CN104893705B - A kind of borate crosslinker and the boron crosslinked fracturing fluid for being applied to high temperature deep well for preparing - Google Patents
A kind of borate crosslinker and the boron crosslinked fracturing fluid for being applied to high temperature deep well for preparing Download PDFInfo
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- CN104893705B CN104893705B CN201510164955.5A CN201510164955A CN104893705B CN 104893705 B CN104893705 B CN 104893705B CN 201510164955 A CN201510164955 A CN 201510164955A CN 104893705 B CN104893705 B CN 104893705B
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- fracturing fluid
- boron
- borate crosslinker
- crosslinked fracturing
- high temperature
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- 239000012530 fluid Substances 0.000 title claims abstract description 75
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 60
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000004971 Cross linker Substances 0.000 title claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- -1 hydroxypropyl Chemical group 0.000 claims abstract description 9
- HMDFOXQIYPYCRX-UHFFFAOYSA-N 1-(2-chloropropan-2-yl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1C(C)(C)Cl HMDFOXQIYPYCRX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims abstract description 6
- 239000001103 potassium chloride Substances 0.000 claims abstract description 6
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 3
- 239000003899 bactericide agent Substances 0.000 claims abstract description 3
- 239000004927 clay Substances 0.000 claims abstract description 3
- 230000003750 conditioning effect Effects 0.000 claims abstract description 3
- 239000002562 thickening agent Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 1
- 150000001642 boronic acid derivatives Chemical group 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000013522 chelant Substances 0.000 abstract description 7
- 239000002738 chelating agent Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 125000000707 boryl group Chemical group B* 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 description 11
- 238000010008 shearing Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000006378 damage Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 208000014674 injury Diseases 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000000887 hydrating effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000004697 chelate complex Chemical class 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
-
- 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
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
- C09K8/608—Polymer compositions
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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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- 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)
- Dispersion Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of borate crosslinker and for preparing the boron crosslinked fracturing fluid suitable for high temperature deep well, the borate crosslinker is a kind of boryl multicomponent chelate thing, using boron-containing compound, chelating agent as major ingredient, using water as solvent, reacts and is made with a temperature of in certain pH value.The boron crosslinked fracturing fluid is made up of by mass percentage following components：Borate crosslinker 0.02~0.04%, thickener hydroxypropyl guar 0.3~0.6%, bactericide dodecyl dimethyl benzyl chloride 0.02~0.03%, clay stabilizer potassium chloride 1~2%, high-temperature stabilizer sodium thiosulfate 0.02~0.03%, fluorocarbon surfactant 0.04~0.05%, PH conditioning agents sodium hydroxide 0.02~0.03%, remaining is water.The borate crosslinker can effectively control crosslinking rate, have good high temperature resistance, a high shear performance with boron crosslinked fracturing fluid of its preparation, and frictional resistance is low, the easy row of returning, and has wide market prospects.
Description
Technical field
The present invention relates to oil-gas field fracturing liquid technical field, and in particular to a kind of borate crosslinker and its preparation are applied to height
The boron crosslinked fracturing fluid of warm deep-well, the fracturing fluid system temperature resistance ability is up to 175 DEG C.
Background technology
With the continuous development of oilfield exploitation technology, oil field easily to adopt reserves fewer and fewer.At present, deep-well oil-gas reservoir is surveyed
Visit the emphasis that exploitation has become people's research.Because deep-well formation temperature is high, porosity is small, this is just to the resistance to gentle of fracturing fluid
Endurance of cutting can propose very high requirement.
Crosslinking agent is the key factor for making fracturing fluid keep superperformance.The crosslinking agent used earliest is borate, sulfuric acid
Aluminium and stibate, but the fracturing fluid configured is significant adverse to pump because being crosslinked fast, base fluid viscosity is high, heat resistance difference etc.
