CN108485638A - Acidic fracturing fluid and preparation method thereof - Google Patents
Acidic fracturing fluid and preparation method thereof Download PDFInfo
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- CN108485638A CN108485638A CN201810404284.9A CN201810404284A CN108485638A CN 108485638 A CN108485638 A CN 108485638A CN 201810404284 A CN201810404284 A CN 201810404284A CN 108485638 A CN108485638 A CN 108485638A
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- fracturing fluid
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- 239000012530 fluid Substances 0.000 title claims abstract description 99
- 230000002378 acidificating effect Effects 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000002562 thickening agent Substances 0.000 claims abstract description 52
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- -1 Alkyl dimethyl ammonium chloride Chemical compound 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 229960000587 glutaral Drugs 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 229940054441 o-phthalaldehyde Drugs 0.000 claims description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- IOJNPSPGHUEJAQ-UHFFFAOYSA-N n,n-dimethyl-4-(pyridin-2-yldiazenyl)aniline Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=N1 IOJNPSPGHUEJAQ-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 230000006378 damage Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920006318 anionic polymer Polymers 0.000 description 3
- 150000001450 anions Chemical group 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- KNMXNVMDTOAYBU-UHFFFAOYSA-N tert-butyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C KNMXNVMDTOAYBU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
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- 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
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an acid fracturing fluid which comprises the following raw materials in percentage by weight: zwitterionic copolymer thickener: 0.4% -0.8%; a crosslinking agent: 1.5% -1.8%; pH regulator: 0.05% -0.2%; a cleanup additive: 0.1% -0.5%; water: and (4) the balance. The acid fracturing fluid has good temperature resistance and shear resistance, and the temperature resistance can reach 200 ℃.
Description
Technical field
The present invention relates to a kind of oil-gas mining acidic fracturing fluids and preparation method thereof.
Background technology
As oil-gas exploration and development constantly develops in depth, the exploration and development change of hypotonic, low pressure, high temperature deep-seated oil gas reservoir
Must be more and more important, pressure break is increasingly taken seriously as the technological means that such oil-gas reservoir is increased production.Fracturing fluid is applied as pressure break
The working solution of work is the principal element for influencing pressing crack construction effect.
The fracturing fluid being currently mainly used is aqueous fracturing fluid, is formulated by thickening agent, crosslinking agent, auxiliary agent and water,
In host agent be thickening agent.According to the difference of thickening agent, existing main fracturing fluid system can be divided into following 3 class：Natural plant gum
Fracturing fluid system, Surfactant Used in Viscoelastic Fracturing Fluids fracturing fluid (VES) system and synthetic polymer hydrofracturing fluid system, with natural plant gum pressure break
Based on liquid.The thickening agent that plant gum fracturing fluid uses is mainly guanidine glue and its modified product, such thickening agent thickening capabilities is strong, can
Bridging property is good, but need to be crosslinked under alkaline condition, and raw material relies on import, and price is unstable, exists simultaneously that residue is more, easily causes ground
The problems such as layer injury；VES fracturing fluid systems overcome the plant gum fracturing fluid disadvantage big to formation damage, but its heat resistance compared with
Difference cannot meet temperature reservoirs pressing crack construction requirement；Synthetic polymer hydrofracturing fluid has the characteristics that thickening agent structure compared with easy-regulating,
It is one of the important development direction of aqueous fracturing fluid technology, has become domestic and international research hotspot.The synthesized polymer that early stage uses
Object thickening agent is polyacrylamide, type methylene polyacrylamide solves the problems, such as polymer high efficiency increasing stick to a certain extent,
But its heat-resistant salt-resistant and shear stability are still unsatisfactory, fail to be widely applied.
