CN112111037A - Binary fluorine-containing polymer wetting reversal agent and preparation method and application thereof - Google Patents
Binary fluorine-containing polymer wetting reversal agent and preparation method and application thereof Download PDFInfo
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- CN112111037A CN112111037A CN202011018481.0A CN202011018481A CN112111037A CN 112111037 A CN112111037 A CN 112111037A CN 202011018481 A CN202011018481 A CN 202011018481A CN 112111037 A CN112111037 A CN 112111037A
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- 238000009736 wetting Methods 0.000 title claims abstract description 74
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 50
- 239000011737 fluorine Substances 0.000 title claims abstract description 50
- 239000012313 reversal agent Substances 0.000 title claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 229920002313 fluoropolymer Polymers 0.000 claims description 20
- 239000004811 fluoropolymer Substances 0.000 claims description 20
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000006073 displacement reaction Methods 0.000 claims description 9
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005553 drilling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 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 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 4
- 239000000203 mixture Substances 0.000 claims 1
- SMGIMBKCWODARY-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,7,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)CC(F)(F)F SMGIMBKCWODARY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 11
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- -1 fluorine-substituted acrylate Chemical class 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 239000008398 formation water Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- BDLVNNJRAIUIMO-UHFFFAOYSA-N amino(hydroxy)silicon Chemical compound N[Si]O BDLVNNJRAIUIMO-UHFFFAOYSA-N 0.000 description 2
- MJYSISMEPNOHEG-UHFFFAOYSA-N anthracen-9-ylmethyl 2-methylprop-2-enoate Chemical compound C1=CC=C2C(COC(=O)C(=C)C)=C(C=CC=C3)C3=CC2=C1 MJYSISMEPNOHEG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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Abstract
The invention relates to a binary fluorine-containing polymer wet reversal agent and a preparation method and application thereof. The binary fluorine-containing polymer microemulsion wetting reversal agent is obtained by the polymerization reaction of a methacrylic acid dodecafluoroheptyl ester, a 2- (perfluorohexyl) ethyl methacrylate binary monomer and an acrylic monomer in the presence of an initiator. The binary fluorine-containing polymer emulsion prepared by the invention is used as a wetting reversal agent, is stably dispersed in a water-based system, can enable the contact angle between a stratum and water to reach 142 degrees after being used, obviously improves the wettability of the stratum, reduces the interface free energy of a reservoir and improves the oil and gas recovery rate.
Description
Technical Field
The invention relates to a binary fluorine-containing polymer wet reversal agent and a preparation method and application thereof, belonging to the technical field of oil and gas exploitation.
Background
In each production operation of oil and gas field exploration and development, as the wettability of a reservoir is generally hydrophilic and oleophilic, the migration resistance of working fluid and oil and gas resources in the reservoir is large, the energy consumption in the exploitation process is increased, and the oil and gas recovery rate and the flowback rate of the working fluid are reduced. Therefore, the wettability of the reservoir plays a crucial role in the production of hydrocarbons and the drainage of the working fluid. The addition of the wetting reversal agent can change the reservoir from water wetting to hydrophobic property, thereby reducing the resistance in the migration and reverse drainage processes and achieving the effects of improving the recovery ratio and the flow-back rate. Wafrielin et al disclose a wetting reversal agent RSFZ-5 based on an amino silanol and a polymeric alcohol. See fenyoulin, liuheng, chen. preparation of wetting reversal agent and performance evaluation [ J ]. drilling and completion fluids, 2013,30(6): 29-32.