Factor limits its application in high temperature deep well.Then the crosslinking agent developed has aluminate and potassium chromium sulfate etc..The seventies and
The eighties makees crosslinking agent using organic titanium and organic chelate.But sent out by a large amount of laboratory experiment field evaluations (including coring)
Existing, organic metal chelate complex (titanium, zirconium) gelled fracturing fluid is to cliping and pasting rate sensitivity, and in the case where height clips and pastes rate action, cross-bond is easily broken
Split, fracturing fluid is injured seriously to propping of subterranean formations, and by contrast, borate crosslinked fracturing fluid then will to stratum and supporting crack injury
Small is more.
Recent research exploitation delay borate crosslinker, have clean it is nontoxic, viscoplasticity is good, cross-bond have shearing invertibity,
, the characteristic such as crosslinking time adjustable, Gel Breakdown thorough low to formation damage, make the master of current fracturing fluid research and application
Want direction.
The beginning of the nineties, high temperature resistance organic borate cross-linker develop rapidly, the organic boron delay crosslinking pressure break that 150 DEG C or so of heatproof
Liquid is more.The boron crosslinked fracturing fluid patent (US5445223) of Schlumberger, controlled and postponed using polymer wrapped boron ion
Crosslinking time, improves heat resistance, and its heatproof has no the report of series of products and filed application up to 176 DEG C.
China develops the borate crosslinker of high temperature resistance since the mid-90, and begins to use in some oil fields, these friendships
Connection agent has many defects：Unstable, easy precipitation, construction friction height, temperature resistance ability, crosslinking are fast, can not meet applying for fracturing fluid
Work requirement.Therefore, on the basis of borate crosslinker is postponed, a kind of pressure that disclosure satisfy that high temperature deep well and easily constructed is developed
Liquid is split to be particularly important.
The content of the invention
It is an object of the invention to provide a kind of borate crosslinker, the crosslinking agent is a kind of boryl multicomponent chelate thing, be with containing
Boron compound, chelating agent are major ingredient, using water as solvent, react and are made with a temperature of in certain pH value, can effectively control crosslinking speed
Degree, and make boron crosslinked fracturing fluid that there is good rheological property under high temperature, shear conditions.
Another object of the present invention, which also resides in provide, to be used to above-mentioned borate crosslinker prepare the boron friendship suitable for high temperature deep well
Join fracturing fluid, the boron crosslinked fracturing fluid is reacted with the borate crosslinker and other components of above-mentioned preparation in certain pH value with a temperature of to be made
Into, have good high temperature resistance, high shear performance, and frictional resistance it is low, easily the row of returning, there are wide market prospects.
To reach above technical purpose, the present invention provides following technical scheme.
A kind of borate crosslinker, is prepared via a method which：
Into reactor with 2:1 mass ratio adds boron-containing compound and chelating agent, with sodium hydroxide regulation pH value be 7~
9,2~4h is reacted under the conditions of 60~70 DEG C, obtains unitary chelate, then into reactor with 1:3 mass ratio adds boracic
Compound and chelating agent, aqueous solvent is added, the quality of water is 4 times of chelating agent quality used in unitary chelate, and stirring is equal
After even, 2~3h is reacted under the conditions of 75~85 DEG C, multicomponent chelate thing is obtained, borate crosslinker is produced after product is cooled down.
The boron-containing compound is borax, borate or trimethylborate, and the chelating agent is methanol, polyalcohol, polynary
Alkynes or triethanolamine, the polyalcohol can be dihydric alcohol, trihydroxylic alcohol etc., and polynary alkynes can be binary alkynes, ternary alkynes etc..
By above-mentioned borate crosslinker be used for prepare suitable for high temperature deep well boron crosslinked fracturing fluid, the boron crosslinked fracturing fluid by with
Lower component forms by mass percentage：Borate crosslinker 0.02~0.04%, thickener hydroxypropyl guar 0.3~0.6%, bactericide
Dodecyl dimethyl benzyl chloride 0.02~0.03%, clay stabilizer potassium chloride 1~2%, high-temperature stabilizer sodium thiosulfate
0.02~0.03%, fluorocarbon surfactant 0.04~0.05%, PH conditioning agents sodium hydroxide 0.02~0.03%, remaining is
Water.
The preparation method of the boron crosslinked fracturing fluid is as follows：
By proportioning, first a certain amount of water, potassium chloride, dodecyl dimethyl benzyl chloride, hydrogen are added to mixed adjust in device of Warring
Sodium oxide molybdena, sodium thiosulfate, fluorocarbon surfactant, then add the hydroxypropyl guar of dry powder-shaped to the inside and be stirred continuously, treat
After liquid is viscous, then crosslinking agent is added thereto, persistently stir 30min, that is, obtain the boron crosslinked fracturing fluid.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) in the borate crosslinker molecule, organic chelate and boron ion bonding, this reduces boron ion and hydroxypropyl
The bonding probability of base guanidine glue, has efficiently controlled the crosslinking rate of fracturing fluid, and crosslinking time is adjustable in 3~10min.Fracturing fluid
The controllability of crosslinking rate greatly reduces fracturing fluid caused frictional resistance in the wellbore, suitable for deep well fracturing.
(2) boron crosslinked fracturing fluid temperature resistant capability prepared by the present invention passes through 511S up to 175 DEG C at 175 DEG C-1Shearing
After 5min, then in 170S-1Its apparent viscosity illustrates that the boron crosslinked fracturing fluid resists in more than 100mPaS after the shearing of lower long-time
High temperature, resistance to high shear function admirable, it is entirely capable of the pressing crack construction requirement for meeting temperature reservoirs.
(3) in China, multiple prospect pits are applied boron crosslinked fracturing fluid prepared by the present invention, fact proved, the boron is handed over
Connection fracturing fluid can be successfully applied to high temperature deep well, and construction friction is low, flowback effect is good, fracturing yield increasing significant effect.
(4) the boron crosslinked fracturing fluid is raw materials used cheap and easy to get, and compound method is simple, and process is easily controlled.
Brief description of the drawings
Fig. 1 be the boron crosslinked fracturing fluid at 130 DEG C, 140 DEG C, 170S-1The curve that lower viscosity changes over time.
Fig. 2 is the boron crosslinked fracturing fluid in 170 DEG C, 170S-1The curve that lower viscosity changes over time.
Fig. 3 is the boron crosslinked fracturing fluid in 175 DEG C, 170S-1The curve that lower viscosity changes over time.
Embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples.
First, suitable for high temperature deep well boron crosslinked fracturing fluid preparation
Embodiment 1
(1) preparation of borate crosslinker：
It is 2 that mass ratio is added into reactor:1 trimethylborate and triethanolamine adds sodium hydroxide as reaction
It is 8 to adjust pH value, and after reacting 3h under the conditions of 68 DEG C, then it is 1 to add mass ratio into reactor:3 borax and isopropanol, and
The water of 4 times of triethanolamine quality is added, after stirring, 2h is reacted under the conditions of 80 DEG C, after reaction terminates, cooling obtains product
As borate crosslinker.
(2) it is used to prepare the boron crosslinked fracturing fluid suitable for high temperature deep well with above-mentioned borate crosslinker：
Using gross mass as 100%, first a certain amount of water, 2% potassium chloride, 0.02% hydrogen-oxygen are added to mixed adjust in device of Warring
Change sodium, 0.02% dodecyl dimethyl benzyl chloride, 0.03% sodium thiosulfate, 0.04% fluorocarbon surfactant, continuous
0.6% hydroxypropyl guar is added to the inside under conditions of stirring, after liquid rises and glued, 0.035% borate crosslinker is added to the inside,
30min is persistently stirred, can obtain the type boron crosslinked fracturing fluids of OCB- I.
Using gross mass as 100%, first a certain amount of water, 2% potassium chloride, 0.025% hydrogen-oxygen are added to mixed adjust in device of Warring
Change sodium, 0.02% dodecyl dimethyl benzyl chloride, 0.025% sodium thiosulfate, 0.04% fc-surfactant, continuous
0.5% hydroxypropyl guar is added to the inside under conditions of stirring, after liquid rises and glued, 0.04% borate crosslinker is added to the inside,
30min is persistently stirred, can obtain the type boron crosslinked fracturing fluids of OCB- II.
2nd, suitable for high temperature deep well boron crosslinked fracturing fluid performance evaluation
(1) temperature resistance anti-shear performance
OCB- I type boron crosslinked fracturing fluid 49mL, 60mL prepared by Example 1, it is anti-to monitor it with RT-20 high temperature rheometers
Cutting performance, shear rate are divided into two stages settings.First rank is broken：Shear rate 511S-1, temperature starts to warm up from room temperature,
Shear time is 5min；Second stage：Shear rate 170S-1, shear time, automatic record shearing are set by different scopes of construction item
The parameters such as speed, viscosity, temperature.
Fig. 1 is the boron crosslinked fracturing fluid at 130 DEG C, 140 DEG C, 170S-1Under hot shearing during the hours of viscosity 1.5
Interior change curve.As seen from the figure, at a temperature of two kinds the viscosity of fracturing fluid shearing 10min just reached later 100mPa.S with
On, and higher viscosity is always maintained in 80min, show on this condition, the boron crosslinked fracturing fluid has good resist
Warm anti-shear performance.
Fig. 2 is the boron crosslinked fracturing fluid in 170 DEG C, 170S-1Under hot shearing during in the hours of viscosity 2 change it is bent
Line.As seen from the figure, the boron crosslinked fracturing fluid system has particularly excellent temperature resistance anti-shear performance.In 170 DEG C of abnormal high temperature
Under the conditions of, within the time up to 120min, boron crosslinked fracturing fluid viscosity is held at more than 100mPa.S, is the large-scale pressure of deep-well
Split and provide good fluid conditions.Also indicate that the heat-resisting property of the boron crosslinked fracturing fluid also has the space lifted simultaneously.
Fig. 3 be the boron crosslinked fracturing fluid at 175 DEG C, 511S-1Shear 5min, 170S-1Shear the viscous of 80min shearing
Degree-time plot, the chart is bright, at 175 DEG C, 511S-15min is sheared, in 170S-1After the process for shearing 80min, boron is handed over
Join fracturing fluid apparent viscosity still in more than 100mPa.S, it is shown that good temperature resistance anti-shear performance.
(2) compatibility
The crude oil and stratum water of a certain prospect pit in Zhongyuan Oil Field are taken, the type boron crosslinked fracturing fluids of OCB- I prepared with embodiment 1
Broken glue hydrating fluid does compatibility experiment.The viscosity of boron crosslinked fracturing fluid hydrating fluid is 3mPa.s, by in-place oil and broken glue
Liquid presses 3 respectively：1、3：2、1：3 volume ratio mixes, and after high-speed stirred, constant temperature observes and records 2hr in 95 DEG C of water-bath
Afterwards, demulsification efficiency 98%.Then glue hydrating fluid and stratum water are taken brokenly, by 1：2、1：1、2：1 volume ratio mixing, constant temperature is at 70 DEG C
Water-bath in, it is no precipitation and flocculation phenomenon.Thus illustrate：The boron crosslinked fracturing fluid has preferable compatibility with formation fluid
Property, it can meet that stratum requires.
(3) core injury ability and filtration property
OCB- I and the type each 60mL of boron crosslinked fracturing fluid of OCB- II prepared by Example 1, given birth to Cole-lab instrument companies
The RPT-124 dynamic filtrations injury instrument of production carries out damage evaluation to stratum core, and experimental results are shown in Table 1.By number in table 1
According to understanding, injury ability of two kinds of boron crosslinked fracturing fluids to stratum is smaller.Determine the type boron crosslinked fracturing fluids of OCB- I under different temperatures
Leakoff coefficent, can obtain the result such as table 2, table 2 shows that the boron crosslinked fracturing fluid has good control filtration property.
The fracturing fluid damage experiment performance evaluation of table 1
The boron crosslinked fracturing fluid leakoff coefficent of table 2
3rd, suitable for high temperature deep well boron crosslinked fracturing fluid application
Example 1：
The a certain prospect pit of NW Hebei, formation temperature be 172 DEG C, be construction formation temperature highest a bite well, its fractured layer
Position:ES3 3；Well section:4740.9~4761.0m；Thickness:9.6m；The number of plies:4.Because the oil well is very deep, stratum geological condition is complicated,
Difficulty of construction is big, and past construction success rate is always than relatively low.Later, this area used the type boron crosslinked fracturing fluid systems of OCB- I
Pressure break is carried out, wherein, pressure break mode:Oil jacket mixed water injection, close lamination and split；Pipe string combination of constructing requires:N80-The additional heat-bodied oils of 73mm
Pipe；Horn mouth position:3200.0m；Requirement to well head:1000# production trees；Well design plus sand (0.45-0.90mm high intensity
Haydite) 61.6 tons, boron crosslinked fracturing fluid 340m3, gel water 95m3, the well construction frictional resistance is low, and operation pressure is steady, is returned after pressure break
Row works well, and increase day by day natural gas 30000m3, create the record of boron crosslinked fracturing fluid high temperature MHF.
Example 2：
The a certain prospect pit in Zhongyuan Oil Field, the well construction well section：3619.7-3946m；Form of construction work：Oil jacket mixed water injection, throw a pressure
Two；Porosity：15.0-23.0%；Proppant haydite：120m3；Formation temperature：160℃.The well is crosslinked using the type boron of OCB- II
Fracturing fluid system carries out pressure break, wherein well design plus 0.45/0.90 haydites 80m3, fracturing fluid 745m3, active water 90m3, pressure break
Afterwards, the well averagely often increases day by day oily 8.5 tons, and the term of validity is 60 days, and accumulative increasing is oily 20.4 ten thousand tons altogether.
Site operation proves that the deep-well high temperature resistance boron crosslinked fracturing fluid has good high temperature resistance high shear ability and the row of returning
Ability, good construction effect can be still especially obtained in the prospect pit of geological condition difference, this has absolutely proved that the boron is crosslinked
Fracturing fluid wide market, it is a kind of fracturing fluid system of function admirable.
Claims (2)
1. a kind of borate crosslinker, is prepared via a method which：It is 2 that mass ratio is added into reactor:1 trimethylborate and three
For monoethanolamine as reactant, it is 8 to add sodium hydroxide regulation pH value, after reacting 3h under the conditions of 68 DEG C, then is added into reactor
Enter mass ratio for 1:3 borax and isopropanol, and the water of 4 times of triethanolamine quality is added, after stirring, under the conditions of 80 DEG C
2h is reacted, after reaction terminates, it is borate crosslinker that cooling, which obtains product,.
2. the borate crosslinker described in claim 1 is used to prepare the boron crosslinked fracturing fluid suitable for high temperature deep well, boron crosslinking
Fracturing fluid is made up of by mass percentage following components：Borate crosslinker 0.02~0.04%, thickener hydroxypropyl guar 0.3~
0.6%, bactericide dodecyl dimethyl benzyl chloride 0.02~0.03%, clay stabilizer potassium chloride 1~2%, high-temperature stable
Agent sodium thiosulfate 0.02~0.03%, fluorocarbon surfactant 0.04~0.05%, pH conditioning agents sodium hydroxide 0.02~
0.03%, remaining is water.
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| CN107469840A (en) * | 2017-09-25 | 2017-12-15 | 西南石油大学 | A kind of preparation method and its usage of the solid complex photochemical catalysts of BiOBrxI1 x/BiOBr |
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| CN111057532A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Fracturing crosslinking agent and guar gum fracturing fluid |
| CN112442066A (en) * | 2020-12-03 | 2021-03-05 | 广东金柏新材料科技股份有限公司 | Phosphate ammonium salt and preparation method and application thereof |
| CN113512414B (en) * | 2021-07-29 | 2022-10-14 | 成都佰椿石油科技有限公司 | Delayed crosslinking type high-temperature-resistant low-friction-resistance aggravated guanidine gum fracturing fluid and application method thereof |
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