CN117777987A - Emulsified acid nanoemulsifier and preparation method and application thereof - Google Patents
Emulsified acid nanoemulsifier and preparation method and application thereof Download PDFInfo
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- CN117777987A CN117777987A CN202311779970.1A CN202311779970A CN117777987A CN 117777987 A CN117777987 A CN 117777987A CN 202311779970 A CN202311779970 A CN 202311779970A CN 117777987 A CN117777987 A CN 117777987A
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- acid
- coupling agent
- chloride
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- silane coupling
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- 239000002253 acid Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003921 oil Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 229960003237 betaine Drugs 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- -1 3-propyl Chemical group 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 6
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 125000001302 tertiary amino group Chemical group 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- HEXHLHNCJVXPNU-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)butane-1,4-diamine Chemical compound CO[Si](OC)(OC)CC(CN)CCN HEXHLHNCJVXPNU-UHFFFAOYSA-N 0.000 claims description 4
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- DICUPLXUNISGAQ-UHFFFAOYSA-N Isooctyl acetate Chemical compound CC(C)CCCCCOC(C)=O DICUPLXUNISGAQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- WEPUZBYKXNKSDH-UHFFFAOYSA-N cyclopentanecarbonyl chloride Chemical compound ClC(=O)C1CCCC1 WEPUZBYKXNKSDH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- ISULZYQDGYXDFW-UHFFFAOYSA-N 3-methylbutanoyl chloride Chemical compound CC(C)CC(Cl)=O ISULZYQDGYXDFW-UHFFFAOYSA-N 0.000 claims description 3
- SVWCVXFHTHCJJB-UHFFFAOYSA-N 4-methylpentanoyl chloride Chemical compound CC(C)CCC(Cl)=O SVWCVXFHTHCJJB-UHFFFAOYSA-N 0.000 claims description 3
- UBZNGKUAUXOIKL-UHFFFAOYSA-N 8-methylnonanoyl chloride Chemical compound CC(C)CCCCCCC(Cl)=O UBZNGKUAUXOIKL-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000005251 aryl acyl group Chemical group 0.000 claims description 3
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 claims description 3
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 3
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 claims description 3
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 claims description 3
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical group 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- WNWVCOXFUHCXJQ-UHFFFAOYSA-N 6-methylheptanoyl chloride Chemical compound CC(C)CCCCC(Cl)=O WNWVCOXFUHCXJQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000000979 retarding effect Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004581 coalescence Methods 0.000 abstract 1
- 239000011435 rock Substances 0.000 description 11
- 239000007908 nanoemulsion Substances 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 239000004579 marble Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- IZWSFJTYBVKZNK-UHFFFAOYSA-N lauryl sulfobetaine Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- SFGBOBMTMFHZJH-UHFFFAOYSA-N 1-chloro-6-methylheptane Chemical compound CC(C)CCCCCCl SFGBOBMTMFHZJH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Abstract
The invention relates to the technical field of oil and gas reservoir acidification modification, and particularly provides an emulsified acid nanoemulsifier, a preparation method and application thereof, wherein modified nanoparticles, betaine surfactant, nonionic surfactant, cationic surfactant, ethanol and synthetic ester are mixed according to the ratio of 10-25:10-15:10-20:20-30:10-20: mixing 20-40 mass ratio, dispersing fully by using a homogenizing dispersing machine, the stirring speed is 20000-30000 rpm, the nano silicon dioxide is grafted and modified by adopting large steric hindrance group, the emulsion is adsorbed on an oil-water interface in a strong acid and strong ion environment, so that emulsion dripping coalescence is effectively inhibited, and the stability of the emulsion in a high-temperature, high-salt and strong acid environment is improved. The invention is used for preparing high-temperature emulsified acid, the prepared emulsified acid with 70-80% of the internal phase content of the acid liquid can be kept stable for more than 2 hours at the high temperature of 180 ℃, the retarding effect is excellent, the final corrosion rate is higher, the adoption of macromolecular polymers to stabilize emulsion is avoided, and the damage of residues to a reservoir is effectively prevented.
Description
Technical Field
The invention belongs to the technical field of acidizing reformation of oil and gas reservoirs, and particularly relates to an emulsified acid nanoemulsifier and a preparation method and application thereof.
Background
Carbonate reservoirs are one of the common reservoir types in our country, has the characteristics of large reserves, wide distribution, high exploration difficulty and the like, therefore, intensive research on the development technology of carbonate reservoirs and improvement of recovery ratio are important problems in the current oil and gas resource development. For carbonate reservoir characteristics, acid fracturing techniques are generally employed, after the reservoir is opened by pumping acid liquor, non-uniform etching is avoided in the cracks through acid rock reaction, and non-uniform etching channels for oil gas circulation are reserved after the cracks are closed. Carbonate reservoirs are buried deeply, stratum temperature is high, and conventional acid liquor systems can be consumed in near-wellbore zones due to the fact that acid rock reaction speed is too high, so that acidizing fails. Therefore, an acid liquor system for acidizing and fracturing the carbonate rock needs to have a certain retarding effect in a high-temperature environment, so that deep penetration of acid liquor is realized, and the action distance of the acid liquor is increased.
The current common retarded acid liquid system comprises gelled acid, cross-linked acid, autogenous acid, emulsified acid and the like. The gelled acid and the crosslinked acid are widely applied, and the acid-rock reaction speed is effectively delayed by thickening the acid liquor, improving the apparent viscosity of the acid liquor and reducing the mass transfer speed of hydrogen ions in the acid liquor to the rock wall surface. Aiming at the high-temperature reservoir environment, the addition amount of the polymer thickener used by the gelled acid or the crosslinked acid is large or the molecular weight of the polymer thickener is large, and insoluble matters are easily formed by the action of the polymer thickener and acid, metal ions and the like in the high-temperature environment, so that an oil gas channel is blocked, and the damage is caused. The self-acid generating system is characterized in that the acid generator is subjected to chemical reaction to generate HCl under a high-temperature environment to etch the rock face, but the acid generation amount is insufficient or difficult to control, so that the self-acid generating system is not commonly applied. The emulsified acid is an oil-phase emulsion formed by wrapping acid liquor with oil phase, carrying the acid liquor into the deep part of cracks, demulsifying under high temperature or strong ion environment, and gradually releasing the acid liquor to etch the rock wall surface. The emulsified acid not only has good retarder, but also can protect the pipe column more effectively. However, the conventional surfactant emulsifier is often poor in stability of emulsified acid prepared, and is rapid in demulsification in a high-temperature environment, so that the acid liquor is difficult to penetrate deeply; in order to improve the stability of the emulsified acid and realize deep acidification, research and development personnel can strengthen the stability of the emulsion by adding a polymer thickener, but the risk of residue damage still exists.
Disclosure of Invention
The invention aims to provide an emulsified acid nanoemulsifier, a preparation method and application thereof, which are used for stabilizing emulsified acid liquor for carbonic acid rock acid pressure in a high-temperature environment, slowing down the reaction speed of acid rock, realizing deep penetration of acid liquor and avoiding residue injury caused by taking a high-molecular thickener and jelly as an acid liquor stabilizer.
In order to solve the technical problems, the invention provides an emulsified acid nanoemulsifier, which is prepared from modified nanoparticles, betaine surfactant, nonionic surfactant, cationic surfactant, ethanol and synthetic ester according to the ratio of 10-25:10-15:10-20:20-30:10-20: 20 to 40 mass ratio, and fully dispersing the mixture by adopting a homogenizing dispersing machine, wherein the stirring speed is 20000 to 30000 rpm.
Further, the modified nano-particles are prepared by grafting modification of nano-silica by an alkyl (aryl) amide silane coupling agent and a betaine silane coupling agent.
Further, the alkyl (aromatic) amide silane coupling agent is prepared by mixing 1-2 of alkyl (aromatic) acyl chloride and an amino silane coupling agent: 1-3 in the molar ratio of 10-50 wt% of the organic solvent, at 5-35 deg.c for 2-5 hr, and vacuum distillation to eliminate solvent after the reaction.
Further, the alkyl (aryl) acyl chloride is any one of phenylacetyl chloride, n-pentanoyl chloride, isopentanoyl chloride, n-hexanoyl chloride, isohexanoyl chloride, n-octanoyl chloride, isooctyl chloride, n-decanoyl chloride, isodecanoyl chloride, cyclopentyl formyl chloride and cyclohexyl formyl chloride with the carbon number between 5 and 14, and aryl acyl chloride molecules;
the aminosilane coupling agent is any one of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane and 2- [ (trimethoxysilyl) methyl ] butane-1, 4-diamine containing 1 or more primary amine and secondary amine structures;
the organic solvent is any one of organic solvents without hydroxyl in dichloromethane, tetrahydrofuran, toluene and acetone.
Further, the betaine silane coupling agent is prepared by reacting 1, 3-propyl sultone with a tertiary amino silane coupling agent.
Further, the betaine silane coupling agent is prepared by dissolving 1, 3-propyl sultone and tertiary amino silane coupling agent in an organic solvent according to a molar ratio of 1-1.3:1, wherein the concentration of reactants is 5-50wt%, the reaction temperature is 30-60 ℃, and the reaction time is 2-5 hours;
the organic solvent is any one solvent of acetone and dichloromethane in which betaine inner salt is not dissolved;
the tertiary amine silane coupling agent is any one of (N, N-dimethyl-3-aminopropyl) trimethoxy silane and N, N-diethyl-3-aminopropyl trimethoxy silane containing tertiary amine structure silane coupling agent.
Further, the nano silicon dioxide grafting modification method comprises the following steps: dispersing an alkane (aryl) amide silane coupling agent, a betaine silane coupling agent and nano silicon dioxide in an organic solvent according to a mass ratio of 1-3:2-5:3-7, fully dispersing the mixture by adopting a homogenizing dispersing machine, wherein the stirring speed is 15000-30000 rpm, the reaction temperature is 40-60 ℃, and the reaction time is 5-6 hours.
Further, the synthetic ester is any one of ethyl acetate, butyl acetate and isooctyl acetate with a melting point lower than 0 ℃.
The invention also provides an application of the emulsified acid nanoemulsion, 2-7 parts of the nanoemulsion are fully dispersed in 25-30 parts of an oil phase, the oil phase is continuously stirred at a mechanical stirring speed of 2000-5000 rpm, 63-73 parts of prepared acid liquor is dripped into the oil phase at a speed of 2-5 parts/min, so that the oil phase is always a dominant phase, and an acid-in-oil system with the internal phase content of 63% -73% is prepared.
Further, the acid liquid is any one of conventional hydrochloric acid, earth acid, organic acid and autogenous acid; the oil phase is any one of diesel oil, white oil or hydrocarbon fluid with the condensation point lower than 0 ℃ in crude oil.
The invention also provides an application of the emulsified acid nanoemulsion, 2-7 parts of the nanoemulsion are fully dispersed in 25-30 parts of an oil phase, the oil phase is continuously stirred at a mechanical stirring speed of 2000-5000 rpm, 63-73 parts of prepared acid liquor is dripped into the oil phase at a speed of 2-5 parts/min, so that the oil phase is always a dominant phase, and an acid-in-oil system with the internal phase content of 63% -73% is prepared.
Further, the acid liquid is any one of conventional hydrochloric acid, earth acid, organic acid and autogenous acid.
Further, the oil phase is any one of diesel oil, white oil or hydrocarbon fluid with the condensation point lower than 0 ℃ in crude oil.
The nanometer emulsifying agent for emulsified acid is used in preparing high temperature emulsified acid, and the prepared emulsified acid with internal phase content of 70-80% may be maintained in high temperature environment of 180 deg.c for over 2 hr to stabilize, so that the nanometer emulsifying agent has excellent retarding effect and high ultimate corrosion rate, and this can avoid stable emulsion with macromolecular polymer and prevent damage of residue to reservoir.
The beneficial effects of the invention are as follows:
1. the invention provides an emulsified acid nanoemulsifier, which is prepared from modified nanoparticles, betaine surfactant, nonionic surfactant, cationic surfactant, ethanol and synthetic ester according to the ratio of 10-25:10-15:10-20:20-30:10-20: 20-40, wherein the unique grafting structure and interfacial activity characteristics of the modified nano particles can be cooperated with various surfactant auxiliary agents to endow the water-in-oil emulsion with good stability;
2. the nano-emulsifier is adsorbed on an oil-water interface, endows the interface with good rigidity characteristics, has good temperature stability and salt resistance, and ensures that the water-in-oil emulsion has stronger stability in a high-temperature complex medium environment;
3. the invention can be used for preparing the emulsified acid liquid for carbonic acid rock acid fracturing at the temperature of more than 180 ℃, can efficiently slow down the reaction speed of acid rock, realize deep penetration of acid liquid, and simultaneously avoid residue injury caused by taking a high-molecular thickener and jelly as acid liquid stabilizers.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a modified structure of silica particles for nanoemulsions;
FIG. 2 is a schematic diagram of the preparation of an alk (en) yl amid silane coupling agent for modifying nanoparticles;
FIG. 3 is a schematic diagram of another alkyl (aryl) amide silane coupling agent preparation route for modifying nanoparticles;
FIG. 4 is a circuit diagram of the preparation of betaine silane coupling agent for modifying nanoparticles;
FIG. 5 is a schematic view of the surface structure of nanoparticles modified by the three silane coupling agents prepared in example 1, example 2, and example 3;
FIG. 6 is a graph showing the change in particle size distribution curves before and after modification of nano-silica particles;
FIG. 7 shows the demulsification of the emulsified acid prepared in example 6 at a high temperature of 180℃at 160℃and 140 ℃.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other examples, which are obtained by a person of ordinary skill in the art without making any inventive effort, based on the examples of the present invention, are within the scope of the present invention, and the specific conditions are not specified in the examples, and the reagents or instruments used are not specified in the manufacturer, and are conventional products available through commercial purchase.
The invention provides an emulsified acid nanoemulsifier, which is prepared from modified nanoparticles, betaine surfactant, nonionic surfactant, cationic surfactant, ethanol and synthetic ester according to the ratio of 10-25:10-15:10-20:20-30:10-20: mixing 20-40 mass percent, fully dispersing by adopting a homogenizing dispersing machine, and stirring at 20000-30000 rpm; the synthetic ester is any one of ethyl acetate, butyl acetate and isooctyl acetate with melting point lower than 0deg.C.
Specifically, the modified nano-particles are prepared by grafting and modifying nano-silicon dioxide by an alkyl (aryl) amide silane coupling agent and a betaine silane coupling agent, and the schematic diagram of the surface structure of the modified nano-particles is shown in figure 1;
specifically, the alkyl (aromatic) amide silane coupling agent is prepared by mixing 1-2 of alkyl (aromatic) acyl chloride and an amino silane coupling agent: 1-3 in the molar ratio of 10-50 wt% of the organic solvent, at 5-35 deg.c for 2-5 hr, and vacuum distillation to eliminate solvent after the reaction.
Specifically, the alkyl (aryl) acyl chloride is any one of phenylacetyl chloride, n-pentanoyl chloride, iso-pentanoyl chloride, n-hexanoyl chloride, iso-hexanoyl chloride, n-octanoyl chloride, iso-octanoyl chloride, n-decanoyl chloride, iso-decanoyl chloride, cyclopentyl formyl chloride and cyclohexyl formyl chloride with the carbon number between 5 and 14, and the aryl acyl chloride molecule improves sufficient lipophilicity for the nano particles.
Specifically, the aminosilane coupling agent is any one of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane and 2- [ (trimethoxysilyl) methyl ] butane-1, 4-diamine containing 1 or more primary amine and secondary amine structures.
Specifically, the organic solvent is any one of dichloromethane, tetrahydrofuran, toluene and acetone without hydroxyl.
Specifically, the betaine silane coupling agent is prepared by reacting 1, 3-propyl sultone with a tertiary amino silane coupling agent, wherein the reaction is that the 1, 3-propyl sultone and the tertiary amino silane coupling agent are dissolved in an organic solvent in a molar ratio of 1-1.3:1, the concentration of reactants is 5-50wt%, the reaction temperature is 30-60 ℃, and the reaction time is 2-5 hours; the organic solvent is any solvent which does not dissolve betaine inner salt in acetone and dichloromethane, so that the reaction product can be directly separated out, and the pure product can be obtained by filtration, drying and the like.
Specifically, the tertiary amine silane coupling agent is any one of (N, N-dimethyl-3-aminopropyl) trimethoxysilane and a tertiary amine structure silane coupling agent contained in N, N-diethyl-3-aminopropyl trimethoxysilane.
The nano silicon dioxide grafting modification method comprises the following steps: dispersing an alkane (aryl) amide silane coupling agent, a betaine silane coupling agent and nano silicon dioxide in an organic solvent according to a mass ratio of 1-3:2-5:3-7, fully dispersing the mixture by adopting a homogenizing dispersing machine, wherein the stirring speed is 15000-30000 rpm, the reaction temperature is 40-60 ℃, and the reaction time is 5-6 hours.
The invention also provides an application of the emulsified acid nanoemulsion, 2-7 parts of the nanoemulsion are fully dispersed in 25-30 parts of an oil phase, the oil phase is continuously stirred at a mechanical stirring speed of 2000-5000 rpm, 63-73 parts of prepared acid liquor is dripped into the oil phase at a speed of 2-5 parts/min to ensure that the oil phase is always a dominant phase, and an acid-in-oil system with the internal phase content of 63% -73% is prepared, specifically, the acid liquor is any one of conventional hydrochloric acid, earthic acid, organic acid and autogenous acid, and the oil phase is any one of hydrocarbon fluid with the condensation point lower than 0 ℃ in diesel oil, white oil or crude oil.
Example 1
The preparation method of the alkyl (aryl) amide silane coupling agent for grafting modified nano particles adopts phenylacetyl chloride and N- (2-aminoethyl) -3-aminopropyl trimethoxy silane as reactants, the reactants are dissolved in methylene dichloride according to the molar ratio of 1:1, the concentration of the reactants is 30wt%, the temperature is set to 35 ℃, the mixture is stirred magnetically, the mixture is refluxed for 4 hours, and the solvent is removed by reduced pressure distillation after the reaction is finished, wherein the reaction route is shown in figure 2.
Example 2
The preparation method of the other alkyl (aryl) amide silane coupling agent for the grafting modified nano particles comprises the steps of selecting cyclopentyl formyl chloride and 2- [ (trimethoxysilyl) methyl ] butane-1, 4-diamine as reactants, dissolving the reactants in methylene dichloride according to a molar ratio of 2:1, setting the concentration of the reactants to 35wt%, setting the temperature to 35 ℃, stirring the reactants with a magnet, refluxing for 6 hours, and removing the solvent by reduced pressure distillation after the reaction is finished, wherein the reaction route is shown in figure 3.
Example 3
The preparation method of the betaine silane coupling agent for the grafting modified nano particles comprises the steps of selecting 1, 3-propyl sultone and (N, N-dimethyl-3-aminopropyl) trimethoxy silane as reactants, dissolving the reactants in acetone according to a molar ratio of 1.2:1, wherein the concentration of the reactants is 25wt%, setting the temperature to 50 ℃, stirring the magnetons, refluxing for 8 hours, filtering out precipitate after the reaction is finished, and drying to obtain a reaction product, wherein the reaction route is shown in figure 4.
Example 4
One method of preparing the grafted modified nanoparticle is as follows:
(1) The specific parameters of the selected nano silicon dioxide material are as follows: spherical structure, average diameter 25.5nm, purity 99.9%, specific surface area 300-400 square meter/g; calcining the nano silicon dioxide raw material in a muffle furnace at 700 ℃ for 12 hours, and activating hydroxyl groups on the surfaces of the nano particles;
(2) Dispersing the three silane coupling agents prepared in the examples 1, 2 and 3 and silicon dioxide in tetrahydrofuran according to the mass ratio of 1:1:3:3, wherein the mass concentration of the reaction substances is 20wt%, and dispersing the mixture for 10min at 30000rpm by using a homogenizing dispersing machine;
(3) Heating to 50deg.C, stirring with magnetic iron, and refluxing for 6 hr;
(4) After the reaction is finished, removing the solvent by reduced pressure distillation to obtain grafted modified nano particles;
(5) The surface modification of the modified silica nanoparticles is shown in fig. 5.
The average particle diameter of the selected nano silicon dioxide particles is increased from 25.5nm to 32.7nm before and after modification, and the particle diameter distribution curve of the nano silicon dioxide particles before and after modification is shown in figure 6. (data are derived from dynamic light scattering experiments: the silica nanoparticles before and after modification were sufficiently dispersed in tetrahydrofuran solvent at a concentration of 0.2wt% and analyzed for particle size distribution by dynamic light scattering).
Example 5
The preparation method of the nanoemulsion comprises the steps of adopting modified nanoparticles prepared in the embodiment 4, dodecyl sulfobetaine (BS-12), polyoxyethylene lauryl ether, dodecyl trimethyl ammonium chloride, ethanol and isooctyl acetate according to the ratio of 10:10:20:20:20:10: 30, and dispersing the mixture sufficiently by using a homogenizing and dispersing machine at a stirring speed of 30000rpm for 2 hours to obtain a uniform dispersion.
Example 6
And (5) preparing emulsified acid and evaluating performance.
Preparing emulsified acid, namely fully dispersing 2-7 parts of the nano-emulsifier prepared in the embodiment 5 in 25-30 parts of 0# diesel oil, continuously stirring an oil phase at a mechanical stirring speed of 5000rpm, and dripping 65 parts of prepared acid liquor into the oil phase at a speed of 4 parts/min to ensure that the oil phase is always a dominant phase, so as to prepare an acid-in-oil system with an internal phase content of 65%; the formula of the acid liquor is 15wt% of HCl+2.0wt% of Mannich base corrosion inhibitor+0.8wt% of EDTA. The prepared emulsified acid was divided into three equal parts, and the relationship between the demulsification rate and time was measured at 140℃and 160℃and 180℃respectively, and the measurement results are shown in FIG. 7. Test results show that the emulsion breaking rate of emulsified acid with 65% of internal phase prepared by the nano-emulsifier prepared in the embodiment 5 is respectively lower than 60%, 45% and 30% after 2 hours at the high temperature of 180 ℃, 160 ℃ and 140 ℃, and the effect advantage of the nano-emulsifier at the high temperature is fully shown.
Example 7
The marble is subjected to corrosion experiments at 180 ℃ by using the gelled acid, the cross-linked acid and the emulsified acid prepared in the embodiment 6, and the retarding capacity of the acid liquor is analyzed, so that the result shows that after 2 hours, the emulsified acid prepared in the embodiment 6 at 180 ℃ has only 18% of the rate of Dan Rongshi of the marble, and the gelled acid and the cross-linked acid have 28% and 25% of the rate of Dan Rongshi of the marble respectively, so that the excellent retarding capacity of the emulsified acid prepared in the embodiment 6 is shown.
The foregoing disclosure is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. The emulsifying acid nanoemulsifier is characterized by comprising modified nanoparticles, betaine surfactant, nonionic surfactant, cationic surfactant, ethanol and synthetic ester according to the ratio of 10-25:10-15:10-20:20-30:10-20: 20 to 40 mass ratio, and fully dispersing the mixture by adopting a homogenizing dispersing machine, wherein the stirring speed is 20000 to 30000 rpm.
2. The emulsified acid nanoemulsifier according to claim 1, wherein the modified nanoparticle is prepared by grafting modification of nanosilica with an alkyl (aryl) amide silane coupling agent, a betaine silane coupling agent.
3. An emulsified acid nanoemulsifier as set forth in claim 2, wherein said alk (aryl) amide silane coupling agent is prepared by reacting an alk (aryl) yl chloride with an aminosilane coupling agent in an amount of 1 to 2: 1-3 in the molar ratio of 10-50 wt% of the organic solvent, at 5-35 deg.c for 2-5 hr, and vacuum distillation to eliminate solvent after the reaction.
4. An emulsified acid nanoemulsifier according to claim 3, wherein the alkyl (aryl) acyl chloride is any one of phenylacetyl chloride, n-pentanoyl chloride, isopentanoyl chloride, n-hexanoyl chloride, isohexanoyl chloride, n-octanoyl chloride, isooctanoyl chloride, n-decanoyl chloride, isodecanoyl chloride, cyclopentyl formyl chloride, cyclohexyl formyl chloride, alkyl having 5 to 14 carbon atoms, and aryl acyl chloride molecules;
the aminosilane coupling agent is any one of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane and 2- [ (trimethoxysilyl) methyl ] butane-1, 4-diamine containing 1 or more primary amine and secondary amine structures;
the organic solvent is any one of organic solvents without hydroxyl in dichloromethane, tetrahydrofuran, toluene and acetone.
5. An emulsified acid nanoemulsifier as set forth in claim 2 wherein said betaine silane coupling agent is prepared by reacting 1, 3-propyl sultone with a tertiary amino silane coupling agent.
6. The emulsified acid nanoemulsifier according to claim 5, wherein the betaine silane coupling agent is prepared by dissolving 1, 3-propyl sultone and tertiary amino silane coupling agent in an organic solvent according to a molar ratio of 1-1.3:1, wherein the concentration of reactants is 5-50 wt%, the reaction temperature is 30-60 ℃ and the reaction time is 2-5 hours;
the organic solvent is any one solvent of acetone and dichloromethane in which betaine inner salt is not dissolved;
the tertiary amine silane coupling agent is any one of (N, N-dimethyl-3-aminopropyl) trimethoxy silane and N, N-diethyl-3-aminopropyl trimethoxy silane containing tertiary amine structure silane coupling agent.
7. The emulsified acid nanoemulsifier as set forth in claim 2, wherein the nanosilica grafting modification method is: dispersing an alkane (aryl) amide silane coupling agent, a betaine silane coupling agent and nano silicon dioxide in an organic solvent according to a mass ratio of 1-3:2-5:3-7, fully dispersing the mixture by adopting a homogenizing dispersing machine, wherein the stirring speed is 15000-30000 rpm, the reaction temperature is 40-60 ℃, and the reaction time is 5-6 hours.
8. The emulsifying acid nanoemulsifier of claim 1 wherein the synthetic ester is any one of ethyl acetate, butyl acetate and isooctyl acetate having a melting point below 0 ℃.
9. The use of an emulsified acid nanoemulsifier, characterized in that 2 to 7 parts of the nanoemulsifier according to any one of claims 1 to 8 are taken to be fully dispersed in 25 to 30 parts of an oil phase, the oil phase is continuously stirred at a mechanical stirring speed of 2000 to 5000rpm, 63 to 73 parts of the prepared acid liquor is dripped into the oil phase at a speed of 2 to 5 parts per minute, so that the oil phase is always a dominant phase, and an acid-in-oil system with an internal phase content of 63 to 73% is prepared.
10. The use of an emulsified acid nanoemulsifier according to claim 9, characterized in that the acid liquid is any one of conventional hydrochloric acid, earth acid, organic acid, autogenous acid; the oil phase is any one of diesel oil, white oil or hydrocarbon fluid with the condensation point lower than 0 ℃ in crude oil.
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