.000 description 1
- 230000002599 biostatic effect Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- QAYICIQNSGETAS-UHFFFAOYSA-N dazomet Chemical compound CN1CSC(=S)N(C)C1 QAYICIQNSGETAS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RGRFMLCXNGPERX-UHFFFAOYSA-L oxozirconium(2+) carbonate Chemical compound [Zr+2]=O.[O-]C([O-])=O RGRFMLCXNGPERX-UHFFFAOYSA-L 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- UUZZMWZGAZGXSF-UHFFFAOYSA-N peroxynitric acid Chemical compound OON(=O)=O UUZZMWZGAZGXSF-UHFFFAOYSA-N 0.000 description 1
- DTEMQJHXKZCSMQ-UHFFFAOYSA-J phosphonato phosphate;zirconium(4+) Chemical compound [Zr+4].[O-]P([O-])(=O)OP([O-])([O-])=O DTEMQJHXKZCSMQ-UHFFFAOYSA-J 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- DDHRIEFNPBEEQJ-UHFFFAOYSA-I potassium;zirconium(4+);pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[Zr+4] DDHRIEFNPBEEQJ-UHFFFAOYSA-I 0.000 description 1
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- QFURYIUEZSWQQB-UHFFFAOYSA-F tetrapotassium;zirconium(4+);tetrasulfate Chemical compound [K+].[K+].[K+].[K+].[Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QFURYIUEZSWQQB-UHFFFAOYSA-F 0.000 description 1
- WHYLHKYYLCEERH-UHFFFAOYSA-J tetrasodium;2-oxidopropanoate;zirconium(4+) Chemical compound [Na+].[Na+].[Na+].[Na+].[Zr+4].CC([O-])C([O-])=O.CC([O-])C([O-])=O.CC([O-])C([O-])=O.CC([O-])C([O-])=O WHYLHKYYLCEERH-UHFFFAOYSA-J 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
- XLMQAUWIRARSJG-UHFFFAOYSA-J zirconium(iv) iodide Chemical compound [Zr+4].[I-].[I-].[I-].[I-] XLMQAUWIRARSJG-UHFFFAOYSA-J 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/605—Compositions for stimulating production by acting on the underground formation containing biocides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
Definitions
- Hydraulic fracturing uses fluid additives such as slickwater additives.
- fluid additives such as slickwater additives.
- the demand for this type of well services has increased over the past decade, especially because of its successful application for shale gas.
- Horizontal wells are often standard, requiring as much as 4.2 million gallons of water per well in as many as 6 to 9 fracture stages. Because of environmental concerns and fresh water availability, the flowback and produced water are collected and used for subsequent fracture treatments.
- Produced water is a perfect environment for sulfate reducing bacteria (SRB) and acid forming bacteria (AFB) due to its anaerobic nature ( ⁇ 2 ppm oxygen content) and high nutrient content (organics, free iron, etc.).
- SRB sulfate reducing bacteria
- AFB acid forming bacteria
- Reuse of water introduces enough oxygen through regular pumping operations to allow aerobic bacteria to grow—mostly slime forming bacteria (SFB).
- the oxygen content is high enough for aerobic bacteria to grow but too low to kill anaerobic bacteria.
- the oxygen content will cause the anaerobic bacteria to stay in a biostatic state which does not kill them but prevents them from multiplying.
- biocides are quaternary amines, glutaraldehyde, tetra-kis-hydroxylmethylphosphonium sulfate, and tetrahydro 3,5-dimethyl-1,3,5-thiadiazinane-2-thione.
- the issues with traditional non-oxidizing biocides like those described above are that they each have compatibility issues with common additives in stimulation fracturing treatments (e.g. quat amines are not compatible with quaternary and zircontate crosslinked fluids fluids or anionic friction reducing polymers) and that they are very toxic.
- FIG. 1 is a bar graph of free active chlorine as a function of hydrochlorous acid concentration for three time periods.
- FIG. 2 is a bar graph of bacterial population as a function of time for three types of bacteria when a fluid comprises a friction reducer.
- FIG. 3 is a bar graph of bacterial population as a function of time for three types of bacteria when a fluid comprises a biocide.
- FIG. 4 is a bar graph of bacterial population as a function of time for three types of bacteria when a fluid comprises a hypochlorous acid.
- FIG. 5 is a photograph comparing produced water before and after addition of hypochlorous acid.
- FIG. 6 is a chart illustrating the percent drag reduction as a function of rate that compares a fluid comprising a viscosity modifying agent with and without hypochlorous acid.
- FIG. 7 is a chart illustrating viscosity as a function of time for the fluid identified by Table 2 and varied concentrations of hypochlorous acid.
- FIG. 8 is a chart illustrating viscosity as a function of time for the fluid identified by Table 3 and varied concentrations of hypochlorous acid.
- FIG. 9 is a chart illustrating viscosity as a function of time for the fluid identified by Table 4 and varied concentrations of hypochlorous acid.
- FIG. 10 is a chart illustrating viscosity as a function of time for the fluid identified by Table 5 and varied concentrations of hypochlorous acid.
- FIG. 11 is a schematic view of mechanical equipment configured to perform an embodiment of the invention.
- FIG. 12 is a chart illustrating bacterial population as a function of types of bacteria in a field trial comparing the microbe content of fresh water, produced water, mix water, mix water and hypochlorous acid, and flowback water and acid after 21 days.
- FIG. 13 illustrates viscosity as a function of time for a guar fluid that contains no sodium hypochlorite and two different concentrations of sodium hypochlorite.
- FIG. 14 shows titration curves for addition of sodium diacetate buffer to various solutions of concentrated industrial sodium hypochlorite in tap water.
- FIG. 15 shows titrations of some produced water samples treated with sodium hypochlorite (0.21 gpt) and one sample of tap water that was pre-acidified using citric acid prior to treatment with concentrated industrial sodium hypochlorite.
- FIG. 16 shows drag reduction in a 0.5′′ pipe using 0.25 gpt friction reducer, versus water.
- FIG. 17 provides friction reduction curves at 0, 15, and 30 minutes.
- Methods and apparatus of embodiments of the invention relate to a system for treating a subterranean formation including mixing equipment to form a fluid comprising sodium hypochlorite and sodium diacetate; and pumps and a tubular to introduce the fluid into the subterranean formation, wherein a surface of the subterranean formation contains at least 15 percent less microorganisms than if no sodium hypochlorite were in the fluid.
- Methods and apparatus of embodiments of the invention relate to a method of producing a petroleum product from a wellbore including using a well treatment system comprising mixing equipment, pumps, and a tubular, forming a fluid comprising sodium hypochlorite and sodium diacetate; and introducing the fluid to the well treatment system to achieve a reduced population of microorganisms in the system.
- Methods and apparatus of embodiments of the invention relate to a system, comprising: a subterranean formation, a well treatment apparatus comprising mixing equipment, pumps, and a tubular, and a fluid comprising sodium hypochlorite and sodium diacetate to achieve a reduced population of microorganisms in the system.
- Methods and apparatus of embodiments of the invention relate to a method for treating a subterranean formation, comprising forming a fluid comprising sodium hypochlorite, a buffer, and a polymer; introducing the fluid to a surface of a subterranean formation; and decreasing a population of microorganisms, wherein the surface of the subterranean formation contains at least 15 percent less microorganisms than if no sodium hypochlorite were in the fluid, and wherein the fluid exhibits a pH of about 4.0 to about 7.5.
- Methods and apparatus of embodiments of the invention relate to a method for treating a subterranean formation, comprising forming a fluid comprising sodium hypochlorite and sodium diacetate; and introducing the fluid to a subterranean formation, wherein forming the fluid does not include introducing an acid, and wherein forming the fluid does not include forming a precipitate.
- compositions of the present invention are described herein as comprising certain materials, it should be understood that the composition could optionally comprise two or more chemically different materials. In addition, the composition can also comprise some components other than the ones already cited.
- Embodiments of the invention relate to the use of sodium hypochlorite as an effective biocide in combination with sodium diacetate for use in operations related to recovering hydrocarbons from subterranean formations, such as fracturing operations, especially those fracturing operations that use fluid additives for viscosity modification. That is, embodiments of this invention relate to the use of sodium hypochlorite and sodium diacetate for killing and managing microbes in water used for fracturing including slickwater fracturing.
- hypochlorous acid can be delivered in a dilute and stable form, such as by using EXCELYTETM composition, which is commercially available from Benchmark of Houston, Tex. Calcium hypochlorite may be selected for some embodiments. It also will form hypochlorous acid upon exposure to water.
- hypochlorous acid is formed according to the equation:
- hypochlorous acid has outstanding bactericidal power. This is generally attributed to its ability to diffuse through cell walls and thereby reach the vital parts of the bacterial cell. A widely accepted theory credits the death of the cell to a reaction between hypochlorous acid and enzyme. The hypochlorite ion has little if any bactericidal effect since its negative charge impedes penetration of the cell wall.
- the bactericidal power of a solution of chlorine, a hypochlorite, or a chloramine is directly proportional to the hypochlorous acid concentration of the solution.
- the percent available chlorine as un-dissociated hypochlorous acid is therefore the true measure of the bactericidal effectiveness of a solution containing one of the chemicals of the available chlorine family.
- the available chlorine family is comprised of the group of chemicals which, when dissolved in water, yield solutions of hypochlorous acid. These compounds may be further subdivided into those which contain free available chlorine and those which contain combined available chlorine.
- Oxidizing power of a hypochlorite and/or hypochlorous acid solution is attributable to the amount of active oxidant, measured as Free Available Chlorine (FAC), irrespective of pH.
- FAC Free Available Chlorine
- Organic chloramines are also a source of FAC, where the low rate of hydrolysis of dissolved organic chloramines to give hypochlorite and/or hypochlorous acid contributes little to the rate of oxidation while maintaining the total oxidizing power, which relates to the amount of organic chloramines present.
- organic chloramines and other reagents that contribute to FAC supply more hypochlorite and/or hypochlorous acid as these oxidizers are depleted.
- hypochlorous acid is 25 to 100 times more effective than bleach as a disinfectant without being corrosive.
- the key active ingredient, hypochlorous acid is a naturally occurring molecule synthesized from an electrolyzed solution of salt and water. When exposed to atmospheric conditions, it quickly degrades into saltwater, therefore not leaving ecological damage at field locations.
- hypochlorous acid does not fully dissociate and has a neutral pH. (around 7.5). In aqueous solutions, hypochlorous acid partially dissociates into a salt (the hypochlorite ion), therefore its use in oil field service application does not leave an undesirable ecological footprint. In contrast, the most commonly used oxidizers do not sterilize and completely kill bacteria. Hypochlorous acid, on the other hand, reacts quickly with any organic-based or readily oxidizable materials (Fe, H 2 S) present in the water. Further, hypochlorous acid is noncorrosive compared to other biocides.
- hypochlorous acid will have a concentration of about 1 to 8,500 ppm in a fluid.
- the pH of hypochlorous acid influences the free available chlorine concentration.
- the relationship between pH and the degree of dissociation acid is illustrated by Table 1. Hydrolysis increases rapidly as the pH rises above neutrality.
- hypochlorous acid may be commercially manufactured using several methods.
- hypochlorous acid may be made by exposing water containing sodium chloride to an electrolytic cell. It can also be made in a more concentrated form in the field by using a buffer, such as sodium diacetate, to lower the pH of a sodium hypochlorite solution in water.
- hypochlorous acid may be generated by dissolving chlorine gas in water.
- Hypochlorous acid can also be formed by introducing sodium hypochlorite into a solution that has a pH that can be synthesized from an electrolyzed solution of salt and water, or generated by lowering the pH of a hypochlorite solution to a pH below 7.5, often tailored to have a pH of 4 to 7.
- a continuous process that includes continuous addition of sodium hypochlorite and pH modifying agent such as a weak acid such as on the fly mixing in oil field service applications may be selected.
- pH modifying agents such as weak acid, a buffer and/or a strong acid may be used to tailor the pH.
- the preferred pH modifying agent may comprise water-soluble organic acids with twelve or fewer carbon atoms.
- the weak acid is an acid that exhibits a pKa of less than 6.
- Weak acids include potassium dihydrogen phosphate, phthalic acid, phthalates such as potassium hydrogen phthalate and related acid salts, chelates, citric acid, sulfamic acid, ascorbic acid, octanoic acid, nonanoic acid, propionic acid, erythorbic acid, succinic acid, glutaric acid, adipic acid, polyacrylic acid, maleic acid, cyanuric acid, orthophosphoric acid, acetic acid, and sodium, potassium, and calcium salts of these acids.
- a weak acid, a buffer, or a combination thereof may be used to tailor the pH.
- the preferred weak acid may comprise water-soluble organic acids with twelve or fewer carbon atoms. The preferred weak acid exhibits a pKa of less than 6.
- a pH modifying agent may include a strong acid that does not contain a halogen, such as sulfuric, nitric, or phosphoric acid may be used in very dilute concentration, such as nanomolar concentration.
- a strong acid such as sulfuric, nitric, or phosphoric acid may be used in very dilute concentration, such as nanomolar concentration.
- Other buffers, buffer solutions, or buffer systems may be selected.
- the pH modifying agent may be selected to activate upon the passage of time or temperature, such that the hypochlorous acid is present in solution after the solution containing sodium hypochlorite and pH modifying agent is pumped into a wellbore.
- the pH modifying agent may be selected to modify the pH of the fluid over a tailored time or temperature.
- Agents most likely to be effective include polylactic acid, polyglycolic acid, or similar hydrolytic polyesters. Delay may be enhanced by isolating the agent in an oil phase and the sodium hypochlorite in the water phase in some embodiments, the acid may be encapsulated. Upon temperature and downhole mixing, delayed formation of hypochlorous acid may be achieved. Fumeric acid encapsulated in wax may also be selected.
- the fluid may be tailored to exhibit a pH of 4.0 to 7.5 using a buffer or weak acid.
- the preferred weak acid may comprise water-soluble organic acids with twelve or fewer carbon atoms.
