CN115215978B - Modified acid thickener and preparation method thereof - Google Patents
Modified acid thickener and preparation method thereof Download PDFInfo
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- CN115215978B CN115215978B CN202211118409.4A CN202211118409A CN115215978B CN 115215978 B CN115215978 B CN 115215978B CN 202211118409 A CN202211118409 A CN 202211118409A CN 115215978 B CN115215978 B CN 115215978B
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- 239000002253 acid Substances 0.000 title claims abstract description 95
- 239000002562 thickening agent Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012071 phase Substances 0.000 claims abstract description 50
- 239000003999 initiator Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229940099563 lactobionic acid Drugs 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 32
- 229920005610 lignin Polymers 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- -1 allyl halohydrocarbon Chemical class 0.000 claims abstract description 25
- 239000008346 aqueous phase Substances 0.000 claims abstract description 22
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 19
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000004945 emulsification Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 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 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 claims description 4
- 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 claims description 4
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000000243 solution Substances 0.000 description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000007762 w/o emulsion Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 230000008719 thickening Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 238000000520 microinjection Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- AEMOLEFTQBMNLQ-YMDCURPLSA-N D-galactopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-YMDCURPLSA-N 0.000 description 5
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 5
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000008101 lactose Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- 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
-
- 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
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a modified acid thickener and a preparation method thereof, which relate to the technical field of polymerization and oil field fracturing, and the method comprises the following steps: performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer; carrying out polycondensation reaction on lactobionic acid and allylamine to obtain a lactobionic acid prepolymer; uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, the lignin prepolymer, the lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; uniformly mixing white oil, a main emulsifier and an auxiliary emulsifier to obtain an oil phase solution; and adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization, and adding a phase inversion agent after the reaction is finished to obtain the modified acid solution thickening agent. The modified acid thickener prepared by the invention has strong tackifying capability in acid liquor and excellent temperature resistance and shear resistance.
Description
Technical Field
The invention relates to the technical field of polymerization and oilfield fracturing, in particular to a modified acid thickener and a preparation method thereof.
Background
With the rapid development of economy and industry, the demand for petroleum and natural gas energy is increasing day by day, and it is important to reasonably develop oil and gas resources and improve oil and gas recovery efficiency to the maximum extent. The acidification modification technology is one of the important technical means for realizing the reservoir modification, yield increase and water well injection increase of oil and gas wells in various oil fields at present, so that the permeability of an underground reservoir is recovered by mainly removing the pollution of the reservoir of the oil and gas wells. The acid fracturing is mainly characterized in that the stratum is reformed by utilizing the corrosion action of acid liquor to form a relatively long acid fracturing crack, so that the backflow capacity of an oil-gas layer is improved, and the yield of an oil-gas well is increased. The acid liquid thickener is used as a main component of thickening acid, reduces the diffusion rate of hydrogen ions to the surface of rock and the fluid loss by improving the viscosity of the acid liquid, and plays a role in delaying acid rock reaction and reducing friction resistance in the acid fracturing process.
The deep acidification is mainly used for preventing the acid liquor from being filtered on the fracture surface, and meanwhile, the acid liquor is filtered on the fracture surface to form acid etching holes. If serious acid fluid loss occurs, the effective action distance of the acid on the fracture surface is greatly shortened. Research shows that the acid liquor with considerable viscosity can effectively slow down the filtration rate of the acid liquor, thereby increasing the effective acid etching action distance. Although the polyacrylamide which is commonly used as the acid liquid thickener at present can meet the requirements of general operation, the polyacrylamide has the defects of tackifying performance, acid resistance stability, shearing resistance, temperature resistance and the like.
Disclosure of Invention
The embodiment of the invention provides a modified acid thickener and a preparation method thereof.
In a first aspect, the present invention provides a preparation method of a modified acid thickener, the preparation method comprising:
(1) Performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer;
(2) Carrying out polycondensation reaction on lactobionic acid and allylamine to obtain a lactobionic acid prepolymer;
(3) Uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, the lignin prepolymer, the lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; mixing white oil, a main emulsifier and an auxiliary emulsifier uniformly to obtain an oil phase solution;
(4) Adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization reaction, and adding a phase inversion agent after the reaction is finished to obtain the modified acid solution thickening agent;
the modified acid solution thickener is prepared from the following raw materials in parts by weight: 150-200 parts of acrylamide, 180-210 parts of (3-acrylamidopropyl) trimethyl ammonium chloride, 5-10 parts of triallyl cyanurate, 20-30 parts of a lignin prepolymer, 20-30 parts of a lactobionic acid prepolymer, 230-325 parts of water, 0.005-0.01 part of a first initiator, 230-270 parts of white oil, 15-30 parts of a main emulsifier, 3-7 parts of an auxiliary emulsifier and 22-24 parts of a phase transfer agent.
Preferably, in the step (1), the mass ratio of the sodium lignin sulfonate to the allyl halogenated hydrocarbon is (3.5 to 4.4): 1.
Preferably, in step (1), the temperature of the polycondensation reaction is 80 ℃ and the reaction time is not less than 24 hours.
Preferably, in step (1), the allylic halohydrocarbon is allyl chloride, allyl bromide or allyl iodide.
Preferably, in the step (2), the mass ratio of the lactobionic acid to the allylamine is (2.5 to 3.2): 1.
Preferably, in the step (2), the temperature of the polycondensation reaction is 50 to 55 ℃, and the reaction time is not less than 12h.
Preferably, the step (3) further comprises: and adjusting the pH value of the aqueous phase solution to 3.8-5.
Preferably, the pH of the aqueous phase solution is adjusted with a pH adjuster; wherein the pH regulator is at least one of adipic acid, acetic acid and hydrochloric acid.
Preferably, the main emulsifier is at least one of span-20, span-60, span-80 and span-83;
the auxiliary emulsifier is at least one of tween-65, tween-81 and tween-85.
Preferably, the first initiator is at least one of ammonium persulfate, potassium persulfate, tert-butyl hydroperoxide and benzoyl peroxide;
the second initiator is at least one of sodium sulfite, sodium bisulfite and sodium metabisulfite.
Preferably, the phase inversion agent is OP-10 or NP-10.
Preferably, in step (4), the temperature of the polymerization reaction is controlled not to exceed 75 ℃ by controlling the amount of the second initiator.
Preferably, in the step (4), the emulsifying time is 20 to 30min;
the temperature for initiating the polymerization reaction is 15 to 20 ℃; the polymerization reaction time is 5 to 7h.
In a second aspect, the invention provides a modified acid thickener, which is prepared by using any one of the preparation methods in the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
the method comprises the steps of introducing a carbon-carbon double bond into sodium lignosulfonate through a polycondensation reaction of sodium lignosulfonate and allyl halohydrocarbon to obtain a lignin prepolymer; simultaneously, carbon-carbon double bonds are introduced into lactobionic acid molecules through the polycondensation reaction of allylamine and lactobionic acid to obtain a lactobionic acid prepolymer; then, the modified acid liquid thickener is obtained after the reversed phase emulsion polymerization reaction with acrylamide, (3-acrylamide propyl) trimethyl ammonium chloride and triallyl cyanurate. The modified acid solution densifier has strong tackifying capability in acid solution and excellent temperature resistance and shear resistance.
The amido group and the cationic group in the modified acid thickener prepared by the invention have good hydrophilicity, so that the modified acid thickener has excellent water solubility; wherein, the cationic group has positive charge and has good acid resistance; the benzene ring structure in the lignin prepolymer improves the rigidity of a molecular chain, enhances the anti-shearing capacity, and in addition, the benzene ring has hydrophobic property, so that a polymer molecular chain can generate hydrophobic association micro-regions, intermolecular association is generated, a space network structure is formed, the tackifying effect is achieved, and the rigidity and the hydrophobic association of the molecular chain jointly improve the thermal stability of the polymer. Meanwhile, the salt resistance and hydrolysis resistance of the sulfonic acid group enable the prepared modified acid thickener to have salt resistance.
In the invention, the hydroxyl in the lactobionic acid prepolymer further enhances the solubility of the polymer and improves the dissolution speed, and the hydroxyl belongs to an insensitive group of hydrogen ions, thereby further improving the acid resistance of the polymer; the triallyl cyanurate is crosslinked in a molecular chain to form a net structure, and the net structure is interlaced and interpenetrated with a six-membered ring in the galacturonic acid prepolymer, so that the thermal stability and the shear resistance of the polymer molecular chain are further improved on the one hand; on the other hand, the interpenetrating network structure can effectively prevent the activity of hydrogen ions in acid, thereby reducing the consumption rate of the acid liquor, increasing the effective action distance and achieving the purpose of slowing down.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.
The invention provides a preparation method of a modified acid thickener, which comprises the following steps:
(1) Performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer;
(2) Carrying out polycondensation reaction on lactobionic acid and allylamine to obtain a lactobionic acid prepolymer;
(3) Uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, a lignin prepolymer, a lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; uniformly mixing white oil, a main emulsifier and an auxiliary emulsifier to obtain an oil phase solution;
(4) Adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization reaction, and adding a phase inversion agent after the reaction is finished to obtain a modified acid solution thickening agent;
the modified acid thickener is prepared from the following raw materials in parts by weight: acrylamide 150 to 200 parts (for example, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, 180 parts, 185 parts, 190 parts, 195 parts, or 200 parts) or (3-acrylamidopropyl) trimethylammonium chloride 180 to 210 parts (for example, 180 parts, 185 parts, 190 parts, 195 parts, 200 parts, 205 parts, or 210 parts) or (5 to 10 parts (for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts) of triallyl cyanurate), a lignin prepolymer 20 to 30 parts (for example, 21 parts, 22 parts, 25 parts, 26 parts, 28 parts, 29 parts, or 30 parts) or (for example, 21 parts, 22 parts, 25 parts, 26 parts, 28 parts, 29 parts, or 30 parts) or a lactobionic acid prepolymer 20 to 30 parts (for example, 21 parts, 22 parts, 25 parts, 26 parts, 28 parts, 29 parts, or 30 parts) or (for example, 230 to 325 parts) or (for example, may be 235 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts, 300 parts, 310 parts, 320 parts or 325 parts), 0.005 to 0.01 part (for example, may be 0.005 parts, 0.006 parts, 0.007 parts, 0.008 parts, 0.009 parts or 0.01 parts), white oil to 230 parts (for example, may be 230 parts, 235 parts, 240 parts, 245 parts, 250 parts, 255 parts, 260 parts, 265 parts or 270 parts), 15 to 30 parts (for example, may be 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 25 parts, 26 parts, 28 parts or 30 parts), 3 to 7 parts (for example, may be 3 parts, 4 parts, 5 parts, 6 parts or 7 parts), 22 to 24 parts (for example, may be 22 parts, 22.5 parts, 23 parts, 23.5 parts or 24 parts) of a phase inversion agent.
In the invention, the water-in-oil modified acid thickener is prepared by introducing the synergistic effect of lignin prepolymer, lactobionic acid prepolymer, acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride and triallyl cyanurate. The modified acid solution densifier has excellent water solubility, strong tackifying capability in acid solution and excellent temperature resistance and shear resistance.
According to some preferred embodiments, in step (1), the mass ratio of sodium lignosulfonate to allylic halohydrocarbon is (3.5 to 4.4): 1 (for example, 1, 3.6.
In the present invention, the allyl halohydrocarbon is slightly in excess to ensure that the sodium lignosulfonate can be completely reacted, so that the mass ratio of the sodium lignosulfonate to the allyl halohydrocarbon is limited to the above range, and the yield of the lignin prepolymer is ensured.
According to some preferred embodiments, in step (1), the temperature of the polycondensation reaction is 80 ℃ and the reaction time is not less than 24 hours (for example, it may be 24 hours, 28 hours, 32 hours, 36 hours, etc.).
According to some preferred embodiments, in step (1), the allylic halohydrocarbon is allyl chloride, allyl bromide or allyl iodide.
Specifically, when the allyl halogenated hydrocarbon is allyl bromide, the solvent medium is acetone, and the reaction formula of the polycondensation reaction in step (1) is as follows:
in this reaction scheme, potassium carbonate is used to provide an alkaline environment and to handle the byproduct hydrogen bromide. It should be noted that the solvent medium includes, but is not limited to, acetone, and may be any solvent that can ensure that the reactants are completely dissolved and do not participate in the reaction.
In the invention, carbon-carbon double bonds are introduced into sodium lignosulfonate through the polycondensation reaction of sodium lignosulfonate and allyl halohydrocarbon to obtain a lignin prepolymer, the benzene ring structure in the lignin prepolymer improves the rigidity of the molecular chain of the prepared modified acid thickener, the anti-shearing capability is enhanced, in addition, the benzene ring has hydrophobic property, a polymer molecular chain can generate hydrophobic association micro-areas, intermolecular association is generated, a space network structure is formed to achieve the adhesion increasing effect, and the rigidity and the hydrophobic association of the molecular chain jointly improve the thermal stability of the polymer.
According to some preferred embodiments, in step (2), the mass ratio of lactobionic acid to allylamine is (2.5 to 3.2): 1 (for example, 2.5.
In the present invention, since the total reaction of lactobionic acid is ensured by slightly excessive allylamine, the mass ratio of lactobionic acid to allylamine is limited to the above range, and the yield of lactobionic acid prepolymer is ensured.
According to some preferred embodiments, in the step (2), the temperature of the polycondensation reaction is 50 to 55 ℃ (for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃ or 55 ℃), and the reaction time is not less than 12h (for example, 12h, 14h, 16h, 18h, 24h, etc.).
Specifically, the reaction formula of the condensation reaction of step (2) is as follows:
it should be noted that, the solvent medium in step (2) includes but is not limited to absolute ethanol, and may be any solvent that can ensure complete dissolution of reactants and does not participate in the reaction.
In the invention, carbon-carbon double bonds are introduced into lactobionic acid molecules through the polycondensation reaction of allylamine and lactobionic acid to obtain a lactobionic acid prepolymer, the solubility of the polymer is further enhanced and the dissolution speed is improved due to the hydroxyl in the lactobionic acid prepolymer, and the hydroxyl belongs to an insensitive group of hydrogen ions, so that the acid resistance of the polymer is further improved; the triallyl cyanurate is crosslinked in a molecular chain to form a net structure, and the net structure is interlaced and interpenetrated with a six-membered ring in the galacturonic acid prepolymer, so that the thermal stability and the shear resistance of the polymer molecular chain are further improved on the one hand; on the other hand, the interpenetrating network structure can effectively prevent the activity of hydrogen ions in acid, thereby reducing the consumption rate of the acid liquor, increasing the effective action distance and achieving the purpose of slowing down.
According to some preferred embodiments, step (3) further comprises: the pH of the aqueous solution is adjusted to 3.8 to 5 (for example, it may be 3.9, 4, 4.2, 4.5, 4.6, 4.8 or 5).
According to some preferred embodiments, the pH of the aqueous phase solution is adjusted with a pH adjuster; wherein the pH regulator is at least one of adipic acid, acetic acid and hydrochloric acid.
At least one of them is a mixture of any one or any several of them mixed in any ratio.
Experiments prove that the pH of the aqueous phase solution is adjusted to 3.8 to 5, so that the influence of the acidity and alkalinity of a reaction medium on the decomposition rate of an initiator can be avoided, and the polymerization degree of the modified acid thickener is ensured.
According to some preferred embodiments, the primary emulsifier is at least one of span-20, span-60, span-80, span-83;
the auxiliary emulsifier is at least one of tween-65, tween-81 and tween-85.
Experiments prove that the water-in-oil system of the prepared modified acid thickener is unstable due to the fact that the HLB value of the single emulsifier is fixed. Therefore, by using the two emulsifiers in a composite way, the HLB value of a water-in-oil system can be adjusted to reach a certain range, so that the modified acid thickener is more stable.
According to some preferred embodiments, the first initiator is at least one of ammonium persulfate, potassium persulfate, tert-butyl hydroperoxide, benzoyl peroxide;
the second initiator is at least one of sodium sulfite, sodium bisulfite and sodium pyrosulfite.
The first initiator is an oxidative initiator and the second initiator is a corresponding reductive initiator.
According to some preferred embodiments, the phase transfer agent is OP-10 or NP-10.
According to some preferred embodiments, in step (4), the emulsification time is 20 to 30min (e.g., can be 20min, 25min, or 30 min);
the temperature at which the polymerization reaction is initiated is 15 to 20 ℃ (for example, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃ or 20 ℃); the polymerization time is 5 to 7h (for example, 5h, 5.5h, 6h, 6.5h or 7 h).
According to some preferred embodiments, in step (4), the temperature of the polymerization reaction is controlled not to exceed 75 ℃ by controlling the amount of the second initiator.
In the invention, because the reaction is exothermic and the temperature is too high, the polymerization degree of the prepared modified acid thickener can be caused by too high reaction rate, and the thickening effect of the modified acid thickener is further influenced. Therefore, the maximum temperature range at the end of the polymerization reaction is limited to 70 to 75 ℃ by controlling the addition amount of the second initiator.
In the invention, water is used as a reaction medium of the polymerization reaction, so that the cost is low, the influence of an organic solvent on environmental pollution can be eliminated, the preparation process is simple, and heating is not required. And the environment of the reaction medium is neutral, the preparation process is environment-friendly, pollution-free, low in energy consumption, nontoxic and noncorrosive in the product, and free of secondary pollution, and the method conforms to the development direction of green and environment-friendly chemical additives.
Specifically, in step (4): and adding the water phase solution with the pH of 3.8 to 5 into the oil phase solution, emulsifying for 20 to 30min, introducing nitrogen for deoxygenation, adding a second initiator to initiate polymerization reaction, and adding a phase transfer agent after the reaction is completed for 5 to 7h to obtain the modified acid liquid thickener.
According to the invention, the parts of the raw materials used by the modified acid thickener are limited, so that the prepared modified acid thickener has strong tackifying capability in acid, good structural stability and excellent temperature resistance and shear resistance.
In the invention, when the using amounts of other components are unchanged, the using amount of the lignin prepolymer used for preparing the modified acid thickener is limited to 20 to 30 parts. Therefore, the problems that when the dosage of the lignin prepolymer is too much, the water-in-oil system is unstable in reaction due to too strong hydrophobicity, and slag or agglomeration is easy to occur in the reaction process can be avoided; meanwhile, the problems that the prepared polymer has poor shear resistance and poor tackifying effect when the dosage of the polymer is too low can be avoided. Similarly, when the dosage of other components is not changed, the dosage of the galacturonic acid prepolymer used for preparing the modified acid thickener is limited to 20 to 30 parts. Therefore, as the lactobionic acid prepolymer has a six-membered ring structure, if the consumption of the lactobionic acid prepolymer is too much, the hydrophobicity is too strong, and the other two double bonds are easy to crosslink, so that the reaction of a water-in-oil system is unstable; if the dosage of the lactose aldehyde acid prepolymer is too small, the solubility and the acid resistance of the prepared polymer are poor.
In the invention, when the usage amount of other components is unchanged, the usage amount of the triallyl cyanurate used for preparing the modified acid thickener is limited to 5 to 10 parts. Therefore, the phenomenon that the water-in-oil system is unstable due to excessive crosslinking reaction in the polymerization reaction process when the dosage of the water-in-oil system is excessive can be avoided.
The invention also provides a modified acid thickener prepared by the preparation method.
In order to more clearly illustrate the technical scheme and advantages of the present invention, a modified acid thickener and a preparation method thereof are described in detail by using several examples.
Preparing a lignin prepolymer:
17.8g of sodium lignosulfonate, 4.5g of allyl bromide and 4.33g of potassium carbonate are weighed and placed in a three-neck flask, 350mL of acetone solvent is added into the three-neck flask, nitrogen protection is started after uniform mixing, the three-neck flask is placed in a hot water bath, the temperature is controlled to be 80 ℃, and the reaction is stopped after heating reflux is carried out for 24 hours. And after the reaction is finished, filtering, recrystallizing the product for 3 times by using absolute ethyl alcohol, and drying to obtain the target product lignin prepolymer.
Preparation of galacturonic acid prepolymer:
12.34g of lactobionic acid was weighed into a three-necked flask with a stirrer containing 200mL of absolute ethanol, and 4.1g of allylamine was weighed and dissolved in 50mL of absolute ethanol. And (3) putting the three-neck flask into a water bath kettle, setting the temperature at 50 ℃, starting nitrogen protection, stirring, dropwise adding an ethanol solution of allylamine into the three-neck flask, and continuing to react for 12 hours after dropwise adding is finished within 30 min. And after the reaction is finished, filtering, washing the product for 3 times by using ether, and performing suction filtration and drying to obtain the target product, namely the lactobionic acid prepolymer.
Example 1
Preparing a modified acid thickener:
adding 305g of deionized water, 150g of acrylamide, 210g of (3-acrylamidopropyl) trimethyl ammonium chloride, 5g of triallyl cyanurate, 20g of lignin prepolymer, 20g of lactose aldehyde acid prepolymer and 0.008g of first initiator (ammonium persulfate) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 3.8 by adopting adipic acid;
adding 15g of main emulsifier (span-20) and 4g of auxiliary emulsifier (Tween-65) into 230g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (sodium sulfite aqueous solution, the mass fraction of sodium sulfite is 1 wt%) by using a micro-injection pump under the nitrogen atmosphere to initiate polymerization reaction, simultaneously controlling the temperature of the reactor by using ice water bath in a coordinated manner to enable the temperature rising rate of the reaction system to be 30 s/0.1-40 s/0.1 ℃, after the reaction is finished for 6h, adding 22g of phase inversion agent (OP-10), and stirring and mixing uniformly to obtain the modified acid thickener.
Example 2
Preparing a modified acid thickener:
adding 300g of deionized water, 160g of acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, 6g of triallyl cyanurate, 21g of lignin prepolymer, 23g of lactose aldehyde acid prepolymer and 0.007g of first initiator (potassium persulfate) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 4.1 by adopting acetic acid;
adding 17g of main emulsifier (span-60) and 3g of auxiliary emulsifier (Tween-81) into 260g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (a sodium bisulfite aqueous solution, the mass fraction of sodium bisulfite is 1 wt%) by using a micro injection pump under the nitrogen atmosphere to initiate polymerization reaction, simultaneously cooperatively controlling the temperature of the reactor by using an ice water bath to ensure that the temperature rising rate of the reaction system is 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 7h, adding 22g of a phase transfer agent (NP-10), and stirring and uniformly mixing to obtain the modified acid solution thickening agent.
Example 3
Preparing a modified acid thickener:
adding 273g of deionized water, 180g of acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, 7g of triallyl cyanurate, 25g of lignin prepolymer, 25g of lactobionic acid prepolymer and 0.01g of first initiator (tert-butyl hydroperoxide) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 4.2 by adopting hydrochloric acid;
adding 19g of main emulsifier (span-80) and 7g of auxiliary emulsifier (Tween-85) into 240g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the uniform water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (sodium metabisulfite aqueous solution with the mass fraction of 1 wt%) by using a micro-injection pump under the nitrogen atmosphere to initiate polymerization, cooperatively controlling the temperature of the reactor by using an ice-water bath to enable the temperature rising rate of the reaction system to be 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 5h, adding 24g of phase transfer agent (OP-10), and stirring and uniformly mixing to obtain the modified acid thickener.
Example 4
Preparing a modified acid thickener:
277g of deionized water, 180g of acrylamide, 190g of (3-acrylamidopropyl) trimethyl ammonium chloride, 8g of triallyl cyanurate, 30g of lignin prepolymer, 25g of lactose aldehyde acid prepolymer and 0.01g of first initiator (ammonium persulfate) are sequentially added into a reactor and mixed uniformly to obtain an aqueous phase solution, and the pH value of the aqueous phase solution is adjusted to 5.0 by adopting adipic acid;
adding 25g of main emulsifier (span-83) and 5g of auxiliary emulsifier (Tween-81) into 250g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (sodium metabisulfite aqueous solution, wherein the mass fraction of the sodium metabisulfite is 1 wt%) by using a micro-injection pump under the nitrogen atmosphere to initiate polymerization, simultaneously controlling the temperature of the reactor by using an ice water bath in a coordinated manner, enabling the temperature rising rate of the reaction system to be 30-0.1-40 s/0.1 ℃, ending the reaction for 6.5h, adding 24g of phase transfer agent (NP-10), and stirring and mixing uniformly to obtain the modified acid thickener.
Example 5
Preparing a modified acid thickener:
adding 260g of deionized water, 200g of acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride 180g, 10g of triallyl cyanurate, 30g of lignin prepolymer, 30g of galacturonic acid prepolymer and 0.009g of first initiator (potassium persulfate) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 4.0 by adopting acetic acid;
adding 30g of main emulsifier (span-80) and 6g of auxiliary emulsifier (Tween-81) into 270g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (an aqueous solution of sodium bisulfite, the mass fraction of which is 1 wt%) by using a micro injection pump under the nitrogen atmosphere to initiate polymerization reaction, simultaneously controlling the temperature of the reactor by using an ice water bath to cooperatively control the temperature of the reaction system, so that the temperature rising rate of the reaction system is 30-0.1-40 s/0.1 ℃, finishing the reaction for 5.5h, adding 23g of a phase transfer agent (NP-10), and stirring and mixing uniformly to obtain the modified acid thickener.
Comparative example 1
Preparing an acid thickener:
adding 350g of deionized water, 170g of acrylamide, 190g of (3-acrylamidopropyl) trimethyl ammonium chloride and 0.01g of first initiator (tert-butyl hydroperoxide) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 5.0 by adopting adipic acid;
adding 20g of main emulsifier (span-80) and 5g of auxiliary emulsifier (Tween-85) into 250g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (a sodium bisulfite aqueous solution, the mass fraction of sodium bisulfite is 1 wt%) by using a micro injection pump under the nitrogen atmosphere to initiate polymerization reaction, simultaneously cooperatively controlling the temperature of the reactor by using an ice water bath to ensure that the temperature rising rate of the reaction system is 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 6h, adding 23g of a phase transfer agent (OP-10), and stirring and uniformly mixing to obtain an acid thickener.
Comparative example 2
Comparative example 2 is substantially the same as example 4 except that: no lignin prepolymer was added, instead of 30g of deionized water, i.e., 307g of deionized water.
Comparative example 3
Comparative example 3 is substantially the same as example 4 except that: lactose aldehyde acid prepolymer is not added, and 25g of deionized water is added instead, namely 302g of deionized water is added.
Comparative example 4
Comparative example 4 is substantially the same as example 4 except that: triallyl cyanurate was not added instead of 8g of deionized water, i.e. 285g of deionized water.
The modified acid viscosifiers obtained in examples 1 to 5 and the acid viscosifiers obtained in comparative examples 1 to 4 are used as samples, 4g of the samples are weighed respectively, slowly added into 396g of hydrochloric acid solution (wherein the mass fraction of hydrochloric acid is 20%) under magnetic stirring, and dispersed and mixed uniformly to obtain sample solutions. Wherein the time for adding the sample is less than 10s, stirring is stopped after no insoluble substances exist and the sample is homogeneous, the stirring is covered, and the mixture is kept still in a constant-temperature water bath kettle at the temperature of 20 ℃ for 0.5h to fully swell the mixture to prepare the thickening acid. The thickening acids obtained above were then tested for apparent viscosity, viscosity retention, and high temperature stability, respectively, and the test results are shown in table 1.
Specifically, the method comprises the following steps: transferring the thickening acid into a sample cup of a six-speed rotational viscometer, standing for 0.5h in an environment at 20 ℃, and then standing for 170s -1 Viscosity eta at 20 ℃ measured at shear rate 0 . Standing the thickening acid in an environment at 120 ℃ for 6h, cooling to 20 ℃, and visually testing the stability (whether the thickening acid is precipitated or layered) under natural light; and using a six-speed rotational viscometer at 170s -1 Measuring viscosity eta at shear rate 1 . Viscosity retention = η 1 /η 0 ×100%。
TABLE 1
As can be seen from the data in Table 1, the modified acid solution thickener prepared by the invention has strong acid-resistant tackifying capability in 20wt% hydrochloric acid solution, and has a viscosity increasing capability within 170s -1 The viscosity reaches more than 60 mPas at the shearing rate, and the high-viscosity polyurethane elastomer has good shearing resistance. The viscosity retention rate after standing for 6 hours at 120 ℃ is kept above 90%, no delamination and no precipitate appear, and the high-temperature stability is good, which indicates that the modified acid thickener has excellent temperature resistance and shear resistance stability.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention. The invention has not been described in detail and is in part known to those of skill in the art.
Claims (10)
1. The preparation method of the modified acid thickener is characterized by comprising the following steps:
(1) Performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer;
(2) Carrying out polycondensation reaction on lactobionic acid and allylamine to obtain a lactobionic acid prepolymer;
(3) Uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, the lignin prepolymer, the lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; uniformly mixing white oil, a main emulsifier and an auxiliary emulsifier to obtain an oil phase solution;
(4) Adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization reaction, and adding a phase inversion agent after the reaction is finished to obtain the modified acid solution thickening agent;
the modified acid solution thickener is prepared from the following raw materials in parts by weight: 150-200 parts of acrylamide, 180-210 parts of (3-acrylamidopropyl) trimethyl ammonium chloride, 5-10 parts of triallyl cyanurate, 20-30 parts of a lignin prepolymer, 20-30 parts of a lactobionic acid prepolymer, 230-325 parts of water, 0.005-0.01 part of a first initiator, 230-270 parts of white oil, 15-30 parts of a main emulsifier, 3-7 parts of an auxiliary emulsifier and 22-24 parts of a phase transfer agent.
2. The production method according to claim 1, wherein in step (1):
the mass ratio of the sodium lignin sulfonate to the allyl halogenated hydrocarbon is (3.5-4.4) to 1; and/or
The temperature of the polycondensation reaction is 80 ℃, and the reaction time is not less than 24h; and/or
The allyl halohydrocarbon is allyl chloride, allyl bromide or allyl iodide.
3. The production method according to claim 1, wherein in step (2):
the mass ratio of the lactobionic acid to the allylamine is (2.5 to 3.2) to 1; and/or
The temperature of the polycondensation reaction is 50 to 55 ℃, and the reaction time is not less than 12h.
4. The method of claim 1, wherein:
the step (3) further comprises: and adjusting the pH value of the aqueous phase solution to 3.8-5.
5. The method of claim 4, wherein:
adjusting the pH of the aqueous phase solution with a pH adjusting agent; wherein the pH regulator is at least one of adipic acid, acetic acid and hydrochloric acid.
6. The method of claim 1, wherein:
the main emulsifier is at least one of span-20, span-60, span-80 and span-83;
the auxiliary emulsifier is at least one of tween-65, tween-81 and tween-85.
7. The method of claim 1, wherein:
the first initiator is at least one of ammonium persulfate, potassium persulfate, tert-butyl hydroperoxide and benzoyl peroxide;
the second initiator is at least one of sodium sulfite, sodium bisulfite and sodium metabisulfite; and/or
The phase transfer agent is OP-10 or NP-10.
8. The production method according to claim 1, wherein in step (4):
controlling the temperature of the polymerization reaction to not exceed 75 ℃ by controlling the amount of the second initiator.
9. The production method according to any one of claims 1 to 8, characterized in that, in step (4):
the emulsifying time is 20 to 30min;
the temperature for initiating the polymerization reaction is 15 to 20 ℃; the polymerization reaction time is 5 to 7h.
10. A modified acid viscosifier characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN118256216B (en) * | 2024-05-30 | 2024-07-26 | 山东海嘉石油化工有限公司 | Acidizing blocking remover, and preparation method and application thereof |
| CN118852535B (en) * | 2024-09-29 | 2024-12-13 | 山东省高新石油技术有限公司 | Environment-friendly composite acid thickener for acidizing and fracturing and preparation method thereof |
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| CN1061033A (en) * | 1990-10-30 | 1992-05-13 | 四川石油管理局天然气研究所 | The gel acid that acidifying strata is used |
| US8067342B2 (en) * | 2006-09-18 | 2011-11-29 | Schlumberger Technology Corporation | Internal breakers for viscoelastic surfactant fluids |
| CN107880869B (en) * | 2017-10-19 | 2020-12-01 | 成都创巨油气工程技术有限公司 | Microcapsule coated acid for oil field and preparation method thereof |
| CN110551250B (en) * | 2018-05-31 | 2021-08-27 | 中国石油天然气股份有限公司 | Emulsion type acid liquid thickener and preparation method thereof |
| CN109135716A (en) * | 2018-08-22 | 2019-01-04 | 中国石油天然气股份有限公司 | Thickening acid, mixed acid system and method for reducing friction resistance of emulsified acid |
| CN113136198B (en) * | 2021-04-07 | 2022-05-20 | 西安石油大油气科技有限公司 | Composite buffer for low-permeability oil field oil exploitation acidification |
| CN113321764B (en) * | 2021-08-03 | 2021-10-01 | 山东诺尔生物科技有限公司 | Acid liquor thickener and preparation method and application thereof |
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