In the preparation of ultraphobic surfaces, lowering the free energy of the interface is a central problem in altering its wettability, while altering the roughness of the interface and coating with low free energy substances are the most common methods. The carbon-fluorine bond has the lowest free energy, and the use of the fluorine-containing compound can remarkably change the wettability of a solid-liquid interface, so that the hydrophobic or super-amphiphobic effect is achieved. However, the fluorocarbon has very low free energy, so that the dispersion problem in the preparation process becomes a difficult point, and especially the variety and cost of monomer raw materials in the polymerization process and the like hinder the development progress of the field. In recent years, the progress of fluorine-containing polymers is promoted by the progress of fluorine industry, and various researches are made by abundant fluorine-containing monomers, wherein fluorine-substituted acrylate monomers are most widely applied to fluorine-containing polymer emulsion, and the dispersion problem of the fluorine-containing polymers in a system is effectively solved by the diversification of emulsifier and emulsion polymerization modes.
Most of the commonly used wetting reversal agents are functional surfactants, and the solvents in the dispersion system can be divided into water-based ones and oil-based ones. For example, the patent document CN105368414A discloses an oil-based combined type wetting reversal agent, which can be used in oil-based drilling fluid to achieve better plugging effect. However, most oil fields are high in water content nowadays, and working fluid is mostly water-based, so that the demand of a water-based wetting reversion agent is larger. For example, CN107384358A provides a method for preparing a wetting inversion agent for improving the depressurization and injection enhancement effects of a water injection well of a low permeability reservoir, which comprises the steps of uniformly mixing water, iso-alcohol polyoxyethylene ether and a dispersing agent, adding sodium alkyl benzene sulfonate and sodium fatty alcohol polyoxyethylene ether sulfate, stirring, adding a dissolution promoter, and uniformly stirring, wherein the prepared wetting inversion agent can be obtained by converting oil wetting into water wetting. The dicationic fluorocarbon surfactant prepared in the patent document CN106634894A is applied to oil and gas drilling as a wetting reversal agent, so that the rock has the effect of hydrophobic and oleophobic properties. The wetting inversion agent obtained has the wetting angle between the formation and water reaching over 100 degrees after being used, but not exceeding 110 degrees, and the wetting inversion capability is limited. The fluoropolymer emulsion provided by CN110982009A has a significantly improved wetting angle compared with the existing wetting reversal agent, but has yet to be improved in terms of wetting reversal capability and cost.
Disclosure of Invention
Aiming at the problem of reservoir wettability, the invention provides a binary fluorine-containing polymer wetting reversal agent capable of obviously changing the reservoir wettability and a preparation method thereof. The binary fluorine-containing polymer prepared by the invention is a microemulsion wetting reversal agent, has stable property, simple and easily-operated preparation process, and can be used for modifying a reservoir under the use condition of lower concentration, remarkably changing the wettability of the reservoir and improving the oil gas recovery ratio.
The invention also provides application of the binary fluorine-containing polymer.
The technical scheme of the invention is as follows:
a preparation method of a binary fluorine-containing polymer microemulsion wetting reversal agent comprises the following steps: in the presence of perfluorooctanoic acid, emulsifying dodecafluoroheptyl methacrylate and 2- (perfluorohexyl) ethyl methacrylate monomers in water to obtain binary fluorine-containing monomer emulsion; dissolving acrylic monomers and an initiator in an organic solvent, then dripping the acrylic monomers and the initiator into binary fluorine-containing monomer emulsion, and carrying out polymerization reaction at 60-90 ℃ to obtain the polymer microemulsion wetting reversal agent.
The invention unexpectedly discovers that the dodecafluoroheptyl methacrylate and 2- (perfluorohexyl) ethyl methacrylate as fluorine-containing monomers can obviously improve the wetting reversal capability of the polymer, the functional groups of the dodecafluoroheptyl methacrylate and the 2- (perfluorohexyl) ethyl methacrylate have extremely small free energy, and the composite use of the dodecafluoroheptyl methacrylate and the 2- (perfluorohexyl) ethyl methacrylate can obviously reduce the free energy of the polymer; on the other hand, the cost of the auxiliary agent in the petroleum industry has important influence on the practical application, and the two fluorine-containing monomers adopted by the invention realize industrial quantitative production and have price advantage in the fluorine-containing monomers at present.