- a weak acid is an acid that exhibits a pKa of less than 6.
- Weak acids include potassium dihydrogen phosphate, thallic acid, phthalates, chelates, citric acid, sulfamic acid, ascorbic acid, octanoic acid, nonanoic acid, propionic acid, erythorbic acid, succinic acid, glutaric acid, adipic acid, polyacrylic acid, maleic acid, cyanuric acid, orthophosphoric acid, acetic acid, and sodium, potassium, and calcium salts of these acids.
- a strong acid that does not contain a halogen, such as sulfuric, nitric, or phosphoric acid may be used in very dilute concentration, such as nanomolar concentration.
- Other buffers, buffer solutions, or buffer systems may be selected.
- Additional chemicals may be added to a hypochlorous acid composition to stabilize the hypochlorous acid concentration and/or to reduce the reactivity of the bacteria's residual enzymes.
- Dichloroisocyanuric acid, cyanuric acid, sulfamic acid, potassium iodate, ethylenediaminetetraacetic acid, or a combination thereof may be selected for some embodiments.
- the method can also include contacting the aqueous medium with an enzyme activity minimizer including a metal.
- the metal can include a heavy metal compound in the aqueous medium including oilfield produced water.
- the heavy metal can include zirconium compound. Zirconium containing chemicals may be used to reduce the reactivity of residual bacteria enzymes.
- zirconium containing chemicals that act as enzyme activity minimizer examples include zirconium nitrate, zirconyl chloride, zirconium phosphate, zirconium potassium chloride, zirconium potassium fluoride, zirconium potassium sulfate, zirconium pyrophosphate, zirconium sulfate, zirconium tetrachloride, zirconium tetrafluoride, zirconium tetrabromide, zirconium tetraiodide, zirconyl carbonate, zirconyl hydroxynitrate, zirconyl sulfate, zirconium complexed with amino acids, zirconium complexed with phosphonic acids, hydrates thereof and combinations thereof.
- Organo-zirconium compound examples include zirconium acetate, zirconyl acetate, zirconium acetylacetonate, zirconium glycolate, zirconium lactate, zirconium naphthenate, sodium zirconium lactate, triethanolamine zirconium, zirconium propionate, hydrates thereof and combinations thereof.
- Zirconium dichloride oxide may be selected for some embodiments.
- the carrier fluid such as water, brines, or produced water
- the carrier fluid may contain other additives to tailor properties of the fluid.
- Rheological property modifiers such as friction reducers, viscosifiers, emulsions, stabilizers, solid particles such as proppant or fibers, or gases such as nitrogen may be included in the fluid.
- the fluid may include viscosity modifying agents such as guar gum, hydroxyproplyguar, hydroxyelthylcellulose, xanthan, or carboxymethylhydroxypropylguar, diutan, chitosan, or other polymers or additives used to modify viscosity for use in the oil field services industry.
- Water based fluids may include crosslinkers such as borate or organometallic crosslinkers.
- the fluid may contain viscosity modifying agents that comprise viscoelastic surfactant.
- Viscoelastic surfactants include cationic, anionic, nonionic, mixed, zwitterionic and amphoteric surfactants, especially betaine zwitterionic viscoelastic surfactant fluid systems or amidoamine oxide viscoelastic surfactant fluid systems.
- the fluid may be used as a fracturing fluid, drilling fluid, completions fluid, coiled tubing fluid, sand control fluids, cementing operations fluid, fracturing pit fluid, or onshore or offshore water injector fluid, or any other fluid that is introduced into a subterranean formation primarily for the recovery of hydrocarbons.
- the fluid is introduced to the subterranean formation by drilling equipment, fracturing equipment, coiled tubing equipment, cementing equipment, or onshore or offshore water injectors.
- the formation may benefit from fracturing, drilling, controlling sand, cementing, or injecting a well.
- hypochlorous acid fluid may include delivery of the fluid to the following mechanical equipment.
- Hypocholorous acid fluid may be delivered to the low pressure side of the operation, that is, into any low pressure hose, connection, manifold, or equipment; before or during treatment.
- Hypochlorous acid fluid may be delivered to the high pressure side of an operation including into any high pressure iron, anywhere. Pumps that may be used, either solo or combined, include positive displacement pumps, centrifugal pumps, and additive pumps. The hypochlorous acid fluid may be added to the water stream in any way. (i.e. pour from a bucket, pump it into the water, etc.).
- FIG. 11 is a schematic view of mechanical equipment configured to perform an embodiment of the invention.
- Working tanks 1101 contain water or liquid that is introduced to water line 1102 .
- Water line 1102 may include an entry port 1103 for acetic acid or sodium diacetate or other pH controlling agent.
- the entry port 1103 includes a connection to the pH control agent line 1104 which is connected to additive skids 1105 , which may be any type of pump or other delivery device.
- the line 1104 may include acetic acid, sodium diacetate, or other pH controlling agent or any other chemical.
- the skids 1105 are controlled, in part, by feedback from a control device 1106 as illustrated by lines 1107 .
- the water line 1102 is also in communication with a pH meter or other online or offline sampling entity 1108 which may be used to determine the pH or other property of the water as it enters water line 1102 .
- the entity 1108 sends a signal via a line 1109 or using a transmitter that does not require lines to a pH meter 1110 or other property measurement device which sends a signal to the control device 1106 via lines 1111 or using a transmitter that does not require lines.
- the entities 1108 and 1112 may be any type of probe such as an electrode.
- the pH meter 1110 also collects information from pH meter or other online or offline sampling entity 1112 via line 1114 or using a transmitter that does not require lines which is connected to a blender 1113 .
- the pH meter 1110 sends a signal via line 1115 or using a transmitter that does not require lines to the control device 1106 .
- the blender 1113 where additional chemicals are introduced via line 1116 , which delivers sodium hypochlorite and/or other biocide and/or any other relevant chemical.
- the delivery of sodium hypochlorite is, in part, controlled by the skids 1105 , which receive a signal from the controller 1106 via lines 1117 or using a transmitter that does not require lines.
- the fluid flows from the blender 1113 on to the manifold 1118 via lines 1119 or using a transmitter that does not require lines, then on to the wellbore through the pumps or other lines or other equipment of the manifold 1118 and on to tubulars or other wellbore equipment.
- the pH control or component concentration control of the system may be performed using an electronic control system as described above.
- manual control may be used, including measuring the pH and/or composition of the water in the tanks 1101 or the line 1102 or the line 1119 .
- no pH metering may be performed at all and the concentration of components may be established based on volume of material.
- a hybrid manual/electronic control system may be used with sampling and addition partially manually controlled, partially electronically controlled.
- addition of one component may be using the skids 1105 described above or using equipment configured for addition at other points in the blender, line 1119 , or in the manifold.
- the controller 1106 and/or pH meter 1110 and/or skids may be the same piece of equipment. In some embodiments, the controller 1106 and/or pH meter 1110 may be omitted altogether, especially if the volume of material is fixed.
- the blender 1113 may be a blender, a tubular, a line, a static mixer, or any other equipment that may provide static or agitated mixing or blending. In some embodiments, the order of mechanical equipment including mixing, blending, introducing components, measuring pH may be altered. Further, the control system may be configured in alternative ways to accommodate changes in the mechanical equipment.
- delivering the components to form the hypochlorous acid fluid to the mechanical equipment in the field must be selected based on the source of the acid.
- Commercially available hypochlorous acid such as EXCELYTETM, is delivered premixed into any size storage containers. It may be added to the system with any way into any of the above points of addition.
- Sodium hypochlorite may be combined with a weak acid on the fly or by batch mixing.
- the material may be added by separate add lines—one for sodium hypochlorite, one for acid/buffer (any order); by a combined system—concentrated mixture of sodium hypochlorite and acid/buffer; or by a slurry system—combined mixture of water, sodium hypochlorite and acid/buffer.
- the components may be mixed together before or during the fracturing job and stored in any type of container. It may be added to the system with any way into any of the above points of addition.
- hypochlorous acid may kill or retard the reproduction of microorganisms.
- hypochlorous acid in the fluid will result in a fluid with at least 25 percent less microorganisms or at least 25 percent less bacteria than if no hypochlorous acid were present.
- the type of water used in these Examples was produced water from the Piceance Basin, which is considered to be among the dirtiest, recycled, produced water with poor quality.
- the sample water was provided to us by a supplier and yielded a pH of 8.0 and a TDS of 142,000 ppm. Titrimetric methods were used to determine the anions present while Inductively Coupled Plasma spectrometry was used for the detection of cations in the sample water.
- the chlorine exists in the water as hypochlorous acid (free available chlorine, FAC). Chlorine is effective against all microorganisms and any readily oxidizable organic matter. If there is a lot of organic matter in the fracturing water, the chlorine will be consumed (or spent) and will be unavailable for killing the bacteria. Therefore, it is necessary to have a residual of FAC in the water to be effective as a biocide.
- the FAC demand test determines the dosage of hypochlorous acid necessary to treat the water and kill the bacteria in the frac water. The FAC demand test was used to determine the dosage of hypochlorous acid necessary to treat and kill the bacteria downhole. The FAC of the sample water was determined at several time points up to 45 minutes using various concentrations of hypochlorous acid.
- FIG. 1 shows data collected on a Piceance Basin water sample.
- 5% (v/v) or 50 gpt hypochlorous acid solution was the lowest effective concentration that showed a positive result of FAC residual which was necessary to sanitize and kill the bacteria. Consequently, 50 gpt hypochlorous acid solution was used as the concentration for all subsequent testing regarding hypochlorous acid.
- Bottle tests were used to evaluate the biocidal efficacy of hypochlorous acid against the three types of bacteria mentioned above as well as compare its performance with friction reducer and commonly used biocide, glutaraldehyde.
- the bacterial population was measured at time points up to seven days.
- FIG. 2 shows the effect of a viscosity modifying agent, that is, a friction reducer has on biological activity.
- a viscosity modifying agent that is, a friction reducer has on biological activity.
- friction reducer had little or no effect on the bacterial population.
- 0.25 gal/Kgal polyacrylamide emulsion was added to the Piceance Basin water sample for a period of seven days to see its effect on the biological activity. The above figure shows that the friction reducer had little or no effect on the bacterial population.
- FIG. 3 shows that glutaraldehyde is not very effective in killing bacteria in Piceance River water containing 0.25 gpt of friction reducer. Note a 2 log reduction in the population of SRB after 24 hours (a 3 log reduction is desirable). However, after 7 days there was re-growth of bacteria. 0.25 gal/Kgal glutaraldehyde was added to the produced water sample along with 0.25 gal/Kgal friction reducer to evaluate the effect of glutaraldehyde on bacterial activity for seven days. The above figure shows that glutaraldehyde in the presence of friction reducer was not effective in killing the bacteria in the water sample; however, there was a 2 log reduction in the SRB population after 24 hours. After seven days, regrowth of bacteria was apparent, suggesting the possibility of sour wells after fracturing treatment.
- FIG. 4 shows the hypochlorous acid is very effective in killing all bacteria in the Piceance River water. After 7 days, the bacterial counts were blow detectable limits and no regrowth was apparent. 5 (v/v) hypochlorous acid solution (500-1000 ppm active) was added to the produced water sample containing 0.25 gal/Kgal friction reducer to evaluate the effect of hypochlorous acid activity on bacterial activity for seven days. Within five minutes, the bacterial population was significantly reduced from 10 6 cells/mL to 10 1 cells/mL. After 24 hours, the SRB population was not detectable and regrowth was not apparent after seven days.
- hypochlorous acid solution 500-1000 ppm active
- Bottle tests were performed with deionized water and produced water, separately.
- 5% (v/v) hypochlorous acid solution was added to a series of individual bottles with slickwater additives, including clay stabilizer, scale inhibitor, friction reducer and a microemulsion.
- the compatibility of hypochlorous acid solution and the slickwater additives were observed at time 0 and 5 minutes. No incompatibilities were observed between the slickwater additives and hypochlorous acid solution in deionized water.
- FIG. 5 shows addition of hypochlorous acid to the produced water eliminated rotten odor and color changed to a lighter shade. The pH remained stable after the hypochlorous acid treatment. Apparently, the hypochlorous acid is very effective in improving the quality of produced water by oxidizing the contaminants.
- a friction loop consisting of a 1 ⁇ 2′′ and a 3 ⁇ 4′′ pipe was used for drag reduction measurements.
- Synthetic water was prepared based on the water analysis of the Piceance Basin produced water sample. Fifteen liters of the source water, along with the slickwater additives and hypochlorous acid solution, were stirred using an overhead stirrer at 1000 rpm for two minutes before being added to the friction loop for evaluation. Before analysis, the differential pressure gauges were purged and the pump was primed prior to recording the data for the test. The test fluid was then pumped for about 10 seconds at incremental intervals of about 6 Kg/min and the percent drag reduction was calculated.
- FIG. 6 shows the friction loop results of slickwater additives and hypochlorous acid measuring the percent drag reduction as a function of flow rate (Kg/min). Varying the viscosity modifying additives with and without hypochlorous acid shows no incompatibilities as illustrated by FIG. 6 .
- FIG. 6 shows the friction loop results of slickwater additives and hypochlorous acid. Data are plotted as the percent drag reduction as a function of flow rate (Kg/min). Hypochlorous acid had no effect on the slickwater additives. This shows that the viscosity difference due to the presence of the hypochlorous acid in about 2 percent or less.
- hypochlorous acid was evaluated with common fracturing fluids currently used in field operations.
- the hypochlorous acid solution was used at concentrations of 0 gal/Kgal, 10 gal/Kgal, and 50 gal/Kgal.
- the fluid compositions are listed in Tables 2-5. Fluids were tested at 150 deg F. for a period of one hour.
- the mixing procedure for the fracturing fluids is as follows: 500 mL of deionized water was placed into a Waring blending cup; subsequently, the hypochlorous acid solution was added and allowed to mix for 20 seconds. The gelling agent was then added and allowed to mix for 10 minutes, after which the linear gel viscosity was checked and compared to the hydration chart (see below).