In recent years, in order to obtain the synthetic polymer hydrofracturing fluid of function admirable, scientific worker, which has carried out, is based on acryloyl
The polymer fracturing fluid of amine copolymer object is studied.For example, CN102206484 discloses one kind using hydrophobic associated polymer as thickening agent
Acidic water repellent associated matter fracturing fluid, which is suitble to the pressure break of alkali quick reservoir, strong retraction reservoir to change
Make, have good delayed cross-linking performance, solid-carrying performance be good, fragile glue returns row, and low frictional resistance small to formation damage, low residue,
The advantages that preventive effect of expansion is good, but its temperature tolerance is also only applicable to 130 DEG C of oil-gas reservoirs；CN102702424 is disclosed with acrylamide
（AM）/ 2- acrylamide-2-methylpro panesulfonic acids (AMPS)/MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride（DMC）Both sexes from
Sub- polymer is the fracturing fluid of thickening agent, which realizes that acid takes sand technique, is applicable to the high quick property mineral formation containing alkali
Acid add sand to be transformed, but its temperature tolerance is only applicable in 120 DEG C of oil-gas reservoirs, and cost of material is higher；CN104194763A discloses one
Kind anionic polymer thickening agent, fracturing fluid and preparation method thereof, the acrylamide of proposition（AM）/ acrylic acid（AA）/ acrylic acid
Octadecyl ester（ODA）Anionic polymer thickening agent made of copolymerization is only applicable to 130 DEG C or less oil-gas reservoirs；CN104177534 is public
A kind of cationic polymer thickening agent, fracturing fluid and preparation method thereof, the acrylamide of proposition are opened（AM）Two allyl of/dimethyl
Ammonium chloride（DMDAAC）Cationic polymer thickening agent is also only applicable to 160 DEG C of oil-gas reservoirs；CN104449643A discloses oil
Field fracturing fluid heat-resistant polymer thickening agent and the preparation method and application thereof, the proposition of proposition is with acrylamide and vinyl monomer
Copolymer be thickening agent, the fracturing fluid heat resistance of preparation reaches 180 DEG C.It is poly- that US4959163 discloses a kind of amphoteric ion
Object fracturing fluid gelatinizer is closed, proposes to take precautions against preparing AM, AMPS and methacryloxypropyl dimethyl-using inverse emulsion polymerization
2- hydroxypropyls ammonium sulfate (MAPDMDHPAS) terpolymer thickening agent, using the amphoteric polymer prepare fracturing fluid have compared with
The good stronger of high temperature resistance and saline-alkaline tolerance
In conclusion most of fracturing fluids are alkaline fracturing fluid at present, 150 DEG C of reservoir environments below are only applicable to, lack energy
The Low Damage high temperature fracture liquid of tolerance 180 DEG C or more, it is existing to be resistant to high temperature fracture liquid there is also thickening agent dosage and system pH
It is higher（Thickening agent dosage >=1%, pH ＞ 5）The problems such as.Amphoteric ion polymer good salt tolerance can inhibit the clay mine in stratum
The formation damage that object is generated by hydration swelling with migration has the structure and performance characteristic of fracturing fluid with low damage, but related at present
The research of amphoteric ion polymer fracturing fluid and application work are few, and the anion structure for the amphoteric ion polymer being related to uses
The monomer containing sulfonic group of AMPS obtains, and product cost is high, is unfavorable for promoting and applying.Acidic polymer fracturing fluid can eliminate alkaline item
Part crosslinking leads to the reservoir secondary injury that the quick fine migration of the alkali on high clay content stratum generates, and can get better pressure break effect
Fruit.Therefore, inexpensive amphoteric ion polymer thickening agent is constructed using carboxylic monomer, researched and developed on this basis heat safe
Amphoteric ion polymer fracturing fluid has a very important significance.
Invention content
The present invention is directed to existing for the above-mentioned prior art defects and deficiency, provide a kind of acidic fracturing fluid, the acid
Property fracturing fluid have good heatproof anti-shear performance, temperature resistant capability is up to 200 DEG C.
The present invention also provides the preparation methods of the acidic fracturing fluid, and this method is easy to operate, and cost is relatively low, have wide
Market prospects.
