CN118047905A - Five-membered hydrophobically associating modified acrylamide polymer, preparation method thereof, suspension type thickening agent and fracturing fluid - Google Patents
Five-membered hydrophobically associating modified acrylamide polymer, preparation method thereof, suspension type thickening agent and fracturing fluid Download PDFInfo
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- 239000012530 fluid Substances 0.000 title claims abstract description 58
- 150000003926 acrylamides Chemical class 0.000 title claims abstract description 32
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 32
- 239000002562 thickening agent Substances 0.000 title claims abstract description 25
- 239000000725 suspension Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003245 coal Substances 0.000 claims abstract description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 14
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000000873 masking effect Effects 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- -1 polyoxyethylene Polymers 0.000 claims description 16
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 230000033558 biomineral tissue development Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 239000003921 oil Substances 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical group CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 229920006197 POE laurate Polymers 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses a five-membered hydrophobically associating modified acrylamide polymer, a preparation method thereof, a suspension type thickening agent and fracturing fluid. The fracturing fluid comprises the following components in percentage by mass: 90-95% of suspension type thickening agent, 1-2% of metal ion masking agent, 1-2% of cleanup additive and 1-2% of clay stabilizer. The five-membered hydrophobic association modified acrylamide polymer is prepared by copolymerizing acrylamide, acrylic acid, sodium p-styrenesulfonate, 4-acryloylmorpholine and hexadecyl methacrylate, mixing with a dispersing agent and an organic solvent to form a suspension type thickening agent, and mixing with a metal ion masking agent, a cleanup additive and a clay stabilizer to prepare fracturing fluid for deep coal seam flowback fluid recycling. The fracturing fluid system has the functions of high tolerance mineralization, quick tackifying, high flowback efficiency, stable clay and the like, and has wide application prospect and good economic benefit in the field of flowback fluid recycling of deep coal seams.
Description
Technical Field
The invention relates to the field of fracturing fluid, in particular to a five-membered hydrophobically associating modified acrylamide polymer, a preparation method thereof, a suspension type thickening agent and fracturing fluid.
Background
The coal bed gas resource reserves of China are rich, the Huidos basin is a block with the largest coalbed gas detectable reserve, more than 90% of the recoverable reserve is a deep coal bed, the development difficulty is high, and the economic and effective development of the deep coal bed gas can be realized through large-scale volumetric fracturing. The water resource in the eastern jaw area is deficient, and a large amount of fracturing flowback fluid is difficult to treat along with the large-scale fracturing operation of the oil and gas field at the landing place, so that the large-scale volume fracturing construction scale and the time efficiency are severely restricted. The whole deep coal seam fracturing flowback fluid has the characteristics of complex components, high mineralization degree and high calcium and magnesium ion content, and the development of a salt-tolerant fracturing fluid system suitable for the deep coal seam fracturing flowback fluid is an important guarantee for realizing the reutilization of the flowback fluid.
The polymer thickener has become an important direction for developing a salt-tolerant fracturing fluid system because of easy modification, rapid dissolution and no mixing, and can improve the tolerance of the thickener to mineralization and calcium and magnesium ions by introducing functional monomers in the polymerization process of acrylamide and acrylic acid, and form an integrated fracturing fluid system by being assisted with metal ion masking agents, cleanup additives, clay stabilizers and the like. In the fracturing operation of oil and gas fields, the commonly used fracturing fluid thickening agent is a quaternary hydrophobic association polymer, which refers to a water-soluble polymer with a small amount of hydrophobic functional monomers on a polymer molecular chain, but the fracturing fluid thickening agent still has the defects of poor salt resistance and weak shearing resistance in the process of recycling deep coal seam flowback fluid.
Disclosure of Invention
The invention aims to solve the technical problems and provides a five-membered hydrophobically associating modified acrylamide polymer, a preparation method thereof, a suspension type thickening agent and a fracturing fluid.
In a first aspect, the invention provides a five-membered hydrophobically associating modified acrylamide polymer, which is realized by adopting the following technical scheme.
Five-membered hydrophobically associating modified acrylamide polymer has the following structural formula:
Wherein a, b, c, d, e is the mole percentage of the monomer, wherein a is 60% -70%, b is 25% -35%, c is 1% -5%, d is 1% -5%, and e is 1% -5%.
In a second aspect, the invention provides a preparation method of a five-membered hydrophobically associating modified acrylamide polymer, which is realized by adopting the following technical scheme.