- FIGS. 7 to 10 illustrate the experimental results generated using the fluids of tables 2-5.
- the fluids did not result in a significant loss in viscosity when the hypochlorous acid solution concentration was increased from 0 gal/Kgal to 50 gal/Kgal. Additionally, the fluid is still viable and capable of transporting proppant.
- TMAC Tetramethyl 2 gpt ammonium chloride
- TMAC Tetramethyl 2 gpt ammonium chloride
- Bottle tests were used to evaluate the stabilization of hypochlorous acid with the following chemicals: dichloroisocyanuric acid (DCCA) and cyanuric acid (CA). Cyanuric acid is known to stabilize the rate of decomposition of hypochlorous acid in ultraviolet conditions. Over a period of four days, a set of bottles with the following components were left open: 1) hypochlorous acid solution (500-1000 ppm active), 2) hypochlorous acid solution +30 ppm CA, 3) hypochlorous acid solution +50 ppm CA, 4) hypochlorous acid solution +30 ppm DCCA, and 5) hypochlorous acid solution +50 ppm DCCA. At the time of preparation, the initial pH and FAC were taken and recorded (see table below).
- DCCA dichloroisocyanuric acid
- CA cyanuric acid
- test points were then taken again after 1 day and four days.
- the pH was stable (within 5% of the starting hypochlorous acid solution) after the addition of DCCA and CA. Additionally, the FAC residual value for all solutions decreased by 5%, with the DCCA-containing solutions obtaining a consistently higher FAC residual than hypochlorous acid solution alone.
- a tank is filled with 400 gallons of city water. To this is added 20 gallons of 12% sodium hypochlorite solution. This result in a 0.6% solution of sodium hypochorite. To this is added an excess of citric acid until the pH of the resulting solution reaches pH equal to 6.5. This stock solution is then added on the fly to the fracturing treatment. The concentration of the stock solution added to the fracturing fluid was 0.2 to 0.6 gallons per thousand gallons. Using 100 mL of 1% (v/v) sodium hypochlorite (10000 ppm), 12.8 mL of 5% (v/v) acetic acid was added to obtain a pH value of 7.0 from an initial pH of 9.7.
- the active concentration (FAC residual) of the resultant solution was then found to be 8500 ppm. After one hour, the active concentration remained the same. In 24 hours, the active concentration decreased by 3.5% to 8210 ppm. Similarly, 55.2 mL of 0.1M succinic acid solution was added to 100 mL 1% (v/v) sodium hypochlorite to obtain a pH value of 7.0. The active concentration was found to be 6040 ppm after titration.
- a fracturing treatment using hypochlorous acid lasted two days. Four stages, at 2 hours per stage, were pumped using a total of 1.86 million gallons of water. 1.6M pounds of proppant were used. In total, 19 k gallons of hypochlorous acid solution (500-1000 ppm active) was pumped. The concentration of hypochlorous acid solution that was required (10 gpt) also required bulk storage and high rate additive pumps. A 12,000 gallon fluid module (modified frac tank) was placed next to the water frac tanks. An additive skid with 2 large Waukesha pumps, capable of 45 gpm, added hypochlorous acid at a rate of 42 gpm. Hypochlorous acid solution was pumped from the bulk module tank and into the 250 bbl batch mixing tank.
- FIG. 12 is a chart illustrating bacterial population as a function of types of bacteria in a field trial comparing the microbe content of fresh water, produced water, mix water, mix water and hypochlorous acid, and flowback water and acid after 21 days. That is, FIG. 12 illustrates the microbe population demise over time. All data points were taken on location. Initial flowback data was taken 21 days after job completion. The final flowback data point was taken 51 days after job completion.
- a control experiment without buffer and concentrated industrial sodium hypochlorite was run in a similar manner to evaluate the decrease in friction pressure inherent in running the fluid through the loop repeatedly.
- FIG. 14 shows titration curves for addition of sodium diacetate buffer to various solutions of concentrated industrial sodium hypochlorite in tap water.
- FIG. 15 shows titrations of some produced water samples treated with concentrated industrial sodium hypochlorite (0.21 gpt) and one sample of tap water that was pre-acidified using citric acid prior to treatment with concentrated industrial sodium hypochlorite.
- FIG. 15 illustrates titration of various acidic and produced waters with sodium diacetate buffer. Even acidic produced waters can have pH correction up into a more benign range using sodium diacetate buffer.
- FIG. 16 shows drag reduction in a 0.5′′ pipe using 0.25 gpt friction reducer, versus water.
- the friction reducer reduces friction by about 65%.
- Test duration is about 3 minutes. The test was repeated after the fluid was simply left to sit in the loop under static conditions, giving the lower (30 min) trace, which shows ⁇ 61% friction reduction.
- sodium diacetate buffer can correct the pH of a hypochlorite solution in produced water from a high pH to below 5.5.
- Sodium diacetate buffer can correct the pH of a more strongly acidic hypochlorous acid solution in produced water from a pH near 3.0 to a pH of almost 5.0.
- Sodium diacetate buffer does not have an adverse effect on the stability of concentrated sodium diacetate solutions at concentrations relevant to slickwater fracturing.
- sodium diacetate buffer adjusts pH of alkaline fluids into a range where the active water cleaning chemical in concentrated industrial sodium hypochlorite is more stable than it would be if the fluid were nearer to neutral pH.
- Sodium diacetate buffer and concentrated sodium hypochlorite together do not have a measurable effect on the friction reducing ability of friction reducer as measured in a friction loop test.
Abstract
Methods and apparatus of embodiments of the invention relate to a system for treating a subterranean formation including mixing equipment to form a fluid comprising sodium hypochlorite and sodium diacetate; and pumps and a tubular to introduce the fluid into the subterranean formation, wherein a surface of the subterranean formation contains at least 15 percent less microorganisms than if no sodium hypochlorite were in the fluid. Methods and apparatus of embodiments of the invention relate to a method of producing a petroleum product from a wellbore including using a well treatment system comprising mixing equipment, pumps, and a tubular, forming a fluid comprising sodium hypochlorite and sodium diacetate; and introducing the fluid to the well treatment system to achieve a reduced population of microorganisms in the system. Methods and apparatus of embodiments of the invention relate to a system, comprising: a subterranean formation, a well treatment apparatus comprising mixing equipment, pumps, and a tubular, and a fluid comprising sodium hypochlorite and sodium diacetate to achieve a reduced population of microorganisms in the system. Methods and apparatus of embodiments of the invention relate to a method for treating a subterranean formation, comprising forming a fluid comprising sodium hypochlorite, a buffer, and a polymer; introducing the fluid to a surface of a subterranean formation; and decreasing a population of microorganisms, wherein the surface of the subterranean formation contains at least 15 percent less microorganisms than if no sodium hypochlorite were in the fluid, and wherein the fluid exhibits a pH of about 4.0 to about 7.5. Methods and apparatus of embodiments of the invention relate to a method for treating a subterranean formation, comprising forming a fluid comprising sodium hypochlorite and sodium diacetate; and introducing the fluid to a subterranean formation, wherein forming the fluid does not include introducing an acid, and wherein forming the fluid does not include forming a precipitate.
Description
- This application claims priority to U.S. Provisional Application No. 61/217,899, filed Jun. 5, 2009, which is incorporated by reference herein in its entirety.
- Hydraulic fracturing uses fluid additives such as slickwater additives. The demand for this type of well services has increased over the past decade, especially because of its successful application for shale gas. Horizontal wells are often standard, requiring as much as 4.2 million gallons of water per well in as many as 6 to 9 fracture stages. Because of environmental concerns and fresh water availability, the flowback and produced water are collected and used for subsequent fracture treatments. Produced water is a perfect environment for sulfate reducing bacteria (SRB) and acid forming bacteria (AFB) due to its anaerobic nature (<2 ppm oxygen content) and high nutrient content (organics, free iron, etc.). Reuse of water introduces enough oxygen through regular pumping operations to allow aerobic bacteria to grow—mostly slime forming bacteria (SFB). The oxygen content is high enough for aerobic bacteria to grow but too low to kill anaerobic bacteria. The oxygen content will cause the anaerobic bacteria to stay in a biostatic state which does not kill them but prevents them from multiplying.
- As soon as the bacteria find an environment that is conducive to their growth, they will become active again and start multiplying. The anaerobic environment in the formation is ideal for growth of bacteria like SRBs and AFBs. The aerobic environment of the wellbore is conducive for SFBs. The growth of SRBs will not only lead to health and safety concerns due to increased sour gas or hydrogen sulfide (H2S) production but also to a slow souring of the reservoir. This also increases operation expenses because of corrosion (H2S pitting, stress cracking, etc.) in surface and subsurface tubulars. Other challenges in production can be related to AFBs (pitting) and SFBs (emulsion like materials may form).
- Various different methods can be applied to prevent bacteria growth and reduce operational expenses related to corrosion prevention, remediation of corrosion effects, and remediation of emulsion-like produced fluids. Common biocides are quaternary amines, glutaraldehyde, tetra-kis-hydroxylmethylphosphonium sulfate, and
tetrahydro 3,5-dimethyl-1,3,5-thiadiazinane-2-thione. The issues with traditional non-oxidizing biocides like those described above are that they each have compatibility issues with common additives in stimulation fracturing treatments (e.g. quat amines are not compatible with quaternary and zircontate crosslinked fluids fluids or anionic friction reducing polymers) and that they are very toxic. Despite the treatment of water with these biocides, post-fracture treatment reservoir souring has been reported. The re-growth of SRB under reservoir conditions may lead to reservoir souring. An effective, low cost biocide that is compatible with other fluid additives and that is easily transportable is needed. -
FIG. 1 is a bar graph of free active chlorine as a function of hydrochlorous acid concentration for three time periods. -
FIG. 2 is a bar graph of bacterial population as a function of time for three types of bacteria when a fluid comprises a friction reducer. -
FIG. 3 is a bar graph of bacterial population as a function of time for three types of bacteria when a fluid comprises a biocide. -
FIG. 4 is a bar graph of bacterial population as a function of time for three types of bacteria when a fluid comprises a hypochlorous acid. -
FIG. 5 is a photograph comparing produced water before and after addition of hypochlorous acid. -
FIG. 6 is a chart illustrating the percent drag reduction as a function of rate that compares a fluid comprising a viscosity modifying agent with and without hypochlorous acid. -
FIG. 7 is a chart illustrating viscosity as a function of time for the fluid identified by Table 2 and varied concentrations of hypochlorous acid. -
FIG. 8 is a chart illustrating viscosity as a function of time for the fluid identified by Table 3 and varied concentrations of hypochlorous acid. -
FIG. 9 is a chart illustrating viscosity as a function of time for the fluid identified by Table 4 and varied concentrations of hypochlorous acid. -
FIG. 10 is a chart illustrating viscosity as a function of time for the fluid identified by Table 5 and varied concentrations of hypochlorous acid. -
FIG. 11 is a schematic view of mechanical equipment configured to perform an embodiment of the invention. -
FIG. 12 is a chart illustrating bacterial population as a function of types of bacteria in a field trial comparing the microbe content of fresh water, produced water, mix water, mix water and hypochlorous acid, and flowback water and acid after 21 days. -
FIG. 13 illustrates viscosity as a function of time for a guar fluid that contains no sodium hypochlorite and two different concentrations of sodium hypochlorite. -
FIG. 14 shows titration curves for addition of sodium diacetate buffer to various solutions of concentrated industrial sodium hypochlorite in tap water. -
FIG. 15 shows titrations of some produced water samples treated with sodium hypochlorite (0.21 gpt) and one sample of tap water that was pre-acidified using citric acid prior to treatment with concentrated industrial sodium hypochlorite. -
FIG. 16 shows drag reduction in a 0.5″ pipe using 0.25 gpt friction reducer, versus water. -
FIG. 17 provides friction reduction curves at 0, 15, and 30 minutes. - Methods and apparatus of embodiments of the invention relate to a system for treating a subterranean formation including mixing equipment to form a fluid comprising sodium hypochlorite and sodium diacetate; and pumps and a tubular to introduce the fluid into the subterranean formation, wherein a surface of the subterranean formation contains at least 15 percent less microorganisms than if no sodium hypochlorite were in the fluid. Methods and apparatus of embodiments of the invention relate to a method of producing a petroleum product from a wellbore including using a well treatment system comprising mixing equipment, pumps, and a tubular, forming a fluid comprising sodium hypochlorite and sodium diacetate; and introducing the fluid to the well treatment system to achieve a reduced population of microorganisms in the system. Methods and apparatus of embodiments of the invention relate to a system, comprising: a subterranean formation, a well treatment apparatus comprising mixing equipment, pumps, and a tubular, and a fluid comprising sodium hypochlorite and sodium diacetate to achieve a reduced population of microorganisms in the system. Methods and apparatus of embodiments of the invention relate to a method for treating a subterranean formation, comprising forming a fluid comprising sodium hypochlorite, a buffer, and a polymer; introducing the fluid to a surface of a subterranean formation; and decreasing a population of microorganisms, wherein the surface of the subterranean formation contains at least 15 percent less microorganisms than if no sodium hypochlorite were in the fluid, and wherein the fluid exhibits a pH of about 4.0 to about 7.5. Methods and apparatus of embodiments of the invention relate to a method for treating a subterranean formation, comprising forming a fluid comprising sodium hypochlorite and sodium diacetate; and introducing the fluid to a subterranean formation, wherein forming the fluid does not include introducing an acid, and wherein forming the fluid does not include forming a precipitate.
- At the outset, it should be noted that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developer's specific goals, such as compliance with system related and business related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time consuming but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. The description and examples are presented solely for the purpose of illustrating the preferred embodiments of the invention and should not be construed as a limitation to the scope and applicability of the invention. While the compositions of the present invention are described herein as comprising certain materials, it should be understood that the composition could optionally comprise two or more chemically different materials. In addition, the composition can also comprise some components other than the ones already cited.