According to the invention, the mol ratio of the dodecafluoroheptyl methacrylate to the 2- (perfluorohexyl) ethyl methacrylate monomer is 1: 0.5-2. Further preferably, the molar ratio of the dodecafluoroheptyl methacrylate to the 2- (perfluorohexyl) ethyl methacrylate monomer is 1: 1.
According to the invention, the mol ratio of the dodecafluoroheptyl methacrylate and 2- (perfluorohexyl) ethyl methacrylate monomer to the acrylic monomer is preferably 1:0.5-2:1-4, and the mol ratio of the dodecafluoroheptyl methacrylate and 2- (perfluorohexyl) ethyl methacrylate monomer to the acrylic monomer is further preferably 1:1: 2.
The acrylic monomer is methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate or methacrylic acid-9-anthracene methyl ester. More preferably, the acrylic monomer is butyl methacrylate, dodecyl methacrylate or 9-anthracenemethylmethacrylate.
The initiator is one of ammonium persulfate, benzoyl peroxide and azobisisobutyronitrile. Further preferably, the initiator is azobisisobutyronitrile.
The organic solvent is selected from ethanol, N-Dimethylformamide (DMF), tetrahydrofuran or dichloromethane. Further preferably, the organic solvent is N, N-Dimethylformamide (DMF).
The dosage of the organic solvent is the dissolving amount. Preferably, the volume ratio of the organic solvent to the binary fluorine-containing monomer emulsifying water is 1: (0.5 to 4). Particularly preferably, the volume ratio of the organic solvent to water is 1: 1. the water is distilled water.
According to the invention, the ratio of the amount of the binary fluorine-containing monomer emulsifying water to the sum of the mass of the dodecafluoroheptyl methacrylate and the 2- (perfluorohexyl) ethyl methacrylate monomers is preferably as follows: 100:15-20, unit mL: g or L: kg.
According to the invention, the amount of the perfluorooctanoic acid is 1-5 mol% and the amount of the initiator is 1-5 mol% based on the total number of moles of double bonds in monomers in the system (the sum of the moles of the three monomers). Further preferably, the amount of the perfluorooctanoic acid is 2 to 2.5 mol% and the amount of the initiator is 2 to 2.5 mol%.
According to the present invention, the dropping rate of the acrylic monomer is preferably 2 to 3 d/s.
According to the invention, the polymerization reaction time is preferably 2-8 h, and more preferably 3-5 h.
In a preferred embodiment, a method for preparing a binary fluoropolymer microemulsion wetting reversal agent comprises the following steps:
50mL of distilled water and 0.4g of perfluorooctanoic acid were added to the reactor, respectively, and after dissolution, 0.01mol of dodecafluoroheptyl methacrylate and 0.01mol of 2- (perfluorohexyl) ethyl methacrylate were added, and ultrasonic emulsification was performed at room temperature for 30 min. And dissolving 0.02mol of acrylic monomer and 0.16g of initiator Azobisisobutyronitrile (AIBN) in 50mL of N, N-Dimethylformamide (DMF), dropwise adding into a three-neck flask at the temperature of 60 ℃ at the speed of 2-3 d/s, heating to 80 ℃ after dropwise adding, and reacting for 4 hours to obtain milky polymer microemulsion, namely the wetting reversal agent.
The binary fluorine-containing polymer microemulsion prepared by the invention has small particle size, the particle size of the emulsion is about 1-5 mu m, and the stability is good. The preferred particle size of the emulsion is about 1-2 μm.
The binary fluorine-containing polymer wetting reversal agent prepared by the invention has a structure shown in a formula I:
in the formula I, R is butyl, dodecyl or 9-anthracenemethyl, and n is 19-21. Further preferably, n is 20. The weight average molecular weight was 21000-28000.
In formula I "+" represents polymer end capping.
The polymer of the invention is a block copolymer, and the common polymer end capping is H free radical end capping.