A preparation method of a five-membered hydrophobically associating modified acrylamide polymer comprises the following steps:
S1, preparing aqueous solution with certain mass concentration from acrylamide, acrylic acid, sodium p-styrenesulfonate, 4-acryloylmorpholine and hexadecyl methacrylate according to the mass ratio of (8-10): (4-6): 1:1 (2-4);
S2, adding sodium dodecyl sulfate into the aqueous solution, fully and uniformly mixing, and introducing nitrogen to perform deoxidization treatment;
S3, continuously adding a redox initiator and a water-soluble azo initiator into the aqueous solution, and continuously stirring under the condition of nitrogen environment and a certain temperature to perform multistage initiation copolymerization reaction;
S4, after the reaction is finished, filtering and collecting the obtained five-membered copolymerization product, drying, solidifying, shearing, crushing, soaking and washing by using absolute ethyl alcohol, filtering, drying and crushing again to obtain the five-membered hydrophobically associating modified acrylamide polymer.
In step S1, the total mass concentration of the mixture in the aqueous solution is 35% -45%.
In step S2, the addition amount of sodium dodecyl sulfate is 1% -2% of the mass of the hexadecyl methacrylate.
In the step S3, the redox initiator is selected from one of ammonium persulfate/sodium bisulfate, tert-butyl ferrous sulfate hydrogen peroxide/sodium sulfite and sodium chlorate/sodium sulfite, and the addition amount of the redox initiator is 0.2-0.5% of the mass of the acrylamide added in the system.
In step S3, the water-soluble azo initiator is selected from one of dimethyl azodiisobutyrate, azodiiso Ding Mi hydrochloride, azodiisobutyl amidine hydrochloride and azoiso Ding Qingji formamide, and the addition amount of the water-soluble azo initiator is 0.6-0.9% of the mass of the acrylamide added in the system.
In the step S3, the reaction temperature of the copolymerization reaction is 80-100 ℃ and the reaction time is 8-10 hours.
In a third aspect, the present invention provides a suspension thickener, which is realized by adopting the following technical scheme.
The suspension type thickener comprises the following components in percentage by mass: 44-60% of the five-membered hydrophobic association modified acrylamide polymer, 1-2% of a dispersing agent and 39-54% of an organic solvent.
Further, the dispersing agent is one of span 40, span 60, span 80, tween 60, tween 80, AEO-7 and AEO-9.
Furthermore, the organic solvent is one of diesel oil, kerosene, white oil and lubricating oil.
In a fourth aspect, the invention provides a fracturing fluid for recycling deep coal seam flowback fluid, which is realized by adopting the following technical scheme.
The fracturing fluid for recycling the deep coal seam flowback fluid comprises the following components in percentage by mass: 90-95% of the suspension type thickening agent, 1-4% of the metal ion masking agent, 1-4% of the cleanup additive and 1-2% of the clay stabilizer.
Further, the metal ion masking agent is one of ethylenediamine tetraacetic acid, oxalate, citric acid and tartaric acid.
Further, the cleanup additive is one of long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester and polyoxyethylene alkyl alcohol amide.
Further, the long-chain fatty alcohol polyoxyethylene ether is selected from one of polyoxyethylene cetyl ether and laurinol polyoxyethylene ether; the alkylphenol polyoxyethylene ether is selected from one of nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether; the fatty acid polyoxyethylene ester is selected from one of polyoxyethylene laurate or polyoxyethylene stearate; the polyoxyethylene alkyl alcohol amide is lauroyl diethanolamine.
Further, the clay stabilizer is one of potassium iodide, ammonium chloride, dimethyl diallyl ammonium chloride and trimethyl allyl ammonium chloride.
In a fifth aspect, the invention provides a preparation method of fracturing fluid for recycling deep coal seam flowback fluid, which is realized by adopting the following technical scheme.
A preparation method of fracturing fluid for recycling deep coal seam flowback fluid comprises the following steps:
Adding the five-membered hydrophobic association modified acrylamide polymer and a dispersing agent into an organic solvent to prepare a uniform suspension system, and then sequentially adding a metal ion masking agent, a cleanup additive and a clay stabilizer.
The rotating speed of the reaction kettle is 100 r/min-120 r/min in the liquid preparation process, and the temperature is set to be 50-80 ℃.
The application has the following beneficial effects.
The fracturing fluid system has the functions of high mineralization tolerance, quick tackifying, high flowback efficiency, stable clay and the like, and is particularly suitable for recycling the deep coal seam fracturing flowback fluid with high calcium and magnesium content and high mineralization.