- In the summary of the invention and this description, each numerical value should be read once as modified by the term “about” (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the summary of the invention and this detailed description, it should be understood that a concentration range listed or described as being useful, suitable, or the like, is intended that any and every concentration within the range, including the end points, is to be considered as having been stated. For example, “a range of from 1 to 10” is to be read as indicating each and every possible number along the continuum between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific, it is to be understood that inventors appreciate and understand that any and all data points within the range are to be considered to have been specified, and that inventors have disclosed and enabled the entire range and all points within the range.
- Embodiments of the invention relate to the use of sodium hypochlorite as an effective biocide in combination with sodium diacetate for use in operations related to recovering hydrocarbons from subterranean formations, such as fracturing operations, especially those fracturing operations that use fluid additives for viscosity modification. That is, embodiments of this invention relate to the use of sodium hypochlorite and sodium diacetate for killing and managing microbes in water used for fracturing including slickwater fracturing. In some embodiments, hypochlorous acid can be delivered in a dilute and stable form, such as by using EXCELYTE™ composition, which is commercially available from Benchmark of Houston, Tex. Calcium hypochlorite may be selected for some embodiments. It also will form hypochlorous acid upon exposure to water.
- Generally, when chlorine is added to water, hypochlorous acid is formed according to the equation:
- Hypochlorous acid has outstanding bactericidal power. This is generally attributed to its ability to diffuse through cell walls and thereby reach the vital parts of the bacterial cell. A widely accepted theory credits the death of the cell to a reaction between hypochlorous acid and enzyme. The hypochlorite ion has little if any bactericidal effect since its negative charge impedes penetration of the cell wall.
- The bactericidal power of a solution of chlorine, a hypochlorite, or a chloramine is directly proportional to the hypochlorous acid concentration of the solution. The percent available chlorine as un-dissociated hypochlorous acid is therefore the true measure of the bactericidal effectiveness of a solution containing one of the chemicals of the available chlorine family.
- The available chlorine family is comprised of the group of chemicals which, when dissolved in water, yield solutions of hypochlorous acid. These compounds may be further subdivided into those which contain free available chlorine and those which contain combined available chlorine.
- Oxidizing power of a hypochlorite and/or hypochlorous acid solution is attributable to the amount of active oxidant, measured as Free Available Chlorine (FAC), irrespective of pH. Organic chloramines are also a source of FAC, where the low rate of hydrolysis of dissolved organic chloramines to give hypochlorite and/or hypochlorous acid contributes little to the rate of oxidation while maintaining the total oxidizing power, which relates to the amount of organic chloramines present. Thus, organic chloramines and other reagents that contribute to FAC supply more hypochlorite and/or hypochlorous acid as these oxidizers are depleted.
- Hypochlorous acid is 25 to 100 times more effective than bleach as a disinfectant without being corrosive. The key active ingredient, hypochlorous acid, is a naturally occurring molecule synthesized from an electrolyzed solution of salt and water. When exposed to atmospheric conditions, it quickly degrades into saltwater, therefore not leaving ecological damage at field locations.
- Hypochlorous acid does not fully dissociate and has a neutral pH. (around 7.5). In aqueous solutions, hypochlorous acid partially dissociates into a salt (the hypochlorite ion), therefore its use in oil field service application does not leave an undesirable ecological footprint. In contrast, the most commonly used oxidizers do not sterilize and completely kill bacteria. Hypochlorous acid, on the other hand, reacts quickly with any organic-based or readily oxidizable materials (Fe, H2S) present in the water. Further, hypochlorous acid is noncorrosive compared to other biocides.
- In some embodiments, hypochlorous acid will have a concentration of about 1 to 8,500 ppm in a fluid. The pH of hypochlorous acid influences the free available chlorine concentration. The relationship between pH and the degree of dissociation acid is illustrated by Table 1. Hydrolysis increases rapidly as the pH rises above neutrality.
-
TABLE 1 Dissociation of Hypochlorous Acid as a Function of pH at 25° C. pH % HOCl Undissociated 5.0 99.6 6.0 96.5 7.0 73.0 7.4 50.0 8.0 21.0 9.0 2.7 10.0 0.3 - Hypochlorous acid may be commercially manufactured using several methods. In some embodiments, hypochlorous acid may be made by exposing water containing sodium chloride to an electrolytic cell. It can also be made in a more concentrated form in the field by using a buffer, such as sodium diacetate, to lower the pH of a sodium hypochlorite solution in water. Finally, in some embodiments, hypochlorous acid may be generated by dissolving chlorine gas in water.
- Hypochlorous acid can also be formed by introducing sodium hypochlorite into a solution that has a pH that can be synthesized from an electrolyzed solution of salt and water, or generated by lowering the pH of a hypochlorite solution to a pH below 7.5, often tailored to have a pH of 4 to 7. For example, a continuous process that includes continuous addition of sodium hypochlorite and pH modifying agent such as a weak acid such as on the fly mixing in oil field service applications may be selected. PH modifying agents such as weak acid, a buffer and/or a strong acid may be used to tailor the pH. In some embodiments, the preferred pH modifying agent may comprise water-soluble organic acids with twelve or fewer carbon atoms. The weak acid is an acid that exhibits a pKa of less than 6. Weak acids include potassium dihydrogen phosphate, phthalic acid, phthalates such as potassium hydrogen phthalate and related acid salts, chelates, citric acid, sulfamic acid, ascorbic acid, octanoic acid, nonanoic acid, propionic acid, erythorbic acid, succinic acid, glutaric acid, adipic acid, polyacrylic acid, maleic acid, cyanuric acid, orthophosphoric acid, acetic acid, and sodium, potassium, and calcium salts of these acids. A weak acid, a buffer, or a combination thereof may be used to tailor the pH. In some embodiments, the preferred weak acid may comprise water-soluble organic acids with twelve or fewer carbon atoms. The preferred weak acid exhibits a pKa of less than 6.
- In some embodiments, a pH modifying agent may include a strong acid that does not contain a halogen, such as sulfuric, nitric, or phosphoric acid may be used in very dilute concentration, such as nanomolar concentration. Other buffers, buffer solutions, or buffer systems may be selected.
- The pH modifying agent may be selected to activate upon the passage of time or temperature, such that the hypochlorous acid is present in solution after the solution containing sodium hypochlorite and pH modifying agent is pumped into a wellbore. Generally, however the hypochlorous acid is manufactured, the pH modifying agent may be selected to modify the pH of the fluid over a tailored time or temperature. Agents most likely to be effective include polylactic acid, polyglycolic acid, or similar hydrolytic polyesters. Delay may be enhanced by isolating the agent in an oil phase and the sodium hypochlorite in the water phase in some embodiments, the acid may be encapsulated. Upon temperature and downhole mixing, delayed formation of hypochlorous acid may be achieved. Fumeric acid encapsulated in wax may also be selected.
- However the hypochlorous acid is formed, to maintain the hypochlorous acid concentration within a fluid, the fluid may be tailored to exhibit a pH of 4.0 to 7.5 using a buffer or weak acid. In some embodiments, the preferred weak acid may comprise water-soluble organic acids with twelve or fewer carbon atoms. A weak acid is an acid that exhibits a pKa of less than 6. Weak acids include potassium dihydrogen phosphate, thallic acid, phthalates, chelates, citric acid, sulfamic acid, ascorbic acid, octanoic acid, nonanoic acid, propionic acid, erythorbic acid, succinic acid, glutaric acid, adipic acid, polyacrylic acid, maleic acid, cyanuric acid, orthophosphoric acid, acetic acid, and sodium, potassium, and calcium salts of these acids. In some embodiments, a strong acid that does not contain a halogen, such as sulfuric, nitric, or phosphoric acid may be used in very dilute concentration, such as nanomolar concentration. Other buffers, buffer solutions, or buffer systems may be selected.
- Additional chemicals may be added to a hypochlorous acid composition to stabilize the hypochlorous acid concentration and/or to reduce the reactivity of the bacteria's residual enzymes. Dichloroisocyanuric acid, cyanuric acid, sulfamic acid, potassium iodate, ethylenediaminetetraacetic acid, or a combination thereof may be selected for some embodiments.
- The method can also include contacting the aqueous medium with an enzyme activity minimizer including a metal. In an embodiment, the metal can include a heavy metal compound in the aqueous medium including oilfield produced water. In an embodiment, the heavy metal can include zirconium compound. Zirconium containing chemicals may be used to reduce the reactivity of residual bacteria enzymes. Examples of zirconium containing chemicals that act as enzyme activity minimizer include zirconium nitrate, zirconyl chloride, zirconium phosphate, zirconium potassium chloride, zirconium potassium fluoride, zirconium potassium sulfate, zirconium pyrophosphate, zirconium sulfate, zirconium tetrachloride, zirconium tetrafluoride, zirconium tetrabromide, zirconium tetraiodide, zirconyl carbonate, zirconyl hydroxynitrate, zirconyl sulfate, zirconium complexed with amino acids, zirconium complexed with phosphonic acids, hydrates thereof and combinations thereof. Organo-zirconium compound examples include zirconium acetate, zirconyl acetate, zirconium acetylacetonate, zirconium glycolate, zirconium lactate, zirconium naphthenate, sodium zirconium lactate, triethanolamine zirconium, zirconium propionate, hydrates thereof and combinations thereof. Zirconium dichloride oxide may be selected for some embodiments.
- The carrier fluid, such as water, brines, or produced water, may contain other additives to tailor properties of the fluid. Rheological property modifiers such as friction reducers, viscosifiers, emulsions, stabilizers, solid particles such as proppant or fibers, or gases such as nitrogen may be included in the fluid. The fluid may include viscosity modifying agents such as guar gum, hydroxyproplyguar, hydroxyelthylcellulose, xanthan, or carboxymethylhydroxypropylguar, diutan, chitosan, or other polymers or additives used to modify viscosity for use in the oil field services industry. Water based fluids may include crosslinkers such as borate or organometallic crosslinkers. In some embodiments, the fluid may contain viscosity modifying agents that comprise viscoelastic surfactant. Viscoelastic surfactants include cationic, anionic, nonionic, mixed, zwitterionic and amphoteric surfactants, especially betaine zwitterionic viscoelastic surfactant fluid systems or amidoamine oxide viscoelastic surfactant fluid systems.
- The fluid may be used as a fracturing fluid, drilling fluid, completions fluid, coiled tubing fluid, sand control fluids, cementing operations fluid, fracturing pit fluid, or onshore or offshore water injector fluid, or any other fluid that is introduced into a subterranean formation primarily for the recovery of hydrocarbons. The fluid is introduced to the subterranean formation by drilling equipment, fracturing equipment, coiled tubing equipment, cementing equipment, or onshore or offshore water injectors. During, before, or after the fluid is added to a subterranean formation, the formation may benefit from fracturing, drilling, controlling sand, cementing, or injecting a well.
- An oil field services application of a hypochlorous acid fluid may include delivery of the fluid to the following mechanical equipment. Hypocholorous acid fluid may be delivered to the low pressure side of the operation, that is, into any low pressure hose, connection, manifold, or equipment; before or during treatment. Examples of the location for addition include into pond, pit, or other water containment source; into inlet hose/manifold of water tanks (upstream of water tanks); frac tanks—all together or separate; into water tanks (frac tanks) themselves; into hose/manifold of outlet side of water tanks; into batch mixing unit; into hose/manifold in between batch mixing unit and blender; into blender itself; into exit side of blender (upstream of fracturing pumps); hose/manifold; directly into low pressure side of pump manifold (missile). Hypochlorous acid fluid may be delivered to the high pressure side of an operation including into any high pressure iron, anywhere. Pumps that may be used, either solo or combined, include positive displacement pumps, centrifugal pumps, and additive pumps. The hypochlorous acid fluid may be added to the water stream in any way. (i.e. pour from a bucket, pump it into the water, etc.).
-
FIG. 11 is a schematic view of mechanical equipment configured to perform an embodiment of the invention. Workingtanks 1101 contain water or liquid that is introduced to water line 1102. Water line 1102 may include anentry port 1103 for acetic acid or sodium diacetate or other pH controlling agent. Theentry port 1103 includes a connection to the pHcontrol agent line 1104 which is connected toadditive skids 1105, which may be any type of pump or other delivery device. Theline 1104 may include acetic acid, sodium diacetate, or other pH controlling agent or any other chemical. Theskids 1105 are controlled, in part, by feedback from acontrol device 1106 as illustrated bylines 1107. The water line 1102 is also in communication with a pH meter or other online or offline sampling entity 1108 which may be used to determine the pH or other property of the water as it enters water line 1102. The entity 1108 sends a signal via aline 1109 or using a transmitter that does not require lines to apH meter 1110 or other property measurement device which sends a signal to thecontrol device 1106 vialines 1111 or using a transmitter that does not require lines. The entities 1108 and 1112 may be any type of probe such as an electrode. ThepH meter 1110 also collects information from pH meter or other online or offline sampling entity 1112 vialine 1114 or using a transmitter that does not require lines which is connected to a blender 1113. ThepH meter 1110 sends a signal vialine 1115 or using a transmitter that does not require lines to thecontrol device 1106. In any event, as the water or liquid flows through line 1102, it continues on into the blender 1113 where additional chemicals are introduced vialine 1116, which delivers sodium hypochlorite and/or other biocide and/or any other relevant chemical. The delivery of sodium hypochlorite is, in part, controlled by theskids 1105, which receive a signal from thecontroller 1106 vialines 1117 or using a transmitter that does not require lines. The fluid flows from the blender 1113 on to themanifold 1118 vialines 1119 or using a transmitter that does not require lines, then on to the wellbore through the pumps or other lines or other equipment of the manifold 1118 and on to tubulars or other wellbore equipment. - In some embodiments, the pH control or component concentration control of the system may be performed using an electronic control system as described above. In some embodiments, manual control may be used, including measuring the pH and/or composition of the water in the
tanks 1101 or the line 1102 or theline 1119. In some embodiments, no pH metering may be performed at all and the concentration of components may be established based on volume of material. In some embodiments, a hybrid manual/electronic control system may be used with sampling and addition partially manually controlled, partially electronically controlled. In some embodiments, addition of one component may be using theskids 1105 described above or using equipment configured for addition at other points in the blender,line 1119, or in the manifold. In some embodiments, thecontroller 1106 and/orpH meter 1110 and/or skids may be the same piece of equipment. In some embodiments, thecontroller 1106 and/orpH meter 1110 may be omitted altogether, especially if the volume of material is fixed. In some embodiments the blender 1113 may be a blender, a tubular, a line, a static mixer, or any other equipment that may provide static or agitated mixing or blending. In some embodiments, the order of mechanical equipment including mixing, blending, introducing components, measuring pH may be altered. Further, the control system may be configured in alternative ways to accommodate changes in the mechanical equipment. - In some alternative embodiments, delivering the components to form the hypochlorous acid fluid to the mechanical equipment in the field must be selected based on the source of the acid. Commercially available hypochlorous acid, such as EXCELYTE™, is delivered premixed into any size storage containers. It may be added to the system with any way into any of the above points of addition. Sodium hypochlorite may be combined with a weak acid on the fly or by batch mixing. In on the fly applications, the material may be added by separate add lines—one for sodium hypochlorite, one for acid/buffer (any order); by a combined system—concentrated mixture of sodium hypochlorite and acid/buffer; or by a slurry system—combined mixture of water, sodium hypochlorite and acid/buffer. In batch mixing applications, the components may be mixed together before or during the fracturing job and stored in any type of container. It may be added to the system with any way into any of the above points of addition. In some embodiments, hypochlorous acid may kill or retard the reproduction of microorganisms. In some embodiments, hypochlorous acid in the fluid will result in a fluid with at least 25 percent less microorganisms or at least 25 percent less bacteria than if no hypochlorous acid were present.