The present invention is realized by using following technical proposals：
A kind of acidic fracturing fluid, it is characterised in that：Raw material weight percentage is as follows：Amphoteric ion copolymer thickening agent：0.4%-
0.8%；Crosslinking agent：1.5%-1.8%；PH adjusting agent：0.05%-0.2%；Cleanup additive：0.1%-0.5%；Water：Surplus.
The amphoteric ion copolymer thickening agent, composition and molal weight percentage are as follows：Acrylamide：70%-
90%；Cationic monomer：5%-15%；Anionic monomer：5%-15%.
The anionic monomer is acrylic acid (AA), methacrylic acid (MAA), itaconic acid, 3- acrylamido -3- first
Base butyric acid (AMB) any one or more of.
The cationic monomer is diallyldimethylammonium chloride（DADMAC）, acrylyl oxy-ethyl-trimethyl chlorination
Ammonium（DAC）, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride（DMC）, acrylic acid-N, N- dimethylaminoethyl（DMAEA）, methyl
Acrylic acid-N, N- dimethylaminoethyl（DMAEMA）Any one or more of.
The crosslinking agent is organic titanium multiple crosslinking agent, and raw material weight percentage is as follows：Butyl titanate：4%；Second two
Alcohol：50%；Glycerine：9%；Lactic acid：27%；Aldehydes organic compound：10%.
The aldehydes organic compound is any one in formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, o-phthalaldehyde
Or it is a variety of.
The pH adjusting agent is one kind in hydrochloric acid, acetic acid, lactic acid, citric acid.
The cleanup additive is one kind in nonionic surfactant or quaternary ammonium salt cationic surfactant.
The pH adjusting agent is hydrochloric acid, and cleanup additive is the cleanup additive for being model SD2-10.
Cleanup additive SD2-10 is fluorine-containing surfactant, commercial product.
A kind of preparation method of acidic fracturing fluid, it is characterised in that：
1）Amphoteric ion polymer thickening agent is added in deionized water, is stirred to complete molten；
2）The cleanup additive for accounting for thickening agent base fluid total amount 0.1%-0.5% is added thereto, stirs to complete molten；
3）Adjusting pH value of solution is 3-4；
3）It is added thereto and accounts for thickening agent base fluid total amount 1.5%-1.8% organic titanium multiple crosslinking agents, stir 2min or so and obtain.
Compared with prior art, what the present invention was reached has the beneficial effect that：
（1）Thickening agent amphoteric ion polymer provided by the present invention, using carboxylic monomer and containing can inhibit clay aquation
The cationic monomer of expansion is constructed, and the comprehensive performance of anion and cationic polymer is had both.With existing using containing sulfonic group
The amphoteric ion polymer fracturing fluid gelatinizer for preparing of monomer compare, have that raw material sources are wide, the advantages such as at low cost.
（2）Thickening agent provided by the invention can mating with it organic titanium multiple crosslinking agent crosslinking in acid condition, disappear
In addition to the fracturing fluids such as guanidine glue and its derivative are because of the quick fine migration of alkali on high clay content stratum caused by alkaline condition is crosslinked
The reservoir damage of generation.
（3）Fracturing fluid provided by the invention can have excellent heatproof anti-shear performance under the conditions of thickening agent dosage is lower
Fracturing fluid, the petroleum resources for Efficient Development high-temperature stratum provide new method.Fracturing fluid gel prepared by the present invention is chosen
It is good to hang performance, elasticity is good.
Description of the drawings
Below in conjunction with specification drawings and specific embodiments, the present invention is described in further detail, wherein：
Fig. 1 is PADA thickening agent Matrix viscosity variation with temperature relational graphs；
Fig. 2 is the variation diagram of the viscosity with temperature of PADA/ organic titanium multiple crosslinking agent fracturing fluids；
Fig. 3 is the variation diagram of the viscosity with temperature and shear time of PADA/ organic titanium multiple crosslinking agent fracturing fluids；
Fig. 4 is influence diagram of the pH value to PADA/ organic titanium multiple crosslinking agent fracturing fluid heatproof anti-shear performances；
Fig. 5 is influence diagram of the NaCl concentration to PADA/ organic titanium multiple crosslinking agent fracturing fluid heatproof anti-shear performances.