Detailed Description
The present application is further illustrated below with reference to examples.
The experimental methods used in the following preparation examples and examples are conventional methods unless otherwise specified; materials, reagents and the like used in the following preparation examples and examples are commercially available unless otherwise specified.
Example 1
Acrylamide, acrylic acid, sodium p-styrenesulfonate, 4-acryloylmorpholine and hexadecyl methacrylate are prepared into an aqueous solution with a total mass concentration of 40% according to a mass ratio of 8:4:1:1:2. Sodium dodecyl sulfate was added to the aqueous solution in an amount of 1% by mass of cetyl methacrylate. After fully and evenly mixing, introducing nitrogen to carry out deoxidization treatment. Continuously adding ammonium sulfate/sodium bisulfate and dimethyl azodiisobutyrate into the aqueous solution, wherein the addition amounts of the ammonium sulfate/sodium bisulfate and the dimethyl azodiisobutyrate are respectively 0.2 percent and 0.6 percent of the mass of the acrylamide added into the system. Continuously stirring under the condition of nitrogen and 80 ℃ to carry out multistage initiation copolymerization reaction for 8 hours. And after the reaction is finished, filtering and collecting the obtained five-membered copolymerization product, drying and solidifying, shearing and crushing, soaking and washing by using absolute ethyl alcohol, filtering again, drying and crushing to obtain the target modified acrylamide polymer. The modified acrylamide polymer is uniformly dispersed in diesel oil, and span 60 is used as an auxiliary material to form a suspension thickener, wherein the modified acrylamide polymer accounts for 44 percent, the dispersant accounts for 2 percent and the solvent oil accounts for 54 percent.
The rotating speed of the reaction kettle is set to be 100r/min, the reaction temperature is set to be 50 ℃, and ethylenediamine tetraacetic acid, polyoxyethylene cetyl ether and dimethyl diallyl ammonium chloride are added and fully and uniformly mixed to prepare the catalyst. Wherein, the mass ratio of the suspension thickening agent is 94%, the mass ratio of the metal ion masking agent is 2%, the mass ratio of the cleanup additive is 2%, and the mass ratio of the clay stabilizer is 2%.
Example 2
Acrylamide, acrylic acid, sodium p-styrenesulfonate, 4-acryloylmorpholine and hexadecyl methacrylate are prepared into an aqueous solution with a total mass concentration of 40% according to a mass ratio of 8:4:1:1:2. Sodium dodecyl sulfate was added to the aqueous solution in an amount of 2% by mass of cetyl methacrylate. After fully and evenly mixing, introducing nitrogen to carry out deoxidization treatment. Continuously adding tert-butyl ferrous hydrogen peroxide/sodium sulfite and dimethyl azodiisobutyrate into the aqueous solution, wherein the addition amounts of the tert-butyl ferrous hydrogen peroxide/sodium sulfite and the dimethyl azodiisobutyrate are respectively 0.5 percent and 0.9 percent of the mass of the acrylamide added into the system. Continuously stirring under the condition of nitrogen and the temperature of 100 ℃ to carry out multistage initiation copolymerization reaction for 10 hours. And after the reaction is finished, filtering and collecting the obtained five-membered copolymerization product, drying and solidifying, shearing and crushing, soaking and washing by using absolute ethyl alcohol, filtering again, drying and crushing to obtain the target modified acrylamide polymer. The modified acrylamide polymer is uniformly dispersed in diesel oil, and span 80 is used as an auxiliary material to form a suspension thickener, wherein the modified acrylamide polymer accounts for 48 percent, the dispersant accounts for 2 percent and the solvent oil accounts for 50 percent.
The rotating speed of the reaction kettle is set to be 100r/min, the reaction temperature is set to be 50 ℃, and ethylenediamine tetraacetic acid, nonylphenol polyoxyethylene ether and ammonium chloride are added and fully and uniformly mixed to prepare the catalyst. Wherein, the mass ratio of the suspension thickening agent is 95%, the mass ratio of the metal ion masking agent is 2%, the mass ratio of the cleanup additive is 2%, and the mass ratio of the clay stabilizer is 1%.