- The following examples are presented to illustrate the preparation and properties of fluid systems, and should not be construed to limit the scope of the invention, unless otherwise expressly indicated in the appended claims. All percentages, concentrations, ratios, parts, etc. are by weight unless otherwise noted or apparent from the context of their use.
- Several analytical tools were selected to confirm the effectiveness of hypochlorous acid, its compatibility with other fluid additives, and its stability over time with optional stabilizing additives.
- The type of water used in these Examples, unless described otherwise, was produced water from the Piceance Basin, which is considered to be among the dirtiest, recycled, produced water with poor quality. The sample water was provided to us by a supplier and yielded a pH of 8.0 and a TDS of 142,000 ppm. Titrimetric methods were used to determine the anions present while Inductively Coupled Plasma spectrometry was used for the detection of cations in the sample water.
- The chlorine exists in the water as hypochlorous acid (free available chlorine, FAC). Chlorine is effective against all microorganisms and any readily oxidizable organic matter. If there is a lot of organic matter in the fracturing water, the chlorine will be consumed (or spent) and will be unavailable for killing the bacteria. Therefore, it is necessary to have a residual of FAC in the water to be effective as a biocide. The FAC demand test determines the dosage of hypochlorous acid necessary to treat the water and kill the bacteria in the frac water. The FAC demand test was used to determine the dosage of hypochlorous acid necessary to treat and kill the bacteria downhole. The FAC of the sample water was determined at several time points up to 45 minutes using various concentrations of hypochlorous acid. 5% (v/v) of hypochlorous acid solution containing 500 to 1000 ppm active ingredient was found to be the lowest effective concentration that showed a positive FAC residual necessary to sanitize and kill the microorganisms present in the produced water.
FIG. 1 shows data collected on a Piceance Basin water sample. As can be seen, 5% (v/v) or 50 gpt hypochlorous acid solution was the lowest effective concentration that showed a positive result of FAC residual which was necessary to sanitize and kill the bacteria. Consequently, 50 gpt hypochlorous acid solution was used as the concentration for all subsequent testing regarding hypochlorous acid. - Bottle tests were used to evaluate the biocidal efficacy of hypochlorous acid against the three types of bacteria mentioned above as well as compare its performance with friction reducer and commonly used biocide, glutaraldehyde. The bacterial population was measured at time points up to seven days.
-
FIG. 2 shows the effect of a viscosity modifying agent, that is, a friction reducer has on biological activity. As can be seen that friction reducer had little or no effect on the bacterial population. 0.25 gal/Kgal polyacrylamide emulsion was added to the Piceance Basin water sample for a period of seven days to see its effect on the biological activity. The above figure shows that the friction reducer had little or no effect on the bacterial population. -
FIG. 3 shows that glutaraldehyde is not very effective in killing bacteria in Piceance River water containing 0.25 gpt of friction reducer. Note a 2 log reduction in the population of SRB after 24 hours (a 3 log reduction is desirable). However, after 7 days there was re-growth of bacteria. 0.25 gal/Kgal glutaraldehyde was added to the produced water sample along with 0.25 gal/Kgal friction reducer to evaluate the effect of glutaraldehyde on bacterial activity for seven days. The above figure shows that glutaraldehyde in the presence of friction reducer was not effective in killing the bacteria in the water sample; however, there was a 2 log reduction in the SRB population after 24 hours. After seven days, regrowth of bacteria was apparent, suggesting the possibility of sour wells after fracturing treatment. -
FIG. 4 shows the hypochlorous acid is very effective in killing all bacteria in the Piceance River water. After 7 days, the bacterial counts were blow detectable limits and no regrowth was apparent. 5 (v/v) hypochlorous acid solution (500-1000 ppm active) was added to the produced water sample containing 0.25 gal/Kgal friction reducer to evaluate the effect of hypochlorous acid activity on bacterial activity for seven days. Within five minutes, the bacterial population was significantly reduced from 106 cells/mL to 101 cells/mL. After 24 hours, the SRB population was not detectable and regrowth was not apparent after seven days. - Compatibility with Slickwater Additives and Piceance River Water
- Visual tests were performed to illustrate that there were no incompatibilities between viscosity modifying additives and hypochlorous acid solution (500-1000 ppm active). Also, bottle tests were performed. Bottle tests (deionized water and produced water) were performed with deionized water and produced water, separately. 5% (v/v) hypochlorous acid solution was added to a series of individual bottles with slickwater additives, including clay stabilizer, scale inhibitor, friction reducer and a microemulsion. The compatibility of hypochlorous acid solution and the slickwater additives were observed at
time FIG. 5 shows addition of hypochlorous acid to the produced water eliminated rotten odor and color changed to a lighter shade. The pH remained stable after the hypochlorous acid treatment. Apparently, the hypochlorous acid is very effective in improving the quality of produced water by oxidizing the contaminants. - A friction loop consisting of a ½″ and a ¾″ pipe was used for drag reduction measurements. Synthetic water was prepared based on the water analysis of the Piceance Basin produced water sample. Fifteen liters of the source water, along with the slickwater additives and hypochlorous acid solution, were stirred using an overhead stirrer at 1000 rpm for two minutes before being added to the friction loop for evaluation. Before analysis, the differential pressure gauges were purged and the pump was primed prior to recording the data for the test. The test fluid was then pumped for about 10 seconds at incremental intervals of about 6 Kg/min and the percent drag reduction was calculated. The figure shows the friction loop results of the slickwater additives and hypochlorous acid measuring the percent drag reduction as a function of flow rate (Kg/min). Varying the viscosity modifying additives with and without hypochlorous acid shows no incompatibilities as illustrated by
FIG. 6 .FIG. 6 shows the friction loop results of slickwater additives and hypochlorous acid. Data are plotted as the percent drag reduction as a function of flow rate (Kg/min). Hypochlorous acid had no effect on the slickwater additives. This shows that the viscosity difference due to the presence of the hypochlorous acid in about 2 percent or less. - Hypochlorous Acid in Combination with Common Fracturing Fluids
- The compatibility of hypochlorous acid was evaluated with common fracturing fluids currently used in field operations. The hypochlorous acid solution was used at concentrations of 0 gal/Kgal, 10 gal/Kgal, and 50 gal/Kgal. The fluid compositions are listed in Tables 2-5. Fluids were tested at 150 deg F. for a period of one hour. The mixing procedure for the fracturing fluids is as follows: 500 mL of deionized water was placed into a Waring blending cup; subsequently, the hypochlorous acid solution was added and allowed to mix for 20 seconds. The gelling agent was then added and allowed to mix for 10 minutes, after which the linear gel viscosity was checked and compared to the hydration chart (see below). The remaining additives were then added to the solution and the vortex was allowed to close (after the addition of the crosslinker). Rheology profiles of the four fluids may be found in
FIGS. 7 to 10 which illustrate the experimental results generated using the fluids of tables 2-5. The fluids did not result in a significant loss in viscosity when the hypochlorous acid solution concentration was increased from 0 gal/Kgal to 50 gal/Kgal. Additionally, the fluid is still viable and capable of transporting proppant. - Common Fracturing fluids that may be utilized with hypochlorous acid are listed in the following tables.
-
TABLE 2 Fluid formulation 1Additive Concentration Tetramethyl 2 gpt ammonium chloride (TMAC) Slurried guar 6.25 gpt Borate crosslinker 3 gpt Hypochlorous acid 0, 10, 50 gal/Kgal solution (500-1000 ppm active) -
TABLE 3 Fluid Formulation 2Additive Concentration Tetramethyl 2 gpt ammonium chloride (TMAC) Slurried guar 6.25 gpt Boric acid 5.5 ppt Sodium Hydroxide 10 ppt d- Sorbitol 2 gpt Hypochlorous acid 0, 10, 50 gal/Kgal solution (500-1000 ppm active) -
TABLE 4 Fluid Formulation 3Additive Concentration Tetramethyl 2 gpt ammonium chloride (TMAC) Slurried guar 6.25 gpt Sodium Borate 1.3 gpt 30% Sodium 0.5 gpt Hydroxide Hypochlorous 0, 10, 50 gal/Kgal acid solution (500-1000 ppm active) -
TABLE 5 Fluid Formulation 4Additive Concentration Polyvinyl acetate/ 6.7 gpt polyvinyl alcohol copolymer Erucic amidopropyl 40 gpt dimethyl betaine Hypochlorous acid 0, 10, 50 gal/Kgal solution (500-1000 ppm active) -
TABLE 6 Linear Gel Viscosities at Increased Biocide Concentrations Biocide Concentration Temperature (gpt) (F.) Viscosity (511, sec−1) 0 71.2 19 10 74.1 18.5 50 68.7 18 - Using 100 mL of 3% (v/v) bleach, 29 mL of 5% (v/v) acetic acid was added to obtain a pH of 6.5 from an initial pH value of 8.48. The FAC residual was greater than 1000 ppm. Additionally, in a separate experiment, 22 mL of 1M sodium citrate was added to the bleach solution to obtain a pH of 6.5. The FAC value was then found to be 24 ppm. More details of this portion of the experimental data are presented below in paragraph 0061.
- Bottle tests were used to evaluate the stabilization of hypochlorous acid with the following chemicals: dichloroisocyanuric acid (DCCA) and cyanuric acid (CA). Cyanuric acid is known to stabilize the rate of decomposition of hypochlorous acid in ultraviolet conditions. Over a period of four days, a set of bottles with the following components were left open: 1) hypochlorous acid solution (500-1000 ppm active), 2) hypochlorous acid solution +30 ppm CA, 3) hypochlorous acid solution +50 ppm CA, 4) hypochlorous acid solution +30 ppm DCCA, and 5) hypochlorous acid solution +50 ppm DCCA. At the time of preparation, the initial pH and FAC were taken and recorded (see table below). The test points were then taken again after 1 day and four days. For all solutions prepared, the pH was stable (within 5% of the starting hypochlorous acid solution) after the addition of DCCA and CA. Additionally, the FAC residual value for all solutions decreased by 5%, with the DCCA-containing solutions obtaining a consistently higher FAC residual than hypochlorous acid solution alone.
-
Time = 0 Time = 1 day Time = 4 days FAC FAC FAC pH (ppm) pH (ppm) pH (ppm) Hypochlorous acid 6.80 726 6.86 692 7.18 628 solution Hypochlorous acid 6.51 660 6.76 646 7.13 587 solution + 30 ppm CA Hypochlorous acid 6.47 670 6.77 637 7.16 580 solution + 50 ppm CA Hypochlorous acid 6.62 739 6.75 705 7.13 639 solution + 30 ppm DCCA Hypochlorous acid 6.79 739 6.99 705 7.20 639 solution + 50 ppm DCCA
Hypochlorous Acid Solution Made from Sodium Hypochorite. - A tank is filled with 400 gallons of city water. To this is added 20 gallons of 12% sodium hypochlorite solution. This result in a 0.6% solution of sodium hypochorite. To this is added an excess of citric acid until the pH of the resulting solution reaches pH equal to 6.5. This stock solution is then added on the fly to the fracturing treatment. The concentration of the stock solution added to the fracturing fluid was 0.2 to 0.6 gallons per thousand gallons. Using 100 mL of 1% (v/v) sodium hypochlorite (10000 ppm), 12.8 mL of 5% (v/v) acetic acid was added to obtain a pH value of 7.0 from an initial pH of 9.7. The active concentration (FAC residual) of the resultant solution was then found to be 8500 ppm. After one hour, the active concentration remained the same. In 24 hours, the active concentration decreased by 3.5% to 8210 ppm. Similarly, 55.2 mL of 0.1M succinic acid solution was added to 100
mL 1% (v/v) sodium hypochlorite to obtain a pH value of 7.0. The active concentration was found to be 6040 ppm after titration. - A fracturing treatment using hypochlorous acid lasted two days. Four stages, at 2 hours per stage, were pumped using a total of 1.86 million gallons of water. 1.6M pounds of proppant were used. In total, 19 k gallons of hypochlorous acid solution (500-1000 ppm active) was pumped. The concentration of hypochlorous acid solution that was required (10 gpt) also required bulk storage and high rate additive pumps. A 12,000 gallon fluid module (modified frac tank) was placed next to the water frac tanks. An additive skid with 2 large Waukesha pumps, capable of 45 gpm, added hypochlorous acid at a rate of 42 gpm. Hypochlorous acid solution was pumped from the bulk module tank and into the 250 bbl batch mixing tank.
