CN112724316A - Salt-tolerant temperature-resistant multipurpose thickening agent for shale gas reservoir volume reconstruction and preparation method thereof - Google Patents
Salt-tolerant temperature-resistant multipurpose thickening agent for shale gas reservoir volume reconstruction and preparation method thereof Download PDFInfo
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- 239000002562 thickening agent Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012530 fluid Substances 0.000 claims abstract description 20
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- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000012966 redox initiator Substances 0.000 claims abstract description 9
- 239000003292 glue Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 38
- 235000015110 jellies Nutrition 0.000 claims description 16
- 239000008274 jelly Substances 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000000129 anionic group Chemical group 0.000 claims description 13
- 238000002407 reforming Methods 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000499 gel Substances 0.000 claims description 9
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- 125000002091 cationic group Chemical group 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical group [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- AVWKSSYTZYDQFG-UHFFFAOYSA-M dimethyl-octadecyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC=C AVWKSSYTZYDQFG-UHFFFAOYSA-M 0.000 claims description 6
- ACWKAVFAONSRKJ-UHFFFAOYSA-M hexadecyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC=C ACWKAVFAONSRKJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical group CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 5
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical group CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 5
- 229940047670 sodium acrylate Drugs 0.000 claims description 5
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical group [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
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- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000012467 final product Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 231100000252 nontoxic Toxicity 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- -1 3-methacrylamidopropyldimethylamino Chemical group 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 240000006829 Ficus sundaica Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
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- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- 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
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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
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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
- C09K8/882—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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- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a salt-tolerant temperature-tolerant multipurpose shale gas reservoir volume modification thickening agent and a preparation method thereof. The preparation method of the thickening agent comprises the following steps: adding the quinary copolymer and water into a reaction kettle for dissolving, adding an azo initiator, and adjusting the pH value; reducing the temperature of the reaction kettle to 4-6 ℃, and introducing nitrogen to remove oxygen; reducing the temperature of the reaction kettle to 1-3 ℃, and adding a molecular regulator; adding a redox initiator after introducing nitrogen and removing oxygen, stopping cooling the reaction kettle, introducing nitrogen and removing oxygen; and (5) preserving the heat after the reaction kettle reaches the highest reaction temperature to obtain the product. The thickening agent prepared by the invention is environment-friendly and easy to degrade, can be used as a slickwater, linear glue and gel fracturing fluid system required by shale gas reservoir volume reconstruction only by changing the concentration, is low in consumption, and has good salt and temperature resistant effects.
Description
Technical Field
The invention relates to the technical field of oil testing engineering, in particular to a salt-tolerant temperature-tolerant multipurpose thickening agent for shale gas reservoir volume reformation and a preparation method thereof.
Background
The volume transformation is an important means for the development of shale gas resources at present, and a mixed fracturing fluid mode which takes emulsion with low viscosity, resistance reduction and slick water as a main body and takes linear gel and cross-linked gel as auxiliary bodies is mostly adopted. Compared with the traditional fracturing mode, the mixed fracturing fluid shows good transformation effect in the application process, but also shows a series of production problems: for example, the process flow is complicated due to different core additives, and when multi-system composite fracturing is performed, due to the different core additives, the conversion between systems can be realized only by switching the process during field construction, so that the process flow is complicated, and the human resources and the additive materials are unnecessarily wasted.
Chinese patent application publication No. CN107739422A, 2/27 in 2018, discloses a betaine type zwitterionic polymer oil-displacing agent and a synthesis method thereof, wherein the zwitterionic copolymer is obtained by polymerizing 80 parts of acrylamide, 18 parts of acrylic acid, 1 part of 3- (3-methacrylamidopropyldimethylamino) propyl-1-sulfonate and 0.3 part of N-allyl-2-phenoxyacetamide as monomers, and 0.2-0.8 part of azobisisobutyramidine hydrochloride as an initiator with 0.5mol/L sodium chloride solution at pH of 5-9 and 50 ℃ for 2-5 hours. The zwitterionic copolymer resists temperature of 110 ℃; the thickening agent and the structural reinforcing agent are synthesized twice, so that the synthesis cost is high; the liquid preparation on site is complex and the use cost is high.
The Chinese patent application with publication number CN111635489A, 9/8 of 2020, discloses a multifunctional supramolecular thickening agent and a preparation method thereof, wherein the multifunctional supramolecular thickening agent is synthesized by hydrophilic nonionic macromonomers, cationic monomers, anionic monomers and solvents, is suitable for oil and gas reservoirs with the temperature of 150 ℃, and can be used as a multipurpose thickening agent in thickening fluids such as hydrophobic associated complex fracturing fluid, slickwater fracturing fluid, thickening acid fluid and the like. The thickening agent has high molecular weight reaching 60-80 ten thousand, is not easy to degrade, has no salt-resistant group and poor salt resistance at the applicable temperature of 150 ℃, and the prepared fracturing fluid system has the mass concentration of 0.2-2% and larger use concentration.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art.
The inventor finds out through research that a multifunctional thickening agent needs to be researched and developed urgently, can be used as slickwater, linear glue and cross-linked gel fracturing fluid systems only by changing the using amount, and can directly prepare a high-salinity (30000-70000 ppm) flowback fluid to achieve the purpose of recycling the fracturing flowback fluid; in addition, with the gradual development of deep shale gas, the well temperature of part of deep shale gas wells also reaches more than 120 ℃, and the temperature resistance of the multifunctional thickening agent needs to be improved to more than 150 ℃ so as to meet the production requirement.
In view of the above, one of the objectives of the present invention is to design a molecular structure of a shale gas fracturing fluid according to performance characteristics of the shale gas fracturing fluid, preferably select a suitable side chain monomer, introduce a salt-resistant group, and form a novel multipurpose thickener for shale gas reservoir volume reformation through a synthesis test and performance evaluation, particularly a multipurpose thickener for shale gas reservoir volume reformation, which is suitable for salt tolerance (for example, salt tolerance can reach about 50000 ppm) and temperature tolerance (for example, temperature tolerance can reach about 150 ℃), and a preparation method and a multipurpose use method thereof.
In order to achieve the above purpose, one aspect of the invention provides a preparation method of a thickening agent for reforming the volume of a salt-tolerant temperature-resistant multipurpose shale gas reservoir, wherein a quinary copolymer is used as a raw material, and the quinary copolymer is composed of 65.5-70.5 parts by mass of a hydrophilic monomer, 1.5-2.0 parts by mass of a cationic monomer, 25.0-30.0 parts by mass of a first anionic monomer, 1.1-1.5 parts by mass of a second anionic monomer and 0.5-2.0 parts by mass of a supramolecular monomer. The supermolecule monomer is a mixture formed by mixing hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride according to the mass ratio of 2.7: 1-3.3: 1.
The preparation method comprises the following steps: adding the quinary copolymer and water into a reaction kettle, dissolving to form 25-30% aqueous solution by mass, adding an azo initiator, and adjusting the pH value to 7.55-7.65; reducing the temperature of the reaction kettle to a first temperature, introducing nitrogen to remove oxygen; reducing the temperature of the reaction kettle to a second temperature, and adding a molecular regulator; adding a redox initiator after introducing nitrogen and removing oxygen, stopping cooling the reaction kettle, introducing nitrogen and removing oxygen; and preserving heat after the highest reaction temperature in the reaction kettle is reached to prepare the thickening agent for modifying the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir. Wherein the first temperature is 4-6 ℃, and the second temperature is 1-3 ℃.
In an exemplary embodiment of the present invention, the azo initiator is azobisisobutyronitrile, and may be added in an amount of 0.15 to 0.20% by mass of the total mass of the pentabasic copolymer. In addition, the molecular regulator is sodium hypophosphite, the addition amount of the molecular regulator can be 0.003-0.004 percent of the total mass of the quinary copolymer, the redox initiator is sodium formaldehyde sulfoxylate and ammonium persulfate, and the addition amount of the redox initiator can be 0.005-0.02 percent and 0.01-0.05 percent of the total mass of the quinary copolymer respectively.
According to another aspect of the invention, the thickening agent for reforming the volume of the salt-tolerant and temperature-tolerant multipurpose shale gas reservoir is prepared by any one of the preparation methods.
In an exemplary embodiment of the invention, the slippery water system prepared by the thickener for modifying the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir can be 0.01-0.03% in mass concentration. In addition, the slickwater system can be directly prepared by 30000-70000 ppm of high-salinity water. The linear gel system is prepared by the thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir, and the mass concentration of the thickening agent can be 0.15-0.25%. The gel system is prepared by the thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir, and the mass concentration of the thickening agent can be 0.3-0.5%.
Compared with the prior art, the invention has the beneficial effects that: the product is more environment-friendly as a whole, is easy to degrade and reaches the non-toxic standard (EC50 is more than 1000000 mg/L); the construction process is greatly simplified, compared with the conventional emulsion resistance reducing agent, the dosage is reduced by more than 70 percent, and the cost for preparing each formula of slickwater fracturing fluid is reduced by more than 50 percent; the method can adopt 30000-70000 ppm of high-salinity flowback liquid or water to prepare a slick water system, and the prepared jelly system can resist the temperature of 150-160 ℃.
Drawings
Fig. 1 shows a flow chart of an exemplary embodiment of the production method of the present invention.
Figure 2 shows the drag reduction performance curve for the product of example 1 formulated with 50000ppm salinity water to form a system useful as slickwater.
Figure 3 shows the drag reduction performance curve for the product of example 1 used as a linear gum system.
Figure 4 shows the temperature and shear resistance curves for the product of example 1 used as a jelly system.
Figure 5 shows the drag reduction performance curve for the product of example 2 used as a slickwater system.
Detailed Description
Hereinafter, the salt-resistant temperature-resistant multipurpose shale thickener for gas reservoir volume reformation and the preparation method thereof according to the present invention will be described in detail with reference to the exemplary embodiments. Herein, the terms "first," "second," and the like are used for convenience of description and for convenience of distinction, and are not to be construed as indicating or implying relative importance or order of parts.
The term "salt tolerance" as used herein means that the content of monovalent ions and divalent ions (for example, sodium ions, potassium ions, chloride ions, calcium ions, magnesium ions, etc.) capable of forming salts, contained in a fracturing fluid system (for example, slickwater, linear gel, and jelly) prepared by using the thickener of the present invention, is 30000 to 70000 ppm; the temperature resistance means that the fracturing fluid system prepared by the thickening agent, such as a jelly system, can resist the temperature of 150-160 ℃.
Fig. 1 shows a flow chart of an exemplary embodiment of the production method of the present invention.
As shown in fig. 1, the preparation method of the thickener for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir comprises the following steps:
(1) adding the pentamer copolymer and water into a reaction kettle, adding an azo initiator, and adjusting the pH
Specifically, a quinary copolymer raw material is added into a reaction kettle, a proper amount of water is added to dissolve the raw material to form an aqueous solution with the mass fraction of 25-30%, an azo initiator is added, and the pH value is adjusted to 7.55-7.65.
The pentapolymer raw material comprises 65.5-70.5 parts by mass of hydrophilic monomer, 1.5-2.0 parts by mass of cationic monomer, 25.0-30.0 parts by mass of first anionic monomer, 1.1-1.5 parts by mass of second anionic monomer and 0.5-2.0 parts by mass of supramolecular monomer. The hydrophilic monomer is acrylamide, the cationic monomer is acryloyloxyethyl trimethyl ammonium chloride, the first anionic monomer is sodium acrylate, the second anionic monomer is 2-acrylamide-2-methylpropanesulfonic acid, and the supermolecule monomer is a mixture formed by mixing hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride according to the mass ratio of 2.7: 1-3.3: 1. The azo initiator is azobisisobutyronitrile. The adding amount is 0.15 to 0.20 percent of the total mass of the quinary copolymer. In the invention, the combination and the proportion of the five-membered copolymer raw materials mutually influence each other, and are determined by comprehensively considering factors such as salt resistance, temperature resistance, instant dissolution within 2min, cost and the like. In addition, the hydrophilic monomer is in the range of 65.5-70.5, so that the expected moisture resistance and solubility are mainly obtained, the construction requirement of instant dissolution within 2min cannot be met below 65.5, and the construction requirement of instant dissolution is easily damped after long-term storage above 70.5. The cationic monomer is used in the range of 1.5-2.0, which is mainly beneficial to improving the salt resistance of the thickening agent, the range of 1.5-2.0 can meet the requirements of the mineralization resistance of 50000ppm, even 70000ppm, the production cost can be increased and the product dissolution speed can be reduced by continuously increasing the addition. The first anionic monomer is in a range of 25.0-30.0, and the second anionic monomer is in a range of 1.1-1.5, so that the temperature resistance of the thickening agent is improved, and the temperature resistance and the cost of the thickening agent can be comprehensively considered. The supermolecule monomer is in the range of 0.5-2.0, so that the shear resistance and temperature stability of the thickening agent are improved, and the shear resistance, temperature stability and cost of the thickening agent can be comprehensively considered.
The reaction kettle is a reaction kettle in a broad sense, has different volumes, and can realize the functions of temperature measurement, sealing, heating, temperature reduction, heat preservation, material feeding, stirring, ventilation, pressure resistance and the like required in preparation. In addition, the water here may be deionized water.
(2) After cooling, nitrogen is introduced to remove oxygen
Specifically, the temperature in the reaction vessel was lowered to a first temperature, and then nitrogen gas was introduced into the reaction vessel to remove oxygen. The second temperature here may be 4 to 6 ℃.
(3) Adding molecular regulator after cooling
Specifically, the temperature in the reaction vessel is lowered to a second temperature, and then a molecular regulator is added to the reaction vessel. The molecular regulator is sodium hypophosphite, and the addition amount of the molecular regulator can be 0.003-0.004 percent of the total mass of the quinary copolymer. The second temperature here may be 1 to 3 ℃.
(4) Adding redox agent after nitrogen is introduced and oxygen is removed, stopping cooling, introducing nitrogen and removing oxygen
Specifically, after nitrogen is introduced for deoxygenation, a redox initiator is added, the reaction kettle is stopped from being cooled, and nitrogen is introduced for fully deoxygenating the reaction kettle. The oxidation reducing agent is sodium formaldehyde sulfoxylate and ammonium persulfate, and the addition amount of the oxidation reducing agent is 0.005-0.02 percent and 0.01-0.05 percent of the total mass of the five-membered copolymer respectively.
After the redox agent is added, the temperature of the reaction kettle is required to be immediately stopped to be reduced, and the processes of stopping the temperature reduction of the reaction kettle and introducing nitrogen for the second time to remove oxygen can be carried out simultaneously without any sequence; or may be performed sequentially.
(5) Keeping the temperature after reaching the highest reaction temperature to obtain the product
Specifically, the temperature in the reaction kettle is monitored in real time in the reaction process, and the maximum temperature is kept after the temperature reaches the maximum temperature, so that the thickening agent for modifying the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir is prepared.
It should be noted that, the introduction of nitrogen for deoxygenation is a routine operation in the field, and the present invention is not described in detail.
In another exemplary embodiment of the invention, the thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir can be also realized by the following steps:
1) adding the quinary copolymer and water into a reaction kettle, dissolving to form 25-30% of water solution by mass, adding azobisisobutyronitrile as an azo initiator, wherein the adding amount is 0.15-0.20% of the total mass of the quinary copolymer, and adjusting the pH value to 7.55-7.65;
the pentabasic copolymer comprises 65.5-70.5 parts by mass of acrylamide, 1.5-2.0 parts by mass of acryloyloxyethyl trimethyl ammonium chloride, 25.0-30.0 parts by mass of sodium acrylate, 1.1-1.5 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, and 0.5-2.0 parts by mass of a mixture formed by mixing hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride according to a mass ratio of 2.7: 1-3.3: 1;
2) reducing the temperature of the reaction kettle to 4-6 ℃, and introducing nitrogen to remove oxygen;
3) reducing the temperature of the reaction kettle to 1-3 ℃, adding sodium hypophosphite serving as a molecular regulator, wherein the adding amount is 0.003-0.004 percent of the total mass of the quinary copolymer;
4) introducing nitrogen to remove oxygen, adding sodium formaldehyde sulfoxylate and ammonium persulfate as redox initiators, wherein the addition amounts of the sodium formaldehyde sulfoxylate and the ammonium persulfate are 0.005-0.02 percent and 0.01-0.05 percent of the total mass of the five-membered copolymer respectively, then stopping cooling the reaction kettle, and introducing nitrogen to further remove oxygen;
5) and (3) after the temperature in the reaction kettle is monitored to reach the highest temperature, heat preservation is carried out for 1 hour for granulation, then drying and powder preparation are carried out, and finally the thickening agent for modifying the volume of the salt-tolerant and temperature-tolerant multipurpose shale gas reservoir can be prepared by sieving with a 100-mesh sieve.
The thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir prepared in the exemplary embodiment passes through a 100-mesh sieve, so that the thickening agent can be dissolved within 2min when each fracturing fluid system is prepared, the preparation and the use are realized immediately, and the problem that the thickening agent can be used after waiting for a long time is solved.
The invention further discloses the thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir and the preparation method thereof by detailed examples.
Example 1
The thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir is produced according to 200kg, and the preparation method comprises the following steps:
adding 500kg of deionized water into a reaction kettle, and then adding 2kg of a mixture of 132kg of acrylamide, 3kg of acryloyloxyethyl trimethyl ammonium chloride, 60kg of sodium acrylate, 3kg of 2-acrylamide-2-methylpropanesulfonic acid, hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride according to the mass ratio of 3: 1; adding 0.3kg of azodiisobutyronitrile, and adjusting the pH value to 7.58; reducing the temperature of the reaction kettle to 5 ℃, and introducing nitrogen for 20-30 min to remove oxygen; when the temperature of the reaction kettle is reduced to 2 ℃, 0.006kg of sodium hypophosphite is added; introducing nitrogen for 10 minutes, adding 0.01kg of sodium formaldehyde sulfoxylate and 0.02kg of ammonium persulfate, stopping cooling the reaction kettle, adjusting the nitrogen to be large, and continuously introducing nitrogen until the nitrogen cannot be introduced again; after the temperature in the reaction kettle reaches the highest temperature, the granulation is started after the temperature is kept for 1 hour; drying, pulverizing into powder, and sieving with 100 mesh sieve to obtain the final product.
A product is prepared into a slick water system, the mass concentration is 0.02 percent, and the drag reduction rate is 74.5 percent; 50000ppm of mineralization water is used for preparing a slick water system, the mass concentration is 0.03%, and the drag reduction rate of the slick water system is more than or equal to 70%; preparing a linear adhesive system, wherein the mass concentration is 0.15%, the apparent viscosity is 25mPa.s, and the resistance reduction rate is 68%; preparing a jelly system, wherein the mass concentration is 0.3%, and the jelly system can be continuously sheared for 60min at 170s-1 when the jelly system resists the temperature of 150 ℃, and the viscosity is 77 mPa.s.
Example 2
The thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir is produced according to 200kg, and the preparation method comprises the following steps:
adding 500kg of clear water into a reaction kettle, and then adding 4kg of a mixture of 140kg of acrylamide, 3kg of acryloyloxyethyl trimethyl ammonium chloride, 50kg of sodium acrylate, 3kg of 2-acrylamide-2-methylpropanesulfonic acid, hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride according to the mass ratio of 3: 1; adding 0.32kg of azodiisobutyronitrile, and adjusting the pH value to 7.60; reducing the temperature of the reaction kettle to 5 ℃, and introducing nitrogen for 20-30 min to remove oxygen; when the temperature of the reaction kettle is reduced to 2 ℃, 0.006kg of sodium hypophosphite is added; after nitrogen is introduced for 10 minutes, 0.015kg of sodium formaldehyde sulfoxylate and 0.03kg of ammonium persulfate are added, the reaction kettle is stopped from cooling, the nitrogen is increased, and the nitrogen is continuously introduced until the nitrogen cannot be introduced again; after the temperature in the reaction kettle reaches the highest temperature, the granulation is started after the temperature is kept for 1 hour; drying, pulverizing into powder, and sieving with 100 mesh sieve to obtain the final product.
A product is prepared into a slick water system, the mass concentration is 0.02 percent, and the drag reduction rate is 75.5 percent; preparing a linear adhesive system, wherein the mass concentration is 0.15%, the apparent viscosity is 24.5mPa.s, and the resistance reduction rate is 66.5%; and preparing a jelly system, wherein the mass concentration is 0.3%, the jelly system can resist temperature of more than 150 ℃, the jelly system can be continuously sheared for 60min within 170s-1, and the viscosity is 73 mPa.s.
FIG. 2 is a plot of drag reduction performance of the product of example 1 formulated to form a slickwater system using 50000ppm mineralized water, using a product mass concentration of 0.03% and a slickwater system drag reduction of greater than or equal to 70%. FIG. 3 is a plot of the drag reduction performance of the linear gum system formed by formulating the product of example 1 using a product mass concentration of 0.15%, an apparent viscosity of greater than or equal to 20mPa.s, and a drag reduction rate of greater than or equal to 65%. FIG. 4 is a temperature and shear resistance curve of a jelly system formed by formulating the product of example 1, wherein the mass concentration of the product used is 0.3%, the jelly system is continuously sheared for 60min at 170s-1 when tested at a temperature of 150 ℃, and the viscosity is not less than 70 mPa.s. FIG. 5 is a plot of the drag reduction performance of the slickwater system formulated with the product of example 2 using a product mass concentration of 0.02% and a drag reduction of greater than or equal to 70%.
In conclusion, the thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir prepared by the invention has the beneficial effects that:
1) compared with the conventional emulsion resistance reducing agent, the emulsion resistance reducing agent does not contain white oil; and the high-efficiency drag reduction can be realized only by small molecular weight by utilizing a trace amount of supermolecule acting monomers; the reduction of molecular weight is also beneficial to the improvement of conversion rate, the content of harmful monomers which are not completely converted is greatly reduced, the product can be instantly dissolved within 2min, the whole product is more environment-friendly and easy to degrade, and the product reaches the non-toxic standard (EC50 is more than 1000000 mg/L).
2) The thickening agent can be used as all 3 fracturing fluid systems required by shale gas reservoir volume transformation, namely slickwater, linear gel and jelly glue, by changing the concentration, the sand carrying capacity is improved, and meanwhile, the construction process is greatly simplified; compared with the conventional emulsion resistance reducing agent, the dosage is reduced by more than 70 percent, and the cost for preparing each formula of slickwater fracturing fluid is reduced by more than 50 percent.
3) The raw materials used in the preparation method are preferably proper side chain monomers, salt-resistant groups are introduced, and the prepared thickening agent can be prepared into a slickwater system directly by adopting 30000-70000 ppm of high-salinity water; the temperature resistance of the prepared jelly system can reach 150-160 ℃.
Although the present invention has been described above in connection with the exemplary embodiments and the accompanying drawings, it will be apparent to those of ordinary skill in the art that various modifications may be made to the above-described exemplary embodiments without departing from the spirit and scope of the claims.
Claims (10)
1. The preparation method of the multipurpose thickening agent for modifying the volume of the salt-resistant and temperature-resistant shale gas reservoir is characterized in that a quinary copolymer is used as a raw material, wherein the quinary copolymer is composed of 65.5-70.5 parts by mass of a hydrophilic monomer, 1.5-2.0 parts by mass of a cationic monomer, 25.0-30.0 parts by mass of a first anionic monomer, 1.1-1.5 parts by mass of a second anionic monomer and 0.5-2.0 parts by mass of a supermolecule monomer, wherein the hydrophilic monomer is acrylamide; the cationic monomer is acryloyloxyethyl trimethyl ammonium chloride; the first anionic monomer is sodium acrylate; the second anionic monomer is 2-acrylamide-2-methylpropanesulfonic acid; the supermolecule monomer is a mixture formed by mixing hexadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride according to the mass ratio of 2.7: 1-3.3: 1.
2. The preparation method of the salt and temperature resistant multipurpose shale thickener for gas reservoir volume reformation according to claim 1, wherein the preparation method comprises the following steps:
adding the quinary copolymer and water into a reaction kettle, dissolving to form 25-30% aqueous solution by mass, adding an azo initiator, and adjusting the pH value to 7.55-7.65;
reducing the temperature of the reaction kettle to a first temperature, introducing nitrogen to remove oxygen;
reducing the temperature of the reaction kettle to a second temperature, and adding a molecular regulator;
adding a redox initiator after introducing nitrogen and removing oxygen, stopping cooling the reaction kettle, introducing nitrogen and removing oxygen;
preserving heat after the highest reaction temperature in the reaction kettle is reached to prepare the salt-tolerant and temperature-tolerant thickening agent for modifying the volume of the multipurpose shale gas reservoir;
wherein the first reaction temperature is 4-6 ℃, and the second reaction temperature is 1-3 ℃.
3. The preparation method of the thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir as claimed in claim 2, wherein the azo initiator is azobisisobutyronitrile, and the addition amount is 0.15-0.20% of the total mass of the penta-copolymer.
4. The preparation method of the viscosifier for modifying the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir as claimed in claim 2, wherein the molecular regulator is sodium hypophosphite, and the addition amount of the viscosifier is 0.003-0.004% of the total mass of the penta-copolymer.
5. The preparation method of the thickening agent for reforming the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir according to claim 2, wherein the redox initiator is sodium formaldehyde sulfoxylate and ammonium persulfate, and the addition amounts of the redox initiator are 0.005-0.02% and 0.01-0.05% of the total mass of the five-membered copolymer respectively.
6. The multipurpose shale gas reservoir volume modifying thickening agent with salt and temperature resistance is characterized by being prepared by the preparation method according to any one of claims 2 to 5.
7. A slickwater system prepared by the thickener for modifying the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir as claimed in claim 6, wherein the mass concentration of the thickener in the slickwater system is 0.01-0.03%.
8. The thickening agent for modifying the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir as claimed in claim 7, wherein the thickening agent can be directly prepared into a slickwater system fracturing fluid by 30000-70000 ppm of hypersalinity water.
9. The linear gel system prepared by the thickener for modifying the volume of the salt-resistant and temperature-resistant multipurpose shale gas reservoir as claimed in claim 6, wherein the mass concentration of the thickener in the linear gel system is 0.15-0.25%.
10. The jelly glue system prepared by the thickener for the volume reformation of the salt-tolerant temperature-tolerant multipurpose shale gas reservoir as claimed in claim 6, wherein the mass concentration of the thickener in the jelly glue system is 0.3-0.5%.
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| CN113684016A (en) * | 2021-08-27 | 2021-11-23 | 西安长庆化工集团有限公司 | Super-salt-tolerant suspended slickwater resistance reducing agent and preparation method thereof |
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| WO2015109917A1 (en) * | 2014-01-21 | 2015-07-30 | 东方宝麟科技发展(北京)有限公司 | Thickener for shale gas fracturing fluid, fracturing fluid and preparation method and use thereof |
| CN106190088A (en) * | 2016-07-08 | 2016-12-07 | 四川奥赛德材料科技有限公司 | Temperature-resistant anti-salt instant dissolving viscosifier for seawater-based fracturing fluid and preparation method thereof |
| CN109054799A (en) * | 2018-07-25 | 2018-12-21 | 中国石油集团川庆钻探工程有限公司 | Environment-friendly multipurpose thickening agent for shale gas reservoir volume reconstruction and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015109917A1 (en) * | 2014-01-21 | 2015-07-30 | 东方宝麟科技发展(北京)有限公司 | Thickener for shale gas fracturing fluid, fracturing fluid and preparation method and use thereof |
| CN106190088A (en) * | 2016-07-08 | 2016-12-07 | 四川奥赛德材料科技有限公司 | Temperature-resistant anti-salt instant dissolving viscosifier for seawater-based fracturing fluid and preparation method thereof |
| CN109054799A (en) * | 2018-07-25 | 2018-12-21 | 中国石油集团川庆钻探工程有限公司 | Environment-friendly multipurpose thickening agent for shale gas reservoir volume reconstruction and preparation method thereof |
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| CN113684016A (en) * | 2021-08-27 | 2021-11-23 | 西安长庆化工集团有限公司 | Super-salt-tolerant suspended slickwater resistance reducing agent and preparation method thereof |
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