Example 3
Acrylamide, acrylic acid, sodium p-styrenesulfonate, 4-acryloylmorpholine and hexadecyl methacrylate are prepared into an aqueous solution with a total mass concentration of 40% according to a mass ratio of 10:4:1:1:2. Sodium dodecyl sulfate was added to the aqueous solution in an amount of 2% by mass of cetyl methacrylate. After fully and evenly mixing, introducing nitrogen to carry out deoxidization treatment. Continuously adding sodium chlorate/sodium sulfite and azodiiso Ding Mi hydrochloride into the aqueous solution, wherein the addition amounts are respectively 0.4% and 0.8% of the mass of acrylamide added into the system, and continuously stirring under the condition of nitrogen environment and 80 ℃ to perform multistage initiation copolymerization reaction for 10 hours. And after the reaction is finished, filtering and collecting the obtained five-membered copolymerization product, drying and solidifying, shearing and crushing, soaking and washing by using absolute ethyl alcohol, filtering again, drying and crushing to obtain the target modified acrylamide polymer. The modified acrylamide polymer is uniformly dispersed in diesel oil, and is assisted with AEO-7 to form a suspension thickener, wherein 47% of the modified acrylamide polymer, 1% of a dispersing agent and 52% of solvent oil.
The rotating speed of the reaction kettle is set to 120r/min, the reaction temperature is set to 80 ℃, tartaric acid, polyoxyethylene laurate and potassium iodide are continuously added, and the mixture is fully and uniformly mixed to prepare the catalyst. Wherein, the mass ratio of the suspension thickening agent is 95%, the mass ratio of the metal ion masking agent is 2%, the mass ratio of the cleanup additive is 1%, and the mass ratio of the clay stabilizer is 2%.
Example 4
Acrylamide, acrylic acid, sodium p-styrenesulfonate, 4-acryloylmorpholine and hexadecyl methacrylate are prepared into an aqueous solution with a total mass concentration of 40% according to a mass ratio of 10:4:1:1:2. Sodium dodecyl sulfate was added to the aqueous solution in an amount of 2% by mass of cetyl methacrylate. After fully and evenly mixing, introducing nitrogen to carry out deoxidization treatment. Continuously adding ammonium sulfate/sodium bisulfate and azobisisobutylamidine hydrochloride into the aqueous solution, wherein the addition amounts are respectively 0.4 percent and 0.8 percent of the mass of acrylamide added into the system, and continuously stirring under the condition of nitrogen environment and 80 ℃ to perform multistage initiation copolymerization reaction for 10 hours. And after the reaction is finished, filtering and collecting the obtained five-membered copolymerization product, drying and solidifying, shearing and crushing, soaking and washing by using absolute ethyl alcohol, filtering again, drying and crushing to obtain the target modified acrylamide polymer. The modified acrylamide polymer is uniformly dispersed in diesel oil, and span 60 is used as an auxiliary material to form a suspension thickener, wherein the modified acrylamide polymer accounts for 48 percent, the dispersant accounts for 2 percent and the solvent oil accounts for 50 percent.
The rotating speed of the reaction kettle is set to 120r/min, the reaction temperature is set to 80 ℃, and ethylenediamine tetraacetic acid, lauroyl diethanolamine and trimethylallyl ammonium chloride are continuously added and fully and uniformly mixed to prepare the catalyst. Wherein the mass ratio of the suspension thickening agent is 95%, the mass ratio of the metal ion masking agent is 2%, the mass ratio of the cleanup additive is 2%, and the mass ratio of the clay stabilizer is 1%.
Performance testing
After flocculation precipitation and multi-medium filtration of the on-site fracturing flowback fluid of a dense gas zone block of a certain northwest gas field, the water quality of the flowback fluid is shown in table 1, and the simply treated flowback fluid is used as a water source to prepare a fracturing fluid solution with the concentration of 0.9 percent according to on-site requirements. The formulated fracturing fluid was sheared at (formation temperature) 80 ℃ for 2 hours at 170s -1 and the apparent viscosity of the solution was measured. Maintaining the constant temperature at 80 ℃, adding 0.2% ammonium persulfate into the fracturing fluid solution to break the gel for 2 hours, and measuring the surface tension and the interfacial tension of the solution after breaking the gel. The experimental results are shown in table 2.
TABLE 1 Water quality data of treated flow-back fluid from field fracturing of dense gas block of certain northwest gas field
TABLE 2 Performance evaluation test results
The fracturing fluid used on site in a dense gas zone block of a certain northwest gas field has the apparent viscosity more than or equal to 60mPa.S, the surface tension of a fracturing fluid gel breaking solution is less than or equal to 28mN/m and the interfacial tension is less than or equal to 2mN/m according to SY/T6376-2008 fracturing fluid general technical condition, and the fracturing fluid prepared in the embodiment 1-4 can meet the requirements, but the conventional fracturing fluid in site cannot meet the indexes, so that the fracturing fluid system is a fracturing fluid system which is specially used for simply treating deep coal seam flowback fluid and is recycled, and the performance indexes are superior to those of the conventional fracturing fluid system under the same condition.