- In another field test, 26 gpt hypochlorous acid solution was added with 1 gpt slickwater fluid and mixed for less 1 min at 80 bbls/min to a form a fluid. To be precise, the pH of the fluid was 6. Thus, the 26 gpt hypochlorous acid was 2.5 percent active hypochlorous acid and 0.075 percent hypochlorite ion.
FIG. 12 is a chart illustrating bacterial population as a function of types of bacteria in a field trial comparing the microbe content of fresh water, produced water, mix water, mix water and hypochlorous acid, and flowback water and acid after 21 days. That is,FIG. 12 illustrates the microbe population demise over time. All data points were taken on location. Initial flowback data was taken 21 days after job completion. The final flowback data point was taken 51 days after job completion. - Sodium Diacetate in Combination with Sodium Hypochlorite
- Several tests were performed to illustrate how sodium diacetate works as a buffer for maintaining the pH and thus the integrity of the sodium hypochlorite. Titrations were performed using Eppendorf-style micropipettors to dispense sodium diacetate into 100 ml fluid samples contained in glass jars. The mixture was continuously stirred at medium shear by a 15 mm Teflon stir bar actuated by an Ika stir plate. The pH was measured using a Fisher Scientific XL-15 pH meter that was calibrated freshly prior to the beginning of each titration. FAC was measured using the Hach spectrophotometer, which colorimetrically evaluates [OCl]. A friction loop consisting of a ½″ and a ¾″ pipe was used for drag reduction (DR) measurements. The pressure difference (denoted as ΔP) across the pipes, as well as the mass flow and the temperature were recorded or each fluid analyzed. Initially, the friction loop was calibrated with local tap water prior to the fluid testing and all tests were run at room temperature. Fluid was prepared by adding 0.25 gpt friction reducer to treated water and stirring for 2 minutes at 100 rpm using an overhead mixer. After the prepared fluid was added to the friction loop hopper, the differential pressure gauges were purged and the pump was primed prior to recording the data for the test. The test fluid was pumped for about 10 seconds at incremental intervals of about 6 Kg/min and the percent drag reduction (% DR) is calculated using the following equation (Eq 3):
-
- Each fluid had its friction pressure measured at
time 0, at time=15 minutes, and at time=30 minutes to gauge the effect of the formation cleaning fluid and buffer on the acrylamide friction reducer. A control experiment without buffer and concentrated industrial sodium hypochlorite was run in a similar manner to evaluate the decrease in friction pressure inherent in running the fluid through the loop repeatedly. - The first round of titrations were performed using various concentrations of concentrated industrial sodium hypochlorite in Sugar Land tap water to ensure the performance of sodium diacetate buffer was as expected in the presence of sodium hypochlorite. Several concentrations of sodium hypochlorite and other readily available reagents were tested. The results are summarized in
FIG. 14 .FIG. 14 shows titration curves for addition of sodium diacetate buffer to various solutions of concentrated industrial sodium hypochlorite in tap water. - In the simplest of these experiments, tap water with an initial pH of 7.82 has its pH changed to 5.43 by the addition of 0.5 gpt buffer. Addition of a further 0.5 gpt or even another 10 gpt preserve apH.of just under 5.4. There is a stir-rate dependence in the experiment—at low shear, the pH reported by the probe is not quickly representative of the bulk solution because the probe is immersed in ˜2.5″ of a 100 ml solution. With increased stirring, this feature went away. The same “high shear” stir rate was used in all the other experiments. Several water samples containing a level of concentrated industrial sodium hypochlorite appropriate to water cleaning were tested in the same manner, and all converge on pH of between 5.4 and 7 with minimal addition of buffer. Note that all the titrations trend out to final pH values between 5 and 7, even when as much as 12.5 gpt buffer is added.
-
FIG. 15 shows titrations of some produced water samples treated with concentrated industrial sodium hypochlorite (0.21 gpt) and one sample of tap water that was pre-acidified using citric acid prior to treatment with concentrated industrial sodium hypochlorite.FIG. 15 illustrates titration of various acidic and produced waters with sodium diacetate buffer. Even acidic produced waters can have pH correction up into a more benign range using sodium diacetate buffer. - The objective of friction pressure measurements was to verify which combinations of friction reducer, formation cleaning agent (concentrated industrial sodium hypochlorite), and buffer have little or no effect on the friction reducing capacity. In order to establish this, a control experiment was performed to quantify the effect of recirculation in the loop on the acrylamide polymer in the friction reducer.
FIG. 16 shows drag reduction in a 0.5″ pipe using 0.25 gpt friction reducer, versus water. - At high rate, the friction reducer reduces friction by about 65%. Test duration is about 3 minutes. The test was repeated after the fluid was simply left to sit in the loop under static conditions, giving the lower (30 min) trace, which shows ˜61% friction reduction.
- This experiment was then performed using a fresh sample with 0.25 gpt friction reducer, 0.21 gpt concentrated industrial sodium hypochlorite, and 0.5 gpt sodium diacetate. The friction reduction curves at 0, 15, and 30 minutes are shown in
FIG. 17 . It is notable that 30 minutes and two cycles of testing cause roughly the same depletion of friction reducing power when sodium diacetate and sodium hypochlorite are present as was observed for the friction reducer itself. One interpretation is that chemical activity of the sodium diacetate and sodium hypochlorite on the friction reducer is negligible as compared to the shear imposed by the test. When extrapolating from a lab scale to a field situation, the shear rates may be considerably higher but the chemistry should be the same. - From this data, it may be concluded that sodium diacetate buffer can correct the pH of a hypochlorite solution in produced water from a high pH to below 5.5. Sodium diacetate buffer can correct the pH of a more strongly acidic hypochlorous acid solution in produced water from a pH near 3.0 to a pH of almost 5.0. Sodium diacetate buffer does not have an adverse effect on the stability of concentrated sodium diacetate solutions at concentrations relevant to slickwater fracturing. In fact, sodium diacetate buffer adjusts pH of alkaline fluids into a range where the active water cleaning chemical in concentrated industrial sodium hypochlorite is more stable than it would be if the fluid were nearer to neutral pH. Sodium diacetate buffer and concentrated sodium hypochlorite together do not have a measurable effect on the friction reducing ability of friction reducer as measured in a friction loop test.
- The particular embodiments disclosed above are illustrative only, as the invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details herein shown, other than as described in the claims below. It is therefore evident that the particular embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the invention. Accordingly, the protection sought herein is as set forth in the claims below.
Claims (17)
1. A system for treating a subterranean formation, comprising:
mixing equipment to form a fluid comprising sodium hypochlorite and sodium diacetate; and
pumps and a tubular to introduce the fluid into the subterranean formation,
wherein a surface of the subterranean formation contains less microorganisms than if no sodium hypochlorite were in the fluid.
2. The system of claim 1 , wherein the fluid is introduced to the subterranean formation by drilling equipment, fracturing equipment, coiled tubing equipment, cementing equipment, or onshore or offshore water injectors.
3. The system of claim 1 , further comprising equipment to control the pH to about 4.0 to about 7.5.
4. The system of claim 1 , wherein the fluid further comprises a viscosity modifying agent.
5. The method of claim 1 , wherein the fluid further comprises an enzyme activity minimizer.
6. A method of producing a petroleum product from a wellbore, comprising:
using a well treatment system comprising mixing equipment, pumps, and a tubular;
forming a fluid comprising sodium hypochlorite and sodium diacetate; and
introducing the fluid to the well treatment system to achieve a reduced population of microorganisms in the system.
7. The method of claim 6 , wherein the fluid has a concentration of 1 to 8,500 ppm hypochlorous acid.
8. The method of claim 6 , wherein the well treatment system further comprises drilling equipment, fracturing equipment, coiled tubing equipment, cementing equipment, or onshore or offshore water injectors.
9. The method of claim 6 , wherein the introducing the fluid to the system further comprises fracturing, drilling, controlling sand, cementing, or injecting a wellbore.
10. The method of claim 6 , further comprising adjusting the pH to about 4.0 to about 7.5.
11. The method of claim 6 , wherein the fluid further comprises a viscosity modifying agent.
12. A method for treating a subterranean formation, comprising:
forming a fluid comprising sodium hypochlorite, a buffer, and a polymer;
introducing the fluid to a surface of a subterranean formation; and
decreasing a population of microorganisms,
wherein the surface of the subterranean formation contains less microorganisms than if no sodium hypochlorite were in the fluid, and
wherein the fluid exhibits a pH of about 4.0 to about 7.5.
13. The method of claim 12 , wherein the fluid is introduced to the subterranean formation by drilling equipment, fracturing equipment, coiled tubing equipment, cementing equipment, or onshore or offshore water injectors.
14. The method of claim 12 , further comprising controlling the pH to about 4.0 to about 7.5.
15. The system of claim 12 , wherein the fluid further comprises an enzyme activity minimizer.
16. A method for treating a subterranean formation, comprising:
forming a fluid comprising sodium hypochlorite and sodium diacetate; and
introducing the fluid to a subterranean formation,
wherein forming the fluid does not include introducing an acid, and
wherein forming the fluid does not include forming a precipitate.
17. A system, comprising:
a subterranean formation,
a well treatment apparatus comprising mixing equipment, pumps, and a tubular, and
a fluid comprising sodium hypochlorite and sodium diacetate to achieve a reduced population of microorganisms in the system.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/793,479 US20100307757A1 (en) | 2009-06-05 | 2010-06-03 | Aqueous solution for controlling bacteria in the water used for fracturing |
CA2706305A CA2706305A1 (en) | 2009-06-05 | 2010-06-04 | Aqueous solution for controlling bacteria in the water used for fracturing |
MX2010006245A MX2010006245A (en) | 2009-06-05 | 2010-06-04 | Aqueous solution for controlling bacteria in the water used for fracturing. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21789909P | 2009-06-05 | 2009-06-05 | |
US12/793,479 US20100307757A1 (en) | 2009-06-05 | 2010-06-03 | Aqueous solution for controlling bacteria in the water used for fracturing |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100307757A1 true US20100307757A1 (en) | 2010-12-09 |
Family
ID=43299925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/793,479 Abandoned US20100307757A1 (en) | 2009-06-05 | 2010-06-03 | Aqueous solution for controlling bacteria in the water used for fracturing |
Country Status (3)
Country | Link |
---|---|
US (1) | US20100307757A1 (en) |
CA (1) | CA2706305A1 (en) |
MX (1) | MX2010006245A (en) |
Cited By (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110137465A1 (en) * | 2010-04-09 | 2011-06-09 | Angelilli Jerome F | Portable Water Treatment Method |
US20110132815A1 (en) * | 2010-04-09 | 2011-06-09 | Angelilli Jerome F | Portable Water Treatment System and Apparatus |
US20120085541A1 (en) * | 2010-10-12 | 2012-04-12 | Qip Holdings, Llc | Method and Apparatus for Hydraulically Fracturing Wells |
WO2012110993A1 (en) * | 2011-02-15 | 2012-08-23 | Medentech Limited | Inhibition of bacterial growth in oil field fluids |
US20130020079A1 (en) * | 2011-07-18 | 2013-01-24 | Zerorez Texas, Inc. | Treatment of subterranean wells with electrolyzed water |
US20130071492A1 (en) * | 2011-09-16 | 2013-03-21 | Carmine J. Durham | Systems and methods for generating germicidal compositions |
WO2013123104A1 (en) * | 2012-02-15 | 2013-08-22 | E. I. Du Pont De Nemours And Company | PROCESS FOR HYDRAULIC FRACTURING WITH pH CONTROL |
US20130248176A1 (en) * | 2012-03-23 | 2013-09-26 | Glori Energy Inc. | Ultra low concentration surfactant flooding |
US9068108B2 (en) | 2013-03-14 | 2015-06-30 | Cesi Chemical, Inc. | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US9200192B2 (en) | 2012-05-08 | 2015-12-01 | Cesi Chemical, Inc. | Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons |
US9222013B1 (en) | 2008-11-13 | 2015-12-29 | Cesi Chemical, Inc. | Water-in-oil microemulsions for oilfield applications |
WO2016010621A1 (en) * | 2014-05-19 | 2016-01-21 | Buckman Laboratories International, Inc. | Systems and methods for generating haloamines and application thereof in oil and gas operations |
US9321955B2 (en) | 2013-06-14 | 2016-04-26 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US9371479B2 (en) | 2011-03-16 | 2016-06-21 | Schlumberger Technology Corporation | Controlled release biocides in oilfield applications |