The invention also provides the application of the binary fluorine-containing polymer as a wetting reversal agent in the drilling fluid. The binary fluorine-containing polymer has a structure shown in a formula I.
The invention also provides application of the binary fluorine-containing polymer as a wetting reversal agent in improving oil and gas recovery efficiency. Preferably, 1-2.5 wt.% of a binary fluoropolymer microemulsion wetting reversal agent is added to the displacement fluid for displacement.
The binary fluorine-containing polymer emulsion prepared by the invention can be stably dispersed in a water-based system as a novel wetting reversal agent, the contact angle between the stratum and water can be maximally more than 142 degrees under the use concentration of 1.0 wt.% after the emulsion is used, the interfacial free energy of the reservoir is greatly reduced (see table 1), the wettability of the stratum is remarkably improved, and the oil-gas recovery rate is improved.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention has the technical characteristics and excellent effects that:
1. the invention provides a novel binary fluorine-containing polymer wetting reversal agent, which is prepared by taking dodecafluoroheptyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate and acrylic monomers as main raw materials and adopting emulsion polymerization, and can be used for remarkably improving the wettability of a reservoir and converting the wettability of the reservoir from water wetting to hydrophobicity. In general, the lower the interfacial free energy, the poorer the wetting ability of a surface, and the lower the roughness of a surface and the lower the free energy of its surface material, the lower the free energy of the surface. The prepared binary fluorine-containing polymer wetting reversal agent has submicron size (see figure 2), so that the depression of the surface can be effectively filled, and the roughness of the surface is reduced; and the fluorine-containing functional groups, namely fluoromethyl and fluoromethylene, have extremely low free energy, so that the free energy of the surface can be greatly reduced, and the surface is changed from water wetting to hydrophobicity.
2. The raw materials used in the invention have realized the industrialized production, the raw materials are easy to obtain, the reaction process is simple, the preparation can be completed under the general chemical conditions, the preparation conditions are mild, the reaction conditions are easy to control, and the reaction process is safe.
3. Compared with the existing fluoropolymer emulsion wetting reversal agent (CN110982009A), the emulsion obtained by the invention has smaller particle size which can reach 1 μm at least and stronger stability; and the contact angle with water is larger, the maximum contact angle can reach 142 degrees, and the wetting reversal capability is stronger.
4. The binary fluorine-containing polymer microemulsion prepared by the invention has stable property, and the latex particles in the emulsion reach the submicron level, and can be stably stored for a long time at normal temperature and normal pressure.
5. The binary fluorine-containing polymer wetting reversal agent prepared by the invention has good compatibility with other water-based systems, and can be directly put into use without purification.
6. The binary fluorine-containing polymer wetting reversal agent prepared by the invention can reduce the free energy of the reservoir interface to a greater extent, has stronger wetting reversal capability, is used for the modification of oil and gas resource reservoirs, and can effectively improve the problems caused by the reservoir wettability problem in the development process of the oil and gas resources.
Drawings
FIG. 1 is an IR spectrum of the binary fluoropolymer product made in example 1. The wave number in the graph is 3400cm-1The absorption peak of hydroxyl in perfluorooctanoic acid is 3000-2815cm-1The peak is 1646cm-1The carbon-oxygen expansion absorption peak is located at ester group, 1545--1A fluorocarbon telescopic absorption peak of fluorine substituted alkyl and a fingerprint area of 670--1The absorption peaks indicate the successful synthesis of the product.
FIG. 2 is a transmission electron micrograph of a binary fluoropolymer microemulsion of example 1. As can be seen from the figure, the polymer particles can be uniformly dispersed in the emulsion, and the particle size distribution is about 2 μm, and can reach 1 μm at the minimum, which shows that the polymer microemulsion with submicron grade is obtained.