Specific implementation mode
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is served only for
The invention will be further described, should not be understood as limiting the scope of the invention, person skilled in the art's root in the field
According to some nonessential modifications and adaptations that foregoing invention content makes the present invention, protection scope of the present invention is still fallen within.
Embodiment 1：The preparation and assessment of performance of amphoteric ion polymer thickening agent
1, the preparation of amphoteric ion polymer thickening agent PADA：
（1）The composition of raw materials of amphoteric ion polymer PADA：
Acrylamide 90%, acrylic acid 5%, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 5%（It is with molal weight percentage
Meter）, initiator is ammonium persulfate, accounts for the 0.08% of monomer gross mass.
（2）The preparation method of amphoteric ion polymer PADA：
1）Quantitative deionized water, acrylamide are added in 250ml there-necked flasks（AM）, after stirring evenly, continuation is dripped thereto
It is AM to add a certain amount of acrylic acid (AA) and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), molal weight ratio:AA:
DMC=90:5:5；
2）It stirs evenly and is placed in 45 DEG C of reactors；
3）It is passed through nitrogen and is bubbled 20min, initiator is added and causes polymerization, stop leading to nitrogen when reaction solution becomes sticky, bubble becomes small
Gas；
（4）White clear colloid is obtained after polymerization 4-5h, drying is taken out and is granulated, obtain polymer thickening agent PADA.
2, the temperature tolerance of amphoteric ion polymer thickening agent PADA measures：
The measuring changing rule of 0.6% thickening agent PADA base fluid viscosity with temperature, in 30 DEG C of initial temperature, heating rate 3
DEG C/min, shear rate 170s-1Under conditions of measure thickening agent Matrix viscosity variation with temperature relationship, laboratory apparatus is Haake
RV20 rotational rheometers, thickening agent Matrix viscosity increases with temperature and declines experimental result such as Fig. 1 as seen from Figure 1, works as temperature
When degree is increased to 180 DEG C, Matrix viscosity still reaches 38mPas, shows good thickening property and heat resistance.
Embodiment 2：The preparation of organic titanium multiple crosslinking agent
1）In the three-necked flask dried to 250mL according to certain sequence be added certain mass score ethylene glycol, glycerine, lactic acid,
Glutaraldehyde and butyl titanate,
2）It is put into 85 DEG C of thermostat water baths, after being stirred to react 3.5h with certain speed, obtains organic titanium multiple crosslinking agent.
The organic titanium multiple crosslinking agent is using Butyl Phthalate as host agent, and polyalcohol and polyacid are ligand, and alcohol is solvent,
It introduces again on the basis of this and can crosslink the aldehyde compound reacted with amide group.Under room temperature, PADA and organic titanium shape
At cross-linked structure, under high temperature, amide groups is crosslinked with active carbonyl group again, stablizes cross-linked structure again, to further increase
The temperature tolerance and endurance of cutting of fracturing fluid gel.
Embodiment 3：The preparation of fracturing fluid
1. pressure break formula of liquid：
Amphoteric ion polymer thickening agent 0.6%；Organic titanium multiple crosslinking agent 1.5%-1.8%；PH adjusting agent hydrochloric acid 0.05%-
0.2%；Cleanup additive SD2-10 contents are 0.25%；Surplus is water（By mass percent in terms of）.
2. the preparation method of fracturing fluid：
1）A certain amount of amphoteric ion polymer thickening agent is added in deionized water, is stirred to complete molten；
2）The cleanup additive for accounting for thickening agent base fluid total amount 0.25% is added thereto, stirs to complete molten；
3）Adjusting pH value of solution is 3-4；
3）It is added thereto and accounts for thickening agent base fluid total amount 1.5%-1.8% organic titanium multiple crosslinking agents, stir 2min or so and obtain.