US9428683B2 (en) | 2013-03-14 | 2016-08-30 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US9464223B2 (en) | 2013-03-14 | 2016-10-11 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
WO2016183481A1 (en) * | 2015-05-14 | 2016-11-17 | Hydro Dynamics, Inc. | Reduction of microorganisms in drilling fluid using controlled mechanically induced cavitation |
US9505970B2 (en) | 2014-05-14 | 2016-11-29 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9868893B2 (en) | 2013-03-14 | 2018-01-16 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9884988B2 (en) | 2013-03-14 | 2018-02-06 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9890625B2 (en) | 2014-02-28 | 2018-02-13 | Eclipse Ior Services, Llc | Systems and methods for the treatment of oil and/or gas wells with an obstruction material |
US9890624B2 (en) | 2014-02-28 | 2018-02-13 | Eclipse Ior Services, Llc | Systems and methods for the treatment of oil and/or gas wells with a polymeric material |
US9951264B2 (en) | 2012-04-15 | 2018-04-24 | Flotek Chemistry, Llc | Surfactant formulations for foam flooding |
US9957779B2 (en) | 2014-07-28 | 2018-05-01 | Flotek Chemistry, Llc | Methods and compositions related to gelled layers in oil and/or gas wells |
US10000693B2 (en) | 2013-03-14 | 2018-06-19 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US10053619B2 (en) | 2013-03-14 | 2018-08-21 | Flotek Chemistry, Llc | Siloxane surfactant additives for oil and gas applications |
CN109258688A (en) * | 2017-07-18 | 2019-01-25 | 朴莲花 | A kind of stable neutral disinfectant and preparation method and application method |
US10202535B2 (en) * | 2014-08-28 | 2019-02-12 | Lamberti Spa | Method for treating subterranean formations |
US10287483B2 (en) | 2013-03-14 | 2019-05-14 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells comprising a terpene alcohol |
US10323051B2 (en) | 2011-05-09 | 2019-06-18 | Rhodia Operations | Methods for controlling depolymerization of polymer compositions |
US10421707B2 (en) | 2013-03-14 | 2019-09-24 | Flotek Chemistry, Llc | Methods and compositions incorporating alkyl polyglycoside surfactant for use in oil and/or gas wells |
US10550316B2 (en) | 2016-07-29 | 2020-02-04 | Canadian Energy Services L.P. | Method of forming a fracturing fluid from produced water |
US10577531B2 (en) | 2013-03-14 | 2020-03-03 | Flotek Chemistry, Llc | Polymers and emulsions for use in oil and/or gas wells |
US10590332B2 (en) | 2013-03-14 | 2020-03-17 | Flotek Chemistry, Llc | Siloxane surfactant additives for oil and gas applications |
US10717919B2 (en) | 2013-03-14 | 2020-07-21 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US10870791B2 (en) | 2017-08-14 | 2020-12-22 | PfP Industries LLC | Compositions and methods for cross-linking hydratable polymers using produced water |
US10934472B2 (en) | 2017-08-18 | 2021-03-02 | Flotek Chemistry, Llc | Compositions comprising non-halogenated solvents for use in oil and/or gas wells and related methods |
US10941106B2 (en) | 2013-03-14 | 2021-03-09 | Flotek Chemistry, Llc | Methods and compositions incorporating alkyl polyglycoside surfactant for use in oil and/or gas wells |
US11053433B2 (en) | 2017-12-01 | 2021-07-06 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US11104843B2 (en) | 2019-10-10 | 2021-08-31 | Flotek Chemistry, Llc | Well treatment compositions and methods comprising certain microemulsions and certain clay control additives exhibiting synergistic effect of enhancing clay swelling protection and persistency |
US11103840B2 (en) * | 2018-03-19 | 2021-08-31 | Process Cleaning Solutions Ltd. | Mixing and dispensing device and method |
US11180690B2 (en) | 2013-03-14 | 2021-11-23 | Flotek Chemistry, Llc | Diluted microemulsions with low surface tensions |
US20210392898A1 (en) * | 2020-06-22 | 2021-12-23 | Parasol Medical, Llc | Stabilized hypochlorous acid solution and method for stabilizing hypochlorous acid for longer shelf life |
US11236609B2 (en) | 2018-11-23 | 2022-02-01 | PfP Industries LLC | Apparatuses, systems, and methods for dynamic proppant transport fluid testing |
US11254856B2 (en) | 2013-03-14 | 2022-02-22 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US11407930B2 (en) | 2012-05-08 | 2022-08-09 | Flotek Chemistry, Llc | Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons |
US11512243B2 (en) | 2020-10-23 | 2022-11-29 | Flotek Chemistry, Llc | Microemulsions comprising an alkyl propoxylated sulfate surfactant, and related methods |
US11905462B2 (en) | 2020-04-16 | 2024-02-20 | PfP INDUSTRIES, LLC | Polymer compositions and fracturing fluids made therefrom including a mixture of cationic and anionic hydratable polymers and methods for making and using same |
Citations (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3370957A (en) * | 1963-05-23 | 1968-02-27 | Merck & Co Inc | Antifungal compositions and methods for their use |
US3443882A (en) * | 1966-03-14 | 1969-05-13 | Dow Chemical Co | Treatment of earth surface and subsurface for prevention of acidic drainage from the soil |
US3482636A (en) * | 1967-04-06 | 1969-12-09 | Dow Chemical Co | Method of lessening the inhibitory effects to fluid flow due to the presence of solid organic substances in a subterranean formation |
US3733266A (en) * | 1971-09-07 | 1973-05-15 | Administrator Of The Environme | Waste water purification by breakpoint chlorination and carbon adsorption |
US3853771A (en) * | 1971-05-17 | 1974-12-10 | Shell Oil Co | Process for dispersing cellular micro-organisms with chelating aqueous alkaline surfactant systems |
US4184953A (en) * | 1977-03-22 | 1980-01-22 | The British Petroleum Company Limited | Physical process |
US4620595A (en) * | 1985-08-22 | 1986-11-04 | Shell Offshore Inc. | Recovering oil by injecting ammoniated and nitrited seawater |
US4701247A (en) * | 1986-07-30 | 1987-10-20 | The Dow Chemical Company | Electrochemical methods for breaking high viscosity fluids |
US4818412A (en) * | 1986-04-01 | 1989-04-04 | Betz Laboratories, Inc. | Apparatus and process for feeding hypochlorite solution |
US4846981A (en) * | 1988-12-19 | 1989-07-11 | Texaco Inc. | Method of restoring permeability around wellbores |
US4997571A (en) * | 1990-01-05 | 1991-03-05 | Mogul Corporation | Method of treating water |
US5016714A (en) * | 1990-05-09 | 1991-05-21 | Halliburton Company | Biocidal well treatment method |
US5069286A (en) * | 1990-04-30 | 1991-12-03 | The Mogul Corporation | Method for prevention of well fouling |
US5118426A (en) * | 1990-07-26 | 1992-06-02 | Olin Corporation | Process for purifying impotable water with hypochlorous acid |
US5413178A (en) * | 1994-04-12 | 1995-05-09 | Halliburton Company | Method for breaking stabilized viscosified fluids |
US5942126A (en) * | 1997-01-03 | 1999-08-24 | Nalco Chemical Company | Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling |
US5955401A (en) * | 1996-05-17 | 1999-09-21 | Baroid Technology, Inc. | Clay-free biodegradable wellbore fluid and method for using same fluid |
US6110875A (en) * | 1997-03-07 | 2000-08-29 | Bj Services Company | Methods and materials for degrading xanthan |
US6162371A (en) * | 1997-12-22 | 2000-12-19 | S. C. Johnson & Son, Inc. | Stabilized acidic chlorine bleach composition and method of use |
US6533958B2 (en) * | 1999-12-13 | 2003-03-18 | Acculab Co., Ltd. | System for controlling microbial fouling |
US20030092581A1 (en) * | 2001-11-13 | 2003-05-15 | Crews James B. | Fracturing fluids for delayed flow back operations |
US20040120853A1 (en) * | 2002-12-20 | 2004-06-24 | Carpenter Joel F. | Biocidal control in recovery of oil by water injection |
US6814144B2 (en) * | 2002-11-18 | 2004-11-09 | Exxonmobil Upstream Research Company | Well treating process and system |
US20060116296A1 (en) * | 2004-11-29 | 2006-06-01 | Clearwater International, L.L.C. | Shale Inhibition additive for oil/gas down hole fluids and methods for making and using same |
US7090016B2 (en) * | 2001-11-14 | 2006-08-15 | Battelle Energy Alliance, Llc | Well having inhibited microbial growth |
US20070102359A1 (en) * | 2005-04-27 | 2007-05-10 | Lombardi John A | Treating produced waters |
US7219735B2 (en) * | 2002-11-01 | 2007-05-22 | Innovative Chemical Technologies Canada Ltd. | Packer fluid |
US7231973B2 (en) * | 2004-03-15 | 2007-06-19 | Total Separation Solutions, Llc | Viscosity control and filtration of well fluids |
US7287593B2 (en) * | 2005-10-21 | 2007-10-30 | Schlumberger Technology Corporation | Methods of fracturing formations using quaternary amine salts as viscosifiers |
US20080099207A1 (en) * | 2006-10-31 | 2008-05-01 | Clearwater International, Llc | Oxidative systems for breaking polymer viscosified fluids |
US20080115930A1 (en) * | 2006-11-22 | 2008-05-22 | Strategic Resource Optimization, Inc. | Electrolytic system and method for enhanced release and deposition of sub-surface and surface components |
US20080160612A1 (en) * | 1999-08-23 | 2008-07-03 | Puricore International Limited | Treatment of infected tissues with hypochlorous acid |
US20080200355A1 (en) * | 2007-01-12 | 2008-08-21 | Emmons Stuart A | Aqueous Solution for Managing Microbes in Oil and Gas Production and Method for their Production |
US7455112B2 (en) * | 2006-09-29 | 2008-11-25 | Halliburton Energy Services, Inc. | Methods and compositions relating to the control of the rates of acid-generating compounds in acidizing operations |
US20090062156A1 (en) * | 2007-08-31 | 2009-03-05 | Halliburton Energy Services, Inc. | Methods of treating a subterranean formation including a biocidal treatment |
US7578968B1 (en) * | 2002-05-03 | 2009-08-25 | Albemarle Corporation | Microbiological control in oil or gas field operations |
US20090229827A1 (en) * | 2008-03-14 | 2009-09-17 | Bryant Jason E | Treatment Fluids Having Biocide and Friction Reducing Properties and Associated Methods |
US20100048429A1 (en) * | 2008-02-29 | 2010-02-25 | Texas United Chemical Company, Llc | Methods, Systems, and Compositions for the Controlled Crosslinking of Well Servicing Fluids |
US20100204068A1 (en) * | 2009-02-12 | 2010-08-12 | Rhodia Operations | Methods for controlling depolymerization of polymer compositions |
-
2010
- 2010-06-03 US US12/793,479 patent/US20100307757A1/en not_active Abandoned
- 2010-06-04 MX MX2010006245A patent/MX2010006245A/en unknown
- 2010-06-04 CA CA2706305A patent/CA2706305A1/en not_active Abandoned
Patent Citations (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3370957A (en) * | 1963-05-23 | 1968-02-27 | Merck & Co Inc | Antifungal compositions and methods for their use |
US3443882A (en) * | 1966-03-14 | 1969-05-13 | Dow Chemical Co | Treatment of earth surface and subsurface for prevention of acidic drainage from the soil |
US3482636A (en) * | 1967-04-06 | 1969-12-09 | Dow Chemical Co | Method of lessening the inhibitory effects to fluid flow due to the presence of solid organic substances in a subterranean formation |
US3853771A (en) * | 1971-05-17 | 1974-12-10 | Shell Oil Co | Process for dispersing cellular micro-organisms with chelating aqueous alkaline surfactant systems |
US3733266A (en) * | 1971-09-07 | 1973-05-15 | Administrator Of The Environme | Waste water purification by breakpoint chlorination and carbon adsorption |
US4184953A (en) * | 1977-03-22 | 1980-01-22 | The British Petroleum Company Limited | Physical process |
US4620595A (en) * | 1985-08-22 | 1986-11-04 | Shell Offshore Inc. | Recovering oil by injecting ammoniated and nitrited seawater |
US4818412A (en) * | 1986-04-01 | 1989-04-04 | Betz Laboratories, Inc. | Apparatus and process for feeding hypochlorite solution |
US4701247A (en) * | 1986-07-30 | 1987-10-20 | The Dow Chemical Company | Electrochemical methods for breaking high viscosity fluids |
US4846981A (en) * | 1988-12-19 | 1989-07-11 | Texaco Inc. | Method of restoring permeability around wellbores |
US4997571A (en) * | 1990-01-05 | 1991-03-05 | Mogul Corporation | Method of treating water |
US5069286A (en) * | 1990-04-30 | 1991-12-03 | The Mogul Corporation | Method for prevention of well fouling |
US5016714A (en) * | 1990-05-09 | 1991-05-21 | Halliburton Company | Biocidal well treatment method |
US5118426A (en) * | 1990-07-26 | 1992-06-02 | Olin Corporation | Process for purifying impotable water with hypochlorous acid |
US5413178A (en) * | 1994-04-12 | 1995-05-09 | Halliburton Company | Method for breaking stabilized viscosified fluids |
US5955401A (en) * | 1996-05-17 | 1999-09-21 | Baroid Technology, Inc. | Clay-free biodegradable wellbore fluid and method for using same fluid |
US5942126A (en) * | 1997-01-03 | 1999-08-24 | Nalco Chemical Company | Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling |
US6110875A (en) * | 1997-03-07 | 2000-08-29 | Bj Services Company | Methods and materials for degrading xanthan |
US6162371A (en) * | 1997-12-22 | 2000-12-19 | S. C. Johnson & Son, Inc. | Stabilized acidic chlorine bleach composition and method of use |
US20080160612A1 (en) * | 1999-08-23 | 2008-07-03 | Puricore International Limited | Treatment of infected tissues with hypochlorous acid |
US6533958B2 (en) * | 1999-12-13 | 2003-03-18 | Acculab Co., Ltd. | System for controlling microbial fouling |
US20030092581A1 (en) * | 2001-11-13 | 2003-05-15 | Crews James B. | Fracturing fluids for delayed flow back operations |
US7090016B2 (en) * | 2001-11-14 | 2006-08-15 | Battelle Energy Alliance, Llc | Well having inhibited microbial growth |
US7578968B1 (en) * | 2002-05-03 | 2009-08-25 | Albemarle Corporation | Microbiological control in oil or gas field operations |
US7219735B2 (en) * | 2002-11-01 | 2007-05-22 | Innovative Chemical Technologies Canada Ltd. | Packer fluid |
US6814144B2 (en) * | 2002-11-18 | 2004-11-09 | Exxonmobil Upstream Research Company | Well treating process and system |