The embodiments of the present invention are all preferred embodiments of the present invention, and are not intended to limit the scope of the present invention in this way, therefore: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.
Claims (10)
1. A five-membered hydrophobic association modified acrylamide polymer is characterized in that: the structural formula is as follows:
Wherein a, b, c, d, e is the mole percentage of the monomer, wherein a is 60% -70%, b is 25% -35%, c is 1% -5%, d is 1% -5%, and e is 1% -5%.
2. A method for preparing the five-membered hydrophobically associating modified acrylamide polymer as defined in claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
S1, preparing aqueous solution with certain mass concentration from acrylamide, acrylic acid, sodium p-styrenesulfonate, 4-acryloylmorpholine and hexadecyl methacrylate according to the mass ratio of (8-10): (4-6): 1:1 (2-4);
S2, adding sodium dodecyl sulfate into the aqueous solution, fully and uniformly mixing, and introducing nitrogen to perform deoxidization treatment;
S3, continuously adding a redox initiator and a water-soluble azo initiator into the aqueous solution, and continuously stirring under the condition of nitrogen environment and a certain temperature to perform multistage initiation copolymerization reaction;
S4, after the reaction is finished, filtering and collecting the obtained five-membered copolymerization product, drying, solidifying, shearing, crushing, soaking and washing by using absolute ethyl alcohol, filtering, drying and crushing again to obtain the five-membered hydrophobically associating modified acrylamide polymer.
3. The method for preparing the five-membered hydrophobically associating modified acrylamide polymer according to claim 2, which is characterized in that: in the step S1, the total mass concentration of the mixture in the aqueous solution is 35% -45%.
4. The method for preparing the five-membered hydrophobically associating modified acrylamide polymer according to claim 2, which is characterized in that: in the step S2, the addition amount of the sodium dodecyl sulfate is 1-2% of the mass of the hexadecyl methacrylate.
5. The method for preparing the five-membered hydrophobically associating modified acrylamide polymer according to claim 2, which is characterized in that: in the step S3, the reaction temperature of the copolymerization reaction is 80-100 ℃.
6. A suspension type thickener is characterized in that: comprises the following components in percentage by mass: the five-membered hydrophobically associating modified acrylamide polymer as defined in claim 1, 44-60%, dispersant 1-2% and organic solvent 39-54%.
7. The fracturing fluid for recycling deep coal seam flowback fluid is characterized in that: comprises the following components in percentage by mass: the suspension thickener of claim 6, wherein the thickener comprises 90% -95%, the metal ion masking agent comprises 1% -4%, the cleanup additive comprises 1% -4% and the clay stabilizer comprises 1% -2%.
8. The fracturing fluid for recycling deep coal seam flowback fluid of claim 7, wherein the fracturing fluid is characterized in that: the metal ion masking agent is one of ethylenediamine tetraacetic acid, oxalate, citric acid and tartaric acid.
9. The fracturing fluid for recycling deep coal seam flowback fluid of claim 7, wherein the fracturing fluid is characterized in that: the cleanup additive is one of long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester and polyoxyethylene alkyl alcohol amide.
10. The fracturing fluid for recycling deep coal seam flowback fluid of claim 7, wherein the fracturing fluid is characterized in that: the clay stabilizer is one of potassium iodide, ammonium chloride, dimethyl diallyl ammonium chloride and trimethyl allyl ammonium chloride.
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| EP0376758A2 (en) * | 1988-12-29 | 1990-07-04 | Exxon Research And Engineering Company | Hydrophobically associating polymers |
| CN104479071A (en) * | 2014-11-20 | 2015-04-01 | 中国石油天然气股份有限公司 | Water-based fracturing fluid thickening agent and preparation method thereof |
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| CN115073660A (en) * | 2022-07-25 | 2022-09-20 | 中海油天津化工研究设计院有限公司 | Integrated thickening agent for fracturing and preparation method thereof |
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| EP0376758A2 (en) * | 1988-12-29 | 1990-07-04 | Exxon Research And Engineering Company | Hydrophobically associating polymers |
| CN104479071A (en) * | 2014-11-20 | 2015-04-01 | 中国石油天然气股份有限公司 | Water-based fracturing fluid thickening agent and preparation method thereof |
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