It is good that fracturing fluid gel prepared by the present invention hangs performance, and elasticity is good.
Embodiment 4：High-temperature high-pressure splits rheological property measurement
The thickening agent in example 1 is chosen, it is thick to weigh 0.6g according to the pressure break liquid and preparation method thereof of example 3 for the crosslinking agent in example 2
Agent dissolves in 100ml deionized waters, and stirring takes 50ml after thickening agent complete swelling, 0.12g is added thereto and helps row to complete molten
Agent SD2-10, stirring is to complete molten, then 0.8g organic titanium multiple crosslinking agents are added thereto, and stirring 2-3min or so can extremely choose completely
It hangs.Fracturing fluid is fitted into Haake RV20 rotational rheometers.
Fracturing fluid gel viscosity variation with temperature is measured under conditions of 3 DEG C 30 DEG C of initial temperature, heating rate/min
Relationship such as Fig. 2.As seen from Figure 2, when temperature rises to 200 DEG C, fracturing fluid gel viscosity is still in 50mPas or more, explanation
The fracturing fluid heatproof obtained is up to 200 DEG C.
Control heating rate is 3 DEG C/min, initial temperature is 30 DEG C, and constant temperature after being warming up to 180 DEG C is in shear rate
170s-1Lower continuous shear stress 90min measures fracturing fluid viscosity and changes with time as Fig. 3 can be seen that in 180 DEG C, 170s-1
Under conditions of shearing 90min after viscosity still in 72mPas or more；It is also seen that in 60min-70min, 120min-140min
There is viscosity rebound in period, can be shown that it the phenomenon that secondary cross-linking occurs.Illustrate that the fracturing fluid has good heatproof
Anti-shear performance.
Example 5：Influence of the pH value to fracturing fluid property
The thickening agent in example 1 is chosen, the crosslinking agent in example 2 is molten in thickening agent according to the pressure break liquid and preparation method thereof of example 3
Liquid a concentration of 0.6%, cleanup additive content are that the 0.25% of base fluid total amount adds pH adjusting agent under conditions of crosslinking agent dosage is 1.5%
Change crosslinking pH preparing fracturing fluids, fracturing fluid is fitted into Haake RV20 rotational rheometers.PH value is investigated to fracturing fluid property
It influences, the results are shown in Table 1 and Fig. 4.It can be seen from figure and table when pH=2, the gelation time of the fracturing fluid system is 5min, pressure break
Liquid viscosity is relatively low, and heatproof anti-shear performance is poor, in 180 DEG C, 170s-1Under conditions of shearing 90min after, viscosity is in 30mPas
Below；When pH=3, the gelation time of fracturing fluid is 2min, and fracturing fluid heatproof anti-shear performance is good, in 180 DEG C, 170s-1Condition
After down cut 90min, viscosity is in 100mPas or more；When pH=4-5, fracturing fluid is in 180 DEG C, 170s-1Under conditions of shear
After 90min, viscosity is in 50-70mPas；When pH ＞ 6, base fluid is not crosslinked with crosslinking agent.Illustrate with both sexes provided by the invention from
Sub- polymer thickening agent can be crosslinked with its mating organic titanium multiple crosslinking agent in acid condition, the good fracturing fluid of forming properties
System.
Embodiment 6：The salt resistant character of fracturing fluid
The thickening agent in example 1 is chosen, the crosslinking agent in example 2 is prepared different according to the pressure break liquid and preparation method thereof of example 3
The fracturing fluid of NaCl concentration is loaded into Haake RV20 rotational rheometers, investigates the polymer pressure break under different NaCl concentrations
Liquid heatproof anti-shear performance, is as a result shown in Fig. 5.It can be seen from the figure that with the increase of NaCl concentration, fracturing fluid originate viscosity by
Gradually decline, after NaCl concentration is more than 1.5%, fracturing fluid viscosity declines no longer apparent.In 180 DEG C, 170s-1After shearing 90min,
The fracturing fluid viscosity gap that various concentration NaCl is added is little, is all higher than 50mPas, and NaCl concentration is 1.5% fracturing fluid
Viscosity is more than the fracturing fluid for being not added with NaCl after shearing 90min, this is because thickening agent strand is simultaneous with anions and canons base
Group, is added after a certain amount of NaCl since the synergistic effect of positive and negative charge may be such that macromolecular chain stretches, and fracturing fluid viscosity increases.