US20040120853A1 (en) * | 2002-12-20 | 2004-06-24 | Carpenter Joel F. | Biocidal control in recovery of oil by water injection |
US7231973B2 (en) * | 2004-03-15 | 2007-06-19 | Total Separation Solutions, Llc | Viscosity control and filtration of well fluids |
US20060116296A1 (en) * | 2004-11-29 | 2006-06-01 | Clearwater International, L.L.C. | Shale Inhibition additive for oil/gas down hole fluids and methods for making and using same |
US20070102359A1 (en) * | 2005-04-27 | 2007-05-10 | Lombardi John A | Treating produced waters |
US7287593B2 (en) * | 2005-10-21 | 2007-10-30 | Schlumberger Technology Corporation | Methods of fracturing formations using quaternary amine salts as viscosifiers |
US7455112B2 (en) * | 2006-09-29 | 2008-11-25 | Halliburton Energy Services, Inc. | Methods and compositions relating to the control of the rates of acid-generating compounds in acidizing operations |
US20080099207A1 (en) * | 2006-10-31 | 2008-05-01 | Clearwater International, Llc | Oxidative systems for breaking polymer viscosified fluids |
US20080115930A1 (en) * | 2006-11-22 | 2008-05-22 | Strategic Resource Optimization, Inc. | Electrolytic system and method for enhanced release and deposition of sub-surface and surface components |
US20080200355A1 (en) * | 2007-01-12 | 2008-08-21 | Emmons Stuart A | Aqueous Solution for Managing Microbes in Oil and Gas Production and Method for their Production |
US20090062156A1 (en) * | 2007-08-31 | 2009-03-05 | Halliburton Energy Services, Inc. | Methods of treating a subterranean formation including a biocidal treatment |
US20100048429A1 (en) * | 2008-02-29 | 2010-02-25 | Texas United Chemical Company, Llc | Methods, Systems, and Compositions for the Controlled Crosslinking of Well Servicing Fluids |
US20090229827A1 (en) * | 2008-03-14 | 2009-09-17 | Bryant Jason E | Treatment Fluids Having Biocide and Friction Reducing Properties and Associated Methods |
US20100204068A1 (en) * | 2009-02-12 | 2010-08-12 | Rhodia Operations | Methods for controlling depolymerization of polymer compositions |
Cited By (71)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10280360B2 (en) | 2008-11-13 | 2019-05-07 | Flotek Chemistry, Llc | Water-in-oil microemulsions for oilfield applications |
US9222013B1 (en) | 2008-11-13 | 2015-12-29 | Cesi Chemical, Inc. | Water-in-oil microemulsions for oilfield applications |
US20110132815A1 (en) * | 2010-04-09 | 2011-06-09 | Angelilli Jerome F | Portable Water Treatment System and Apparatus |
WO2011126607A1 (en) * | 2010-04-09 | 2011-10-13 | Nch Ecoservices, Llc | Portable water treatment method |
US8211296B2 (en) * | 2010-04-09 | 2012-07-03 | Nch Ecoservices, Llc | Portable water treatment system and apparatus |
US8226832B2 (en) * | 2010-04-09 | 2012-07-24 | Nch Ecoservices, Llc | Portable water treatment method |
US20110137465A1 (en) * | 2010-04-09 | 2011-06-09 | Angelilli Jerome F | Portable Water Treatment Method |
US20120085541A1 (en) * | 2010-10-12 | 2012-04-12 | Qip Holdings, Llc | Method and Apparatus for Hydraulically Fracturing Wells |
WO2012110993A1 (en) * | 2011-02-15 | 2012-08-23 | Medentech Limited | Inhibition of bacterial growth in oil field fluids |
US9371479B2 (en) | 2011-03-16 | 2016-06-21 | Schlumberger Technology Corporation | Controlled release biocides in oilfield applications |
US10323051B2 (en) | 2011-05-09 | 2019-06-18 | Rhodia Operations | Methods for controlling depolymerization of polymer compositions |
US20130020079A1 (en) * | 2011-07-18 | 2013-01-24 | Zerorez Texas, Inc. | Treatment of subterranean wells with electrolyzed water |
US20130071492A1 (en) * | 2011-09-16 | 2013-03-21 | Carmine J. Durham | Systems and methods for generating germicidal compositions |
EP2755922A4 (en) * | 2011-09-16 | 2015-06-10 | Zurex Pharmagra Llc | Systems and methods for generating germicidal compositions |
US8945355B2 (en) | 2011-09-16 | 2015-02-03 | Zurex Pharmagra, Llc | Systems and methods for generating germicidal compositions |
US8771753B2 (en) * | 2011-09-16 | 2014-07-08 | Zurex Pharmagra, Llc | Systems and methods for generating germicidal compositions |
EP3424885A1 (en) * | 2011-09-16 | 2019-01-09 | Zurex Pharmagra, LLC | Systems and methods for generating germicidal compositions |
WO2013123104A1 (en) * | 2012-02-15 | 2013-08-22 | E. I. Du Pont De Nemours And Company | PROCESS FOR HYDRAULIC FRACTURING WITH pH CONTROL |
US20130248176A1 (en) * | 2012-03-23 | 2013-09-26 | Glori Energy Inc. | Ultra low concentration surfactant flooding |
US9951264B2 (en) | 2012-04-15 | 2018-04-24 | Flotek Chemistry, Llc | Surfactant formulations for foam flooding |
US9200192B2 (en) | 2012-05-08 | 2015-12-01 | Cesi Chemical, Inc. | Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons |
US11407930B2 (en) | 2012-05-08 | 2022-08-09 | Flotek Chemistry, Llc | Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons |
US10144862B2 (en) | 2012-05-08 | 2018-12-04 | Flotek Chemistry, Llc | Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons |
US11560351B2 (en) | 2013-03-14 | 2023-01-24 | Flotek Chemistry, Llc | Methods and compositions incorporating alkyl polyglycoside surfactant for use in oil and/or gas wells |
US9464223B2 (en) | 2013-03-14 | 2016-10-11 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9868893B2 (en) | 2013-03-14 | 2018-01-16 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9884988B2 (en) | 2013-03-14 | 2018-02-06 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US11254856B2 (en) | 2013-03-14 | 2022-02-22 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US11180690B2 (en) | 2013-03-14 | 2021-11-23 | Flotek Chemistry, Llc | Diluted microemulsions with low surface tensions |
US10590332B2 (en) | 2013-03-14 | 2020-03-17 | Flotek Chemistry, Llc | Siloxane surfactant additives for oil and gas applications |
US11149189B2 (en) | 2013-03-14 | 2021-10-19 | Flotek Chemistry, Llc | Siloxane surfactant additives for oil and gas applications |
US9994762B2 (en) | 2013-03-14 | 2018-06-12 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US10000693B2 (en) | 2013-03-14 | 2018-06-19 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US10053619B2 (en) | 2013-03-14 | 2018-08-21 | Flotek Chemistry, Llc | Siloxane surfactant additives for oil and gas applications |
US9850418B2 (en) | 2013-03-14 | 2017-12-26 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9428683B2 (en) | 2013-03-14 | 2016-08-30 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US11034879B2 (en) | 2013-03-14 | 2021-06-15 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US10941106B2 (en) | 2013-03-14 | 2021-03-09 | Flotek Chemistry, Llc | Methods and compositions incorporating alkyl polyglycoside surfactant for use in oil and/or gas wells |
US10731071B2 (en) | 2013-03-14 | 2020-08-04 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells comprising microemulsions with terpene, silicone solvent, and surfactant |
US11634625B2 (en) | 2013-03-14 | 2023-04-25 | Flotek Chemistry, Llc | Siloxane surfactant additives for oil and gas applications |
US10287483B2 (en) | 2013-03-14 | 2019-05-14 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells comprising a terpene alcohol |
US10717919B2 (en) | 2013-03-14 | 2020-07-21 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9068108B2 (en) | 2013-03-14 | 2015-06-30 | Cesi Chemical, Inc. | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US10421707B2 (en) | 2013-03-14 | 2019-09-24 | Flotek Chemistry, Llc | Methods and compositions incorporating alkyl polyglycoside surfactant for use in oil and/or gas wells |
US10544355B2 (en) | 2013-03-14 | 2020-01-28 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations using emulsions comprising terpene |
US10703960B2 (en) | 2013-03-14 | 2020-07-07 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US10577531B2 (en) | 2013-03-14 | 2020-03-03 | Flotek Chemistry, Llc | Polymers and emulsions for use in oil and/or gas wells |
US9321955B2 (en) | 2013-06-14 | 2016-04-26 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US10196557B2 (en) | 2013-06-14 | 2019-02-05 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US10738235B2 (en) | 2013-06-14 | 2020-08-11 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US9890624B2 (en) | 2014-02-28 | 2018-02-13 | Eclipse Ior Services, Llc | Systems and methods for the treatment of oil and/or gas wells with a polymeric material |
US9890625B2 (en) | 2014-02-28 | 2018-02-13 | Eclipse Ior Services, Llc | Systems and methods for the treatment of oil and/or gas wells with an obstruction material |
US9505970B2 (en) | 2014-05-14 | 2016-11-29 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
WO2016010621A1 (en) * | 2014-05-19 | 2016-01-21 | Buckman Laboratories International, Inc. | Systems and methods for generating haloamines and application thereof in oil and gas operations |
US10294757B2 (en) | 2014-07-28 | 2019-05-21 | Flotek Chemistry, Llc | Methods and compositions related to gelled layers in oil and/or gas wells |
US9957779B2 (en) | 2014-07-28 | 2018-05-01 | Flotek Chemistry, Llc | Methods and compositions related to gelled layers in oil and/or gas wells |
US10202535B2 (en) * | 2014-08-28 | 2019-02-12 | Lamberti Spa | Method for treating subterranean formations |
WO2016183481A1 (en) * | 2015-05-14 | 2016-11-17 | Hydro Dynamics, Inc. | Reduction of microorganisms in drilling fluid using controlled mechanically induced cavitation |
US10550316B2 (en) | 2016-07-29 | 2020-02-04 | Canadian Energy Services L.P. | Method of forming a fracturing fluid from produced water |
CN109258688A (en) * | 2017-07-18 | 2019-01-25 | 朴莲花 | A kind of stable neutral disinfectant and preparation method and application method |
US10870791B2 (en) | 2017-08-14 | 2020-12-22 | PfP Industries LLC | Compositions and methods for cross-linking hydratable polymers using produced water |
US11248163B2 (en) | 2017-08-14 | 2022-02-15 | PfP Industries LLC | Compositions and methods for cross-linking hydratable polymers using produced water |
US10934472B2 (en) | 2017-08-18 | 2021-03-02 | Flotek Chemistry, Llc | Compositions comprising non-halogenated solvents for use in oil and/or gas wells and related methods |
US11053433B2 (en) | 2017-12-01 | 2021-07-06 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US11103840B2 (en) * | 2018-03-19 | 2021-08-31 | Process Cleaning Solutions Ltd. | Mixing and dispensing device and method |
US11236609B2 (en) | 2018-11-23 | 2022-02-01 | PfP Industries LLC | Apparatuses, systems, and methods for dynamic proppant transport fluid testing |
US11104843B2 (en) | 2019-10-10 | 2021-08-31 | Flotek Chemistry, Llc | Well treatment compositions and methods comprising certain microemulsions and certain clay control additives exhibiting synergistic effect of enhancing clay swelling protection and persistency |
US11597873B2 (en) | 2019-10-10 | 2023-03-07 | Flotek Chemistry, Llc | Well treatment compositions and methods comprising certain microemulsions and certain clay control additives exhibiting synergistic effect of enhancing clay swelling protection and persistency |
US11905462B2 (en) | 2020-04-16 | 2024-02-20 | PfP INDUSTRIES, LLC | Polymer compositions and fracturing fluids made therefrom including a mixture of cationic and anionic hydratable polymers and methods for making and using same |
US20210392898A1 (en) * | 2020-06-22 | 2021-12-23 | Parasol Medical, Llc | Stabilized hypochlorous acid solution and method for stabilizing hypochlorous acid for longer shelf life |
US11512243B2 (en) | 2020-10-23 | 2022-11-29 | Flotek Chemistry, Llc | Microemulsions comprising an alkyl propoxylated sulfate surfactant, and related methods |
Also Published As
Publication number | Publication date |
---|---|
MX2010006245A (en) | 2010-12-22 |
CA2706305A1 (en) | 2010-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20100307757A1 (en) | Aqueous solution for controlling bacteria in the water used for fracturing | |
US7712534B2 (en) | Treatment fluids having biocide and friction reducing properties and associated methods | |
EP2078066B1 (en) | Biocide for well stimulation | |
US8609594B2 (en) | Chlorine dioxide precursor and methods of using same | |
US8211835B2 (en) | Composition and method for slickwater application | |
US20090062156A1 (en) | Methods of treating a subterranean formation including a biocidal treatment | |
US20130206398A1 (en) | PROCESS FOR HYDRAULIC FRACTURING WITH pH CONTROL | |
US20140303045A1 (en) | Biocidal Systems and Methods of Use | |
US11499089B2 (en) | Biocide composition and use thereof | |
US20150329387A1 (en) | Systems and methods for generating haloamines and application thereof in oil and gas operations | |
US7578968B1 (en) | Microbiological control in oil or gas field operations | |
US10113102B2 (en) | Activity enhanced scale dispersant for treating inorganic sulfide scales | |
CA2687910A1 (en) | Environmentally favorable aqueous solution for controlling bacteria in the water used for fracturing | |
WO2015057664A1 (en) | Composition and method including mixed oxidants for treating liquids injected into or received from subterranean formations | |
WO2014062673A1 (en) | Disinfecting water used in a fracturing operation | |
US20220055896A1 (en) | Reduced Corrosion Chlorine Dioxide for Oil & Gas Well Clenaing and Sanitization | |
EP3174950B1 (en) | Microbiocides and uses thereof | |
US20220259487A1 (en) | Compositions and methods using chlorate to break polyacrylamide | |
US20150076401A1 (en) | Chlorine dioxide precursor composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SCHLUMBERGER TECHNOLOGY CORPORATION, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BLOW, KRISTEL A.;ALI, SYED A.;HOWARD, PAUL R.;AND OTHERS;SIGNING DATES FROM 20100614 TO 20100621;REEL/FRAME:024695/0240 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |