CN106318366A - Reversible physical crosslinking agent and preparation method thereof - Google Patents
Reversible physical crosslinking agent and preparation method thereof Download PDFInfo
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- C09K8/62—Compositions for forming crevices or fractures
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Abstract
The invention relates to a reversible physical crosslinking agent and a preparation method thereof. The reversible physical crosslinking agent comprises an anionic surfactant and low carbon alcohol, and forms physical crosslinking with a polymer thickening agent through static electricity, hydrogen bonds or Van der Waals force, so the purpose of thickening is achieved, and good viscoelasticity is obtained. According to the invention, the fracturing fluid prepared from the reversible physical crosslinking agent and the polymer thickening agent is measured at room temperature, wherein the viscosity before shearing is 90 to 340 mPa-s; the viscosity after shearing is measured to be 100 to 300 mPa-s by shearing for 2 hours at 120 to 160 DEG C under 170 S-1 and by temperature cooling to room temperature, so the shearing recoverability is proved to be good; the delayed crosslinking time of the reversible physical crosslinking agent is controllable in 30 to 180 s; and the prepared fracturing fluid has the advantages of low frictional resistance, easy gel breaking, easy flowback and low damage. The reversible physical crosslinking agent has the following advantages: raw materials needed for industrial production have few varieties, extensive sources and low price; the synthetic process has simple operation; and the application prospects is wide.
Description
Technical field
The invention belongs to oil gas field stimulation technology field, be specifically related to a kind of reversible physical cross-linking agent and system thereof
Preparation Method.
Background technology
Cross-linking agent is one of main additive of aqueous fracturing fluid, it and natural polymers or synthesis
High molecular polymer interacts, and forms high viscosity frozen glue so that fracturing fluid has excellent making and meets and take
Sand ability.Conventional cross-linking agent is roughly divided into chemical cross-linking agent and reversible physical cross-linking agent.
Chemical cross-linking agent and thickening agent, by covalent bond or coordinate bond effect, play Efficient Adhesive Promotion, domestic and foreign literature
More for the type cross-linking agent report.Chinese patent CN102040995A discloses a kind of high temperature retarding-type to be had
The preparation method of machine zirconium crosslink agent, this invention Applicable temperature is 80~120 DEG C, and crosslinking slack time is 50~300
S, the reservoir that this invention is more than 120 DEG C for temperature is inapplicable.Chinese patent CN103396780A discloses one
Plant high temperature resistance retarding-type organic boron cross-linking agent, consisting of 20~45 parts of water, 5~15 parts of Organic Alcohols, 8~20
Part boron compound, 0.5~3 part of sulfate, 5~15 parts of organic acid compounds, 10~40 parts of polyhydric alcohol, 1~4
Part sodium hydroxide, this invention temperature resistant capability is 140 DEG C, and the delayed cross-linking time is 3 minutes.Chinese patent CN
102838781 A describe the superhigh temperature organic zirconium crosslinker of a kind of applicable crosslinked polymer, consisting of 200~
350 parts of water, 170~280 parts of Organic Alcohols, 40~100 parts of zirconium compoundss, 20~50 parts of organic acid, 300~
350 parts of alkanolamines, this invention heatproof can reach 200 DEG C, and injury rate is 24.75%, although this patent heatproof
Ability increases, but the injury to reservoir is bigger.It is many that Chinese patent CN 102108294 discloses one
The preparation method of hydroxyl alcohol fracturing fluid organic titanium cross-linking agent, consisting of alkali, sugar, dihydroxylic alcohols and butyl titanate
Mixing according to a certain percentage, reaction temperature is 110~150 DEG C, and the response time is 1~5 hour, and this patent is not
Introduce delay crosslinking time and the heat resistance of cross-linking agent.Chinese invention patent CN 103275690 A describes
A kind of by gathering that organic acid, inorganic base, organic amine, trivalent metal ion salts, tetravalence zirconates, aldehyde and water form
Compound fracturing fluid cross-linking agent, this cross-linking agents time 10~180s is controlled, and cross-link intensity is high, and crosslinking is frozen
Glue heat resistance reaches 150 DEG C.Above-mentioned patent is chemical cross-linking agent, mainly includes machine borate crosslinker, has
Machine zirconium crosslink agent and organic titanium cross-linking agent.The problem that chemical cross-linking agent is primarily present is the required raw material types of synthesis
More, cost of material is high, and toxicity is big, and synthesis technique is more complicated;The frictional resistance being configured to fracturing fluid system is big, broken
Glue is not thorough, is difficult to the row of returning.