It is possible thereby to illustrate, fracturing fluid system provided by the invention has good salt resistant character.
Embodiment 7：The broken colloidality energy of fracturing fluid
The ammonium persulfate that content is 0.02%-0.08% is added into the fracturing fluid system of embodiment 4, passes through in confined conditions
After 180 DEG C of processing 5h, breaking glue solution is obtained, its viscosity is measured and is less than 5mPas, surface tension is less than 28mN/m, and fracturing fluid is broken
Glue is functional.
Table 1 is influence of the pH value to PADA/ organic titanium multiple crosslinking agent fracturing fluid gel-forming properties.
Claims (10)
1. a kind of acidic fracturing fluid, it is characterised in that：Raw material weight percentage is as follows：Amphoteric ion copolymer thickening agent：0.4%-
0.8%；Crosslinking agent：1.5%-1.8%；PH adjusting agent：0.05%-0.2%；Cleanup additive：0.1%-0.5%；Water：Surplus.
2. a kind of acidic fracturing fluid according to claim 1, it is characterised in that：The amphoteric ion copolymer thickening
Agent, composition and molal weight percentage are as follows：Acrylamide：70%-90%；Cationic monomer：5%-15%；Anionic monomer：
5%-15%。
3. a kind of acidic fracturing fluid according to claim 2, it is characterised in that：The anionic monomer be acrylic acid,
Methacrylic acid, itaconic acid, 3- acrylamidos -3 Methylbutanoic acid any one or more of.
4. a kind of acidic fracturing fluid according to claim 2, it is characterised in that：The cationic monomer is diallyl
Alkyl dimethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylic acid-N,
N- dimethylaminoethyls, methacrylic acid-N, N- dimethylaminoethyl any one or more of.
5. a kind of acidic fracturing fluid according to claim 1, it is characterised in that：The crosslinking agent is the compound friendship of organic titanium
Join agent, raw material weight percentage is as follows：Butyl titanate：4%；Ethylene glycol：50%；Glycerine：9%；Lactic acid：27%；Aldehydes is organic
Compound：10%.
6. a kind of acidic fracturing fluid according to claim 5, it is characterised in that：The aldehydes organic compound is first
Any one or more in aldehyde, acetaldehyde, glyoxal, glutaraldehyde, o-phthalaldehyde.
7. a kind of acidic fracturing fluid according to claim 1, it is characterised in that：The pH adjusting agent be hydrochloric acid, acetic acid,
One kind in lactic acid, citric acid.
8. a kind of acidic fracturing fluid according to claim 1, it is characterised in that：The cleanup additive is lived for non-ionic surface
One kind in property agent or quaternary ammonium salt cationic surfactant.
9. a kind of acidic fracturing fluid according to claim 1, it is characterised in that：The pH adjusting agent is hydrochloric acid, the row of helping
Agent is the cleanup additive for being model SD2-10.
10. a kind of preparation method of acidic fracturing fluid according to claim 1, it is characterised in that：
1）Amphoteric ion polymer thickening agent is added in deionized water, is stirred to complete molten；
2）The cleanup additive for accounting for thickening agent base fluid total amount 0.1%-0.5% is added thereto, stirs to complete molten；
3）Adjusting pH value of solution is 3-4；
3）It is added thereto and accounts for thickening agent base fluid total amount 1.5%-1.8% organic titanium multiple crosslinking agents, stir 2min or so and obtain.
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| CN116590000A (en) * | 2023-05-06 | 2023-08-15 | 郑州德赛尔陶粒有限公司 | Fracturing propping agent taking red mud as additive and preparation method thereof |
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