Figure 3 is the contact angle of the core of the example 1 binary fluoropolymer microemulsion wetting reversal experiment (experimental example 1) with water and n-hexadecane. Wherein a is the contact angle of a blank group of cores and water; b is the contact angle of the blank group of cores and n-hexadecane; c is the core to water contact angle of the product of example 1; d is the contact angle of the core of the product of example 1 with n-hexadecane.
Fig. 4 is a photograph of the product stability experiment of example 1 in experimental example 2, in which a is a photograph of the synthesized product on day 1 and b is a photograph of the synthesized product on day 30.
Fig. 5 is a saturated oil model of experimental example 3.
Fig. 6 is a visual displacement recovery curve under different conditions for experimental example 3. Wherein a is the recovery curve without the addition of a wet-inversion agent; b is the recovery curve with the addition of 2.0 wt.% of a binary fluoropolymer microemulsion wetting inverter.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the scope of the invention thereto.
Example 1
50mL of distilled water and 0.4g of perfluorooctanoic acid were added to a 250mL three-necked flask equipped with a reflux apparatus and an electromagnetic stirrer, respectively, and after dissolution, 4.0g (0.01mol) of dodecafluoroheptyl methacrylate and 4.3g (0.01mol) of 2- (perfluorohexyl) ethyl methacrylate were added, followed by ultrasonic emulsification at room temperature for 30 minutes. And dissolving 2.8g (0.02mol) of butyl methacrylate (acrylic monomer) and 0.16g of initiator Azobisisobutyronitrile (AIBN) in 50mL of N, N-Dimethylformamide (DMF), dropwise adding into a three-neck flask at the temperature of 60 ℃ at the speed of 2-3 d/s, heating to 80 ℃ after completing dropwise adding, and reacting for 4 hours to obtain milky binary fluoropolymer microemulsion, namely the wetting reversal agent. The transmission electron microscope picture of the binary fluorine-containing polymer microemulsion is shown in figure 2, the emulsion has small particle size which can reach 1 μm at least and strong stability.
The resulting product has the structure shown in formula I, wherein R is butyl, n is 20, and the weight average molecular weight is about 23000. The infrared spectrum of the obtained binary fluoropolymer product is shown in figure 1.
Example 2
The preparation was carried out as described in example 1, except that the acrylic monomer was 5.0g (0.02mol) of dodecyl methacrylate. The resulting product has the structure shown in formula I, wherein R is dodecyl, n is 20, and the weight average molecular weight is about 27000.
Example 3
The preparation was carried out as described in example 1, except that the acrylic monomer was 5.5g (0.02mol) of 9-anthracenemethylmethacrylate.
The resulting product has the structure shown in formula I, where R is 9-anthracenemethyl, n is 20, and the weight average molecular weight is about 28000.
Example 4
The preparation was carried out as described in example 1, except that the acrylic monomer butyl methacrylate was 1.4g (0.01 mol). The resulting product has the structure shown in formula I, wherein R is a hydrogen radical, n is 20, and the weight average molecular weight is about 21000.
Comparative example 1
The wetting reversal agent RSFZ-5 takes amino silanol and polymeric alcohol as main raw materials. Reference documents: preparation and performance evaluation of fenfrierin, Liuheng, Chenjun and wetting reversal agent [ J ]. drilling fluid and completion fluid, 2013,30(6): 29-32.
Comparative example 2
Dicationic fluorocarbon surfactant a4 prepared in example 4 of patent document CN106634894 a.
Comparative example 3
The fluoropolymer microemulsion prepared in example 1 of patent document CN110982009a wets the inverter.
Experimental example 1: wetting reversal capability experiment.
The binary fluorine-containing polymer microemulsion wetting reversal agents synthesized in the embodiments 1 to 4 of the invention are respectively added with water to prepare 1.0 wt.% of emulsion, then the natural core slice is soaked in the emulsion, kept for 12 hours at normal temperature and normal pressure and then taken out, dried for 4 hours at 60 ℃, the contact angles of the emulsion with water and n-hexadecane are respectively measured, and the interface free energy is calculated, wherein the data is shown in table 1.
TABLE 1 contact angle and interfacial free energy of core surface after Redox treatment
Note: the data for comparative examples 1-3 are derived from the corresponding original literature.
The data in the table 1 show that the core shows hydrophilic and lipophilic wettability in a natural state, has larger interface free energy, and can convert the wettability into hydrophobicity after being treated by the wetting reversal agent, so that the interface free energy is greatly reduced. In comparative examples 1-4, as the alkyl substituted chain segment in the acrylic monomer in the polymer increases, the contact angle of the product with water gradually increases, but the contact angle with n-hexadecane continuously increases, which is caused by the natural lipophilic and hydrophobic properties of the alkyl. Example 1 a picture of the financial contact angle is shown in figure 3.
After the binary fluorine-containing polymer wetting reversal agent is used, the interfacial free energy of the core can be reduced to 1.13mN/m from the initial 66.8mN/m at most, and the wettability of a reservoir is effectively improved. And the performance of the product is better than that of the wetting reversal agent in the comparative example, and the interface free energy can be reduced to a greater degree compared with that of the ionic wetting reversal agent containing fluorine (comparative example 2). The contact angle with water is greater than that of the same fluorine-containing polymer microemulsion wetting reversal agent (comparative example 3). Therefore, the prepared wetting reversal agent has strong wetting reversal capability, and can effectively solve the problems caused by reservoir wettability problems in the development process of oil and gas resources.
Experimental example 2: stability test
And taking a picture of the product in the example 1 in 50mL, sealing, standing and storing at room temperature for 30 days to obtain the picture of the apparent appearance of the product at different time in the figure 4. As can be seen from the figure, the product still has stable emulsibility after being placed for 30 days, no precipitate is generated, and the product has good Tyndall phenomenon, which indicates that the product can be stably stored for a long time at normal temperature and normal pressure.
Experimental example 3: application experiment for improving recovery ratio
And exploring the influence of the wetting reversal agent on the recovery ratio by adopting a visual displacement experiment.
And vacuumizing the micro glass, injecting formation water, injecting simulated oil into the model at a constant speed after the formation water is injected, and driving out the formation water to obtain the saturated oil model in the figure 4. In the experiment, formation water is firstly injected for water flooding for 3 hours, and then partially Hydrolyzed Polyacrylamide (HPAM) is injected for polymer flooding until the recovery rate is stable. For comparison, a displacement experiment was conducted with 2.0 wt.% of the binary fluoropolymer wetting reversal agent of example 1 added to HPAM under otherwise identical conditions. Finally, the recovery curves under different conditions in fig. 6 are obtained.
As can be seen in fig. 6, both have the same recovery factor in the waterflood section. However, in the HPAM displacement part, after the binary fluorine-containing polymer wetting reversal agent is added, the system can reach the displacement balance more quickly, and the ultimate recovery rate can be improved by more than 13 percent, which shows that the wetting reversal agent can obviously improve the recovery rate of crude oil.
Claims (10)
1. A preparation method of a binary fluorine-containing polymer microemulsion wetting reversal agent comprises the following steps: in the presence of perfluorooctanoic acid, emulsifying dodecafluoroheptyl methacrylate and 2- (perfluorohexyl) ethyl methacrylate monomers in water to obtain binary fluorine-containing monomer emulsion; dissolving acrylic monomers and an initiator in an organic solvent, then dripping the acrylic monomers and the initiator into binary fluorine-containing monomer emulsion, and carrying out polymerization reaction at 60-90 ℃ to obtain the polymer microemulsion wetting reversal agent.
2. The method for preparing the dual fluoropolymer microemulsion wetting inverter of claim 1, wherein the molar ratio of the dodecafluoroheptyl methacrylate to the 2- (perfluorohexyl) ethyl methacrylate monomer is 1: 0.5-2; the molar ratio of the dodecafluoroheptyl methacrylate to the 2- (perfluorohexyl) ethyl methacrylate monomer is 1: 1.
3. The method for preparing the dual fluoropolymer microemulsion wetting inverter of claim 1, wherein the molar ratio of the dodecafluoroheptyl methacrylate, the 2- (perfluorohexyl) ethyl methacrylate monomer and the acrylic monomer is 1:0.5-2: 1-4; preferably, the mole ratio of the dodecafluoroheptyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate monomer and the acrylic monomer is 1:1: 2.
4. The method of preparing the dual fluoropolymer microemulsion wetting inverter of claim 1, wherein the reacting comprises one or more of the following conditions:
a. the acrylic monomer is methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate or methacrylic acid-9-anthracene methyl ester;
b. the initiator is one of ammonium persulfate, benzoyl peroxide and azobisisobutyronitrile;
c. based on the total mole number of double bonds in the monomer, the usage amount of the perfluorooctanoic acid is 1 to 5 percent of the mole ratio, and the usage amount of the initiator is 1 to 5 percent of the mole ratio;
d. the organic solvent is selected from ethanol, N-Dimethylformamide (DMF), tetrahydrofuran or dichloromethane;
e. the volume ratio of the organic solvent to the binary fluorine-containing monomer emulsifying water is 1: (0.5 to 4); the volume ratio of the organic solvent to the water is 1: 1; preferably, the water is distilled water;
f. the proportion of the amount of the binary fluorine-containing monomer emulsifying water to the sum of the mass of the dodecafluoroheptyl methacrylate and the 2- (perfluorohexyl) ethyl methacrylate monomer is 100:15-20, and the unit mL: g or L: kg.
5. The preparation method of the binary fluorine-containing polymer microemulsion wetting reversal agent as claimed in claim 1, wherein the dropping speed of the acrylic monomer is preferably 2-3 d/s; preferably, the polymerization reaction time is 2-8 h, and more preferably 3-5 h.
6. The method for preparing the dual fluoropolymer microemulsion wetting inverter of claim 1, comprising the steps of: respectively adding 50mL of distilled water and 0.4g of perfluorooctanoic acid into a reactor, dissolving, then adding 0.01mol of dodecafluoroheptyl methacrylate and 0.01mol of 2- (perfluorohexyl) ethyl methacrylate, and ultrasonically emulsifying for 30min at normal temperature; and then 0.02mol of acrylic monomer and 0.16g (0.01mol) of initiator Azobisisobutyronitrile (AIBN) are dissolved in 50mL of N, N-Dimethylformamide (DMF), the mixture is dripped into a three-neck flask at the temperature of 60 ℃ at the speed of 2-3 d/s, and after the dripping is finished, the temperature is raised to 80 ℃ for reaction for 4 hours to obtain milky polymer microemulsion, namely the wetting reversal agent.
7. The method for preparing the binary fluorine-containing polymer microemulsion wetting reversal agent as claimed in claim 1, wherein the prepared binary fluorine-containing polymer microemulsion has a small particle size, and the particle size of the emulsion is 1-5 μm.
8. The binary fluoropolymer wetting inverter prepared according to any of claims 1-7 having the structure of formula I:
in the formula I, R is butyl, dodecyl or 9-anthracenemethyl, and n is 19-21; preferably, n is 20.
9. Use of the binary fluoropolymer microemulsion prepared according to any one of claims 1 to 7 as a wetting reversal agent in a drilling fluid.
10. Use of the binary fluoropolymer microemulsion prepared according to any one of claims 1 to 7 as a wet-inversion agent for enhanced oil and gas recovery; preferably, 1-2.5 wt.% of a binary fluoropolymer microemulsion wetting reversal agent is added to the displacement fluid for displacement.
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| CN115895629A (en) * | 2022-11-03 | 2023-04-04 | 中国石油大学(华东) | Double-lyophobic sulfonated carbon nanotube/modified graphene oxide wetting reversal agent and preparation method and application thereof |
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