Reversible physical cross-linking agent and thickening agent by electrostatic, hydrogen bond or van der Waals interaction, its intermolecular or
Intramolecular produces some strength and reversible association, forms tridimensional network, thus plays thickening effect
Really.Till up to now, domestic and foreign literature is less for the special report of reversible physical cross-linking agent.
Summary of the invention
The technical problem to be solved is the deficiency for existing chemical cross-linking agent, it is provided that a kind of reversible thing
Reason cross-linking agent.This reversible physical cross-linking agent commercial production needed raw material kind is few, wide material sources, cheap,
And technological operation is simple;The fracturing fluid using this reversible physical cross-linking agent and polymer viscosifier to be made into has heatproof
Ability is strong, shear restoration good, crosslinking time is controlled, low frictional resistance, fragile glue, the easily row of returning and Low Damage etc.
Advantage, has a extensive future.
To this end, the invention provides a kind of reversible physical cross-linking agent, it contains anion surfactant and low-carbon (LC)
Alcohol.
According to the present invention, in described reversible physical cross-linking agent, described anion surfactant and described low-carbon (LC)
The mass ratio of alcohol is (0.1~5): 1.The most described anion surfactant and the mass ratio of described low-carbon alcohols
For (0.5~2): 1.The described anion surfactant being more highly preferred to is 1:1 with the mass ratio of described low-carbon alcohols.
In some currently preferred embodiments of the present invention, possibly together with water in described reversible physical cross-linking agent.
In some further preferred embodiments of the present invention, described reversible physical cross-linking agent group by mass
Become as follows:
Anion surfactant 20%~40%;
Low-carbon alcohols 20%~40%;And
The water of surplus.
In some embodiments of the invention, described anion surfactant include dodecyl sodium sulfate, ten
At least one in dialkyl benzene sulfonic acids sodium, sodium lauryl sulphate and alkylpolyoxyethylene sodium sulfate.
The most described anion surfactant is dodecylbenzene sodium sulfonate.
In other embodiments of the present invention, described low-carbon alcohols include methanol, ethanol, propanol, isopropanol,
At least one in butanol and isobutanol.The most described low-carbon alcohols is methanol.
In the present invention, above-mentioned reversible physical cross-linking agent is by anion surfactant and low-carbon alcohols being mixed with water
Merging stirs prepares.
According to the present invention, the temperature of described mixing is 40~60 DEG C;The rotating speed of described stirring is 400~600
rad/min;The time 25~40min of described stirring.
The present invention is above-mentioned prepare reversible physical cross-linking agent during, for anion surfactant and low-carbon (LC)
The mode that alcohol mixes with water has no particular limits, after both can anion surfactant and low-carbon alcohols being mixed
Mix with water again, will mix with water as a kind of compositions the mixture of anion surfactant and low-carbon alcohols
Close, it is also possible to anion surfactant and low-carbon alcohols are mixed with water simultaneously, it is also possible to anionic surface is lived
Property agent and low-carbon alcohols mix with water successively.Preferably anion surfactant and low-carbon alcohols are mixed with water successively.
According to the preferred embodiment of the present invention, the preparation method of described reversible physical cross-linking agent includes:
Step A, mixes anion surfactant with water, and aqueous solution of anionic surfactant is made in stirring;
Step B, adds low-carbon alcohols in aqueous solution of anionic surfactant, makes reversible physical and hand over after stirring
Connection agent.
According to the present invention, in step A or step B, the temperature of described mixing is 40~60 DEG C;Described stir
The rotating speed mixed is 400~600rad/min.
According to the present invention, in step, the time of described stirring is 5~10min.
According to the present invention, in stepb, the time of described stirring is 20~30min.
The present invention still further provides a kind of reversible physical cross-linking agent of the present invention or according to of the present invention
Reversible physical cross-linking agent prepared by the preparation method application in preparing fracturing fluid, described fracturing fluid can be used in
The pressing crack construction of 160 DEG C of reservoirs.
In the present invention, " water " word used, in the case of not specifying, refers to deionized water.
In the present invention, described polymer viscosifier be acrylates, hydrophobic association monomer, p styrene sulfonic acid salt,
2-acrylamide-2-methyl propane sulfonic, the copolymer of five kinds of monomers of acrylamide, molecular weight is 500~10,000,000.
According to the present invention, described hydrophobic association monomer include alkyl acrylate, alkyl dimethyl ethyl ammonium bromide,
In 2-acrylamido-2-alkyl ethyl sulfonic acid and (2-methylacryloyl) oxygen ethyl dimethyl alkyl bromination ammonium
At least one, wherein the carbon number of alkyl is 8~18;The preferably carbon number of alkyl is 12~16.
In some currently preferred embodiments of the present invention, in described polymer viscosifier, the ratio of five kinds of monomers is:
Acrylates is (0.03~0.38) with the mol ratio of acrylamide: 1;Hydrophobic association monomer rubs with acrylamide
Your ratio is (9.39 × 10-4~6 × 10-2):1;P styrene sulfonic acid salt with the mol ratio of acrylamide is
(6.89×10-5~1.72 × 10-3):1;2-acrylamide-2-methyl propane sulfonic with the mol ratio of acrylamide is
(6.86×10-4~1.72 × 10-2): 1, molecular weight is 500~10,000,000.
In some embodiments of the invention, during described acrylates includes acrylic acid sodium salt, potassium salt and lithium salts
At least one.The most described acrylates is sodium acrylate.
In some embodiments of the invention, described p styrene sulfonic acid salt include p styrene sulfonic acid sodium salt,
At least one in potassium salt and lithium salts.The most described p styrene sulfonic acid salt is sodium p styrene sulfonate.
Reversible physical cross-linking agent provided by the present invention, containing anion surfactant and low-carbon alcohols, it passes through
Electrostatic, hydrogen bond or Van der Waals force and polymer viscosifier are formed and are physical crosslinking to reach to viscosify purpose, and viscoelasticity is good.
The fracturing fluid prepared by this reversible physical cross-linking agent and polymer viscosifier at room temperature measures, the viscosity before shearing
It is 100~350mPa s;At 120~160 DEG C and 170S-1Under the conditions of shear 2 hours, then by temperature cool down
Viscosity after recording shearing to room temperature is 90~340mPa s, it was demonstrated that its shear restoration is good;This is reversible simultaneously
It is 30~180s controlled that physical crosslinking agent postpones crosslinking time;Its low frictional resistance of fracturing fluid prepared, fragile glue,
The easily row of returning, Low Damage.Reversible physical cross-linking agent commercial production needed raw material kind is few, wide material sources, price are low
Honest and clean, synthesis technique is simple to operate, has a extensive future.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described.
Fig. 1 is 0.2% reversible physical cross-linking agent and the polymer viscosifier preparation of 0.5% in the embodiment of the present invention 1
Become the rheological curve (120 DEG C) of fracturing fluid.
Fig. 2 be in the embodiment of the present invention 2 0.25% reversible physical cross-linking agent and 0.55% polymer viscosifier join
Make the rheological curve (140 DEG C) of fracturing fluid.
Fig. 3 is 0.3% reversible physical cross-linking agent and the polymer viscosifier preparation of 0.6% in the embodiment of the present invention 3
Become the rheological curve (160 DEG C) of fracturing fluid.
Fig. 4 is 0.3% reversible physical cross-linking agent and the polymer viscosifier preparation of 0.6% in the embodiment of the present invention 4
Become the rheological curve (160 DEG C) of fracturing fluid.
Detailed description of the invention
For making the present invention easier to understand, describe this in detail below in conjunction with embodiment, comparative example and accompanying drawing
Invention, these embodiments only play illustrative effect, it is not limited to the range of application of the present invention.
Unless otherwise indicated, in embodiment and comparative example, all percentage ratios are mass percent.Embodiment and right
Ratio relates to fracturing fluid property assay method with reference to People's Republic of China's oil and gas industry standard
" SY/T 6216-1996 pressure break cross-linking agent method for testing performance " and " SY/T5107-2005 aqueous fracturing fluid performance
Evaluation methodology ".
Embodiment
Embodiment 1: prepare reversible physical cross-linking agent.
In beaker, add a certain amount of deionized water, be heated to 40 DEG C, weigh the dodecyl sodium sulfonate of 20%
Sodium joins in above-mentioned beaker, mechanical agitation 5min, and stir speed (S.S.) is 400rad/min, weighs the first of 20%
Alcohol joins in above-mentioned beaker, and mechanical agitation 20min prepares colourless transparent liquid, is reversible physical
Cross-linking agent.
The rheology that the above-mentioned reversible physical cross-linking agent of 0.2% and the polymer viscosifier of 0.5% are configured to fracturing fluid is bent
Line (120 DEG C) is as shown in Figure 1.
The above-mentioned reversible physical cross-linking agent of 0.2% and polymer viscosifier (sodium acrylate, the hydrophobic association list of 0.5%
Body, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic and the copolymer of five kinds of monomers of acrylamide,
Molecular weight is 5,000,000) produce physical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 180
mPa·s;At 120 DEG C and 170S-1Under the conditions of shear 2 hours, then temperature is cooled to after room temperature records shearing
The viscosity of fracturing fluid is 168mPa s, and shear restoration is good;Delay crosslinking time is 120s;The broken glue time is
2 hours, breaking glue solution viscosity was 1.43mPa s, and breaking glue solution surface tension is 24.93mN/m.
Comparative example 1:
In order to the invention effect of embodiment 1 is described, chooses organic zirconium chemical cross-linking agent and be contrast experiment.
The organic zirconium chemical cross-linking agent of 0.2% and 0.5% polymer viscosifier (sodium acrylate, hydrophobic association monomer,
Sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic, the copolymer of five kinds of monomers of acrylamide, molecule
Amount is 5,000,000) produce chemical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 243mPa s;
At 120 DEG C and 170S-1Under the conditions of shear 2 hours, then temperature be cooled to room temperature record fracturing fluid after shearing
Viscosity is 69mPa s, and shear restoration is poor;The broken glue time is 8 hours, and breaking glue solution viscosity is 5.91mPa s,
Breaking glue solution surface tension is 28.26mN/m.
Embodiment 2: prepare reversible physical cross-linking agent.
In beaker, add a certain amount of deionized water, be heated to 50 DEG C, weigh the detergent alkylate sulphur of 25%
Acid sodium joins in above-mentioned beaker, and mechanical agitation 8min, stir speed (S.S.) is 500rad/min, weighs 25%
Propanol joins in above-mentioned beaker, and mechanical agitation 25min prepares colourless transparent liquid, is reversible thing
Reason cross-linking agent.
The above-mentioned reversible physical cross-linking agent of 0.25% and the polymer viscosifier of 0.55% are configured to the rheology of fracturing fluid
Curve (140 DEG C) is as shown in Figure 2.
The above-mentioned reversible physical cross-linking agent of 0.25% and polymer viscosifier (sodium acrylate, the hydrophobic association of 0.55%
Monomer, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic, the copolymer of five kinds of monomers of acrylamide,
Molecular weight is 5,000,000) produce physical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 195
mPa·s;At 140 DEG C, 170S-1Under the conditions of shear 2 hours, then temperature is cooled to after room temperature records shearing
The viscosity of fracturing fluid is 189mPa s, and shear restoration is good;Delay crosslinking time is 150s;The broken glue time is
2 hours, breaking glue solution viscosity was 1.71mPa s, and breaking glue solution surface tension is 25.28mN/m.
Comparative example 2:
In order to the invention effect of embodiment 2 is described, chooses organic zirconium chemical cross-linking agent and be contrast experiment.0.25%
Organic zirconium chemical cross-linking agent and 0.55% polymer viscosifier (sodium acrylate, hydrophobic association monomer, to benzene
Vinyl sulfonic acid sodium, 2-acrylamide-2-methyl propane sulfonic and the copolymer of five kinds of monomers of acrylamide, molecular weight is
5000000) producing chemical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 285mPa s;?
140 DEG C and 170S-1Down cut 2 hours, then temperature is cooled to the viscosity of fracturing fluid after room temperature records shearing is
57mPa s, shear restoration is poor;The broken glue time is 10 hours, and breaking glue solution viscosity is 5.63mPa s, broken glue
Liquid surface tension is 28.79mN/m.
Embodiment 3: prepare reversible physical cross-linking agent.
In beaker, add a certain amount of deionized water, be heated to 60 DEG C, weigh the dodecyl polyoxy of 40%
Vinyl Ether sodium sulfate joins in above-mentioned beaker, mechanical agitation 10min, and stir speed (S.S.) is 600rad/min, claims
The butanol taking 40% joins in above-mentioned beaker, and mechanical agitation 30min prepares colourless transparent liquid, i.e.
For reversible physical cross-linking agent.
The rheology that the above-mentioned reversible physical cross-linking agent of 0.3% and the polymer viscosifier of 0.6% are configured to fracturing fluid is bent
Line (160 DEG C) is as shown in Figure 3.
The above-mentioned reversible physical cross-linking agent of 0.3% and polymer viscosifier (sodium acrylate, the hydrophobic association list of 0.6%
Body, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic and the copolymer of five kinds of monomers of acrylamide,
Molecular weight is 10,000,000) produce physical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 303
mPa·s;At 160 DEG C and 170S-1Under the conditions of shear 2 hours, then temperature is cooled to after room temperature records shearing
The viscosity of fracturing fluid is 276mPa s, and shear restoration is good;Delay crosslinking time is 180s;The broken glue time is
2 hours, breaking glue solution viscosity was 1.39mPa s, and breaking glue solution surface tension is 25.63mN/m.
Comparative example 3:
In order to the invention effect of embodiment 3 is described, chooses organic zirconium chemical cross-linking agent and be contrast experiment.0.3%
Organic zirconium chemical cross-linking agent and 0.6% polymer viscosifier (sodium acrylate, hydrophobic association monomer, to styrene
Sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic and the copolymer of five kinds of monomers of acrylamide, molecular weight is 1000
Ten thousand) producing chemical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 396mPa s;At 160 DEG C
And 170S-1Under the conditions of shear 2 hours, then temperature be cooled to the viscosity of fracturing fluid after room temperature records shearing be
51mPa s, shear restoration is poor;The broken glue time is 12 hours, and breaking glue solution viscosity is 6.74mPa s, broken glue
Liquid surface tension is 30.23mN/m.
Embodiment 4: prepare reversible physical cross-linking agent.
In beaker, add a certain amount of deionized water, be heated to 60 DEG C, weigh the dodecyl polyoxy of 40%
Vinyl Ether sodium sulfate and 40% butanol join in above-mentioned beaker, mechanical agitation 40min, prepare colourless
Transparency liquid, is reversible physical cross-linking agent.
The rheology that the above-mentioned reversible physical cross-linking agent of 0.3% and the polymer viscosifier of 0.6% are configured to fracturing fluid is bent
Line (160 DEG C) is as shown in Figure 4.
The above-mentioned reversible physical cross-linking agent of 0.3% and polymer viscosifier (sodium acrylate, the hydrophobic association list of 0.6%
Body, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic and the copolymer of five kinds of monomers of acrylamide,
Molecular weight is 10,000,000) produce physical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 336
mPa·s;At 160 DEG C and 170S-1Under the conditions of shear 2 hours, then temperature is cooled to after room temperature records shearing
The viscosity of fracturing fluid is 282mPa s, and shear restoration is good;Delay crosslinking time is 150s;The broken glue time is
2 hours, breaking glue solution viscosity was 1.96mPa s, and breaking glue solution surface tension is 24.7mN/m.
Comparative example 4:
In order to the invention effect of embodiment 4 is described, chooses organic zirconium chemical cross-linking agent and be contrast experiment.
The organic zirconium chemical cross-linking agent of 0.3% and 0.6% polymer viscosifier (sodium acrylate, hydrophobic association monomer,
Sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic and the copolymer of five kinds of monomers of acrylamide, molecule
Amount is 10,000,000) produce chemical crosslinking effect, measuring the viscosity of fracturing fluid before shearing under room temperature is 423mPa s;
At 160 DEG C and 170S-1Under the conditions of shear 2 hours, then temperature be cooled to room temperature record fracturing fluid after shearing
Viscosity is 54mPa s, and shear restoration is poor;The broken glue time is 12 hours, and breaking glue solution viscosity is 6.18mPa s,
Breaking glue solution surface tension is 31.47mN/m.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. a reversible physical cross-linking agent, it contains anion surfactant and low-carbon alcohols.
Reversible physical cross-linking agent the most according to claim 1, it is characterised in that hand at described reversible physical
In connection agent, described anion surfactant is (0.1~5) with the mass ratio of described low-carbon alcohols: 1;Preferably institute
The mass ratio stating anion surfactant and described low-carbon alcohols is (0.5~2): 1;The described the moon being more highly preferred to
Ionic surface active agent is 1:1 with the mass ratio of described low-carbon alcohols.
Reversible physical cross-linking agent the most according to claim 1 and 2, it is characterised in that described reversible physical
Possibly together with water in cross-linking agent.
Reversible physical cross-linking agent the most according to claim 3, it is characterised in that described reversible physical cross-links
Agent composition by mass is as follows:
Anion surfactant 20%~40%;
Low-carbon alcohols 20%~40%;And
The water of surplus.
5. according to the reversible physical cross-linking agent described in any one in Claims 1 to 4, it is characterised in that institute
State anion surfactant and include dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, sodium lauryl sulphate
With at least one in alkylpolyoxyethylene sodium sulfate;The most described anion surfactant is 12
Sodium alkyl benzene sulfonate;Described low-carbon alcohols includes in methanol, ethanol, propanol, isopropanol, butanol and isobutanol
At least one;The most described low-carbon alcohols is methanol.
6. a preparation method for the reversible physical cross-linking agent as described in any one in Claims 1 to 5, its
Including:
Step A, mixes anion surfactant with water, and aqueous solution of anionic surfactant is made in stirring;
Step B, adds low-carbon alcohols in aqueous solution of anionic surfactant, makes reversible physical and hand over after stirring
Connection agent.
Preparation method the most according to claim 6, it is characterised in that in step A or step B,
The temperature of described mixing is 40~60 DEG C;The rotating speed of described stirring is 400~600rad/min.
8. according to the preparation method described in claim 6 or 7, it is characterised in that in step, described
The time of stirring is 5~10min.
9. according to the preparation method described in any one in claim 6 to 8, it is characterised in that in step B
In, the time of described stirring is 20~30min.
10. reversible physical cross-linking agent as described in any one in claim 1 to 5 or as claim 6 arrives
The reversible physical cross-linking agent that in 9 prepared by preparation method described in any one application in preparing fracturing fluid, institute
State fracturing fluid and can be used in the pressing crack construction of 160 DEG C of reservoirs.
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CN107686723B (en) * | 2017-08-11 | 2020-03-10 | 中国石油天然气股份有限公司 | CO (carbon monoxide)2Response in-situ gel channeling sealing sol and preparation method and application thereof |
CN110616067A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Low-temperature-resistant clean polymer fracturing fluid crosslinking agent and preparation method thereof |
CN110616067B (en) * | 2018-06-20 | 2022-06-07 | 中国石油化工股份有限公司 | Low-temperature-resistant clean polymer fracturing fluid crosslinking agent and preparation method thereof |
CN111117592A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Method for preparing cross-linking acid |
CN111117593A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Crosslinking agent and preparation method thereof |
CN109679640A (en) * | 2019-03-05 | 2019-04-26 | 西南石油大学 | A kind of good fracturing fluid system of small, the outstanding sand of frictional resistance |
CN116064023A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Oil displacement fracturing fluid with low damage to reservoir and application thereof |
CN116445149A (en) * | 2022-01-07 | 2023-07-18 | 中国石油化工股份有限公司 | Temperature-sensitive foam fracturing fluid and preparation method and application thereof |
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Application publication date: 20170111 |