CN109456744A - A kind of nanometer wetting agent and its preparation method and application based on nonionic surfactant modification - Google Patents
A kind of nanometer wetting agent and its preparation method and application based on nonionic surfactant modification Download PDFInfo
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- CN109456744A CN109456744A CN201710797557.6A CN201710797557A CN109456744A CN 109456744 A CN109456744 A CN 109456744A CN 201710797557 A CN201710797557 A CN 201710797557A CN 109456744 A CN109456744 A CN 109456744A
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- 239000000080 wetting agent Substances 0.000 title claims abstract description 50
- 239000002736 nonionic surfactant Substances 0.000 title claims abstract description 23
- 230000004048 modification Effects 0.000 title claims abstract description 18
- 238000012986 modification Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 amino silicane Chemical compound 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- ZHUWIYQJHBMTCY-UHFFFAOYSA-N 3-[ethoxy(2,2,2-triethoxyethoxy)silyl]propan-1-amine Chemical compound NCCC[SiH](OCC(OCC)(OCC)OCC)OCC ZHUWIYQJHBMTCY-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- GTXWPZRNXZAPGM-UHFFFAOYSA-N NCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCC[SiH](OC(OCC)(OCC)OCC)OC GTXWPZRNXZAPGM-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000012530 fluid Substances 0.000 description 7
- 238000009736 wetting Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
Classifications
-
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—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 surfactants
-
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a kind of nanometer wetting agents and its preparation method and application based on nonionic surfactant modification.This nanometer of wetting agent is the nano silica aggregate for being grafted with nonionic surfactant, and the nano silica aggregate is coupling agent modified nano silica aggregate.The described method includes: preparing coupling agent modified nanometer aggregate；Link surfactant；Separating-purifying.Nanometer wetting agent of the invention is the link by surfactant in the nanometer aggregate surface of coupling modifier, make its dilute aqueous solution that there is the ability for improving reservoir wettability, can make the performance of the improvement reservoir wettability of the aqueous solution of surface finish nano wetting agent of the invention adjustable by using different surfactant and concentration.Nanometer wetting agent of the invention can be configured to surfactant displacement liquid, be used for waterflooding reservoir, and provided wetting agent can be effectively improved reservoir wettability, to play the effect for improving recovery ratio.
Description
Technical field
The invention belongs to field of oil development, more particularly, to a kind of receiving based on nonionic surfactant modification
Rice wetting agent and its preparation method and application.
Background technique
The medium to high permeable rate old filed of China's major part waterflooding extraction has entered High water cut, " the double height " of high recovery percent of reserves is opened
The hair stage.Under China's background increasing to oil demand, increasing is particularly important the exploitation of remaining oil.It is general next
It says, remaining oil can be divided into two kinds of fundamental types: macroscopical and microcosmic.Macroscopical remaining oil, which refers to, not to be arrived by water-driven still
Reserves, and the reserves in zone of stagnation and lithologic lens.Microscopic remaining oil refers to be arrived by water-driven, but Analysis of Water-drive Energy is still
It is not enough to be produced, is in remanent state, in adsorption-like and fetter shape such as the petroleum of filminess, and on pore surface
Petroleum, such as the residual oil that capillary force fetters, it, which remains in, injects the area that fluid passes through, and the quilt completely in tiny hole
Capillary force constraint etc..This kind of oil distribution is microcosmic, and mostly discontinuous.
Microscopic remaining oil occupies larger proportion in current petroleum reserves, how to improve its recovery percent of reserves, becomes pendulum in oil
Major issue in face of the developer of field.
Reservoir wettability is a key factor for controlling formation fluid regional location, distribution and flow behavior.Storage
The wetability of layer pore surface is to capillary pressure, remaining oil-containing or water saturation, relative permeability, electrical property feature and water filling
Development features have the influence of essence.Studies have shown that water-wet stratum is changed to generally make oleic permeability after oil wet formation
15~85% are reduced, averagely reduces by 40%, the percentage of permeability reduction is bigger in tight rock.Therefore reservoir wettability
Variation it is in close relations related to oil recovery factor.Therefore, by changing reservoir wettability, adopting for the type crude oil can be improved
Degree out.
For reservoir wettability, researcher is adjusted by changing injection fluid pH value, surfactant and phase permeability
The means such as agent realize the change to reservoir wettability, to improve crude oil recovery percent of reserves.
Nano particle is due to unique small-size effect itself and skin effect, in the exploration and development process of petroleum industry
In more and more paid attention to.As report by wettability modification improves recovery ratio, water injection well increasing injection, prevents stratum
Injure and prevent scale deposition etc..
104449631 B of Chinese patent CN (strong gas wetability nano silica Xie Shui lock agent, preparation method and rock
The method of stone moistened surface reversion) a kind of gas wetting nano silica Xie Shui lock agent is reported, the system is by modified Nano two
Silica, emulsifier op-10, lauryl sodium sulfate, ethyl alcohol and water compound to be formed, and show good super-hydrophobic oleophobic property
Energy.
Document (Jin Jiafeng air humidity Nano-meter SiO_22Particle to rock core wettability reversal and solution water lock machine reason [J] drilling fluid with
Completion fluid, 2015,32 (6): 5-11), use ethyl orthosilicate and ammonium hydroxide to prepare nano silica for raw material, and by from
The absorption of subtype fluorocarbon surfactant is modified, and the nano particle wetting agent for having air humidity reverse function is prepared.
It is prepared in conclusion the nano silica wetting agent of report is modified using directly compounding or absorption, to oil
It hides in injection process, similar products inevitably will lead to chromatographic isolation or unstable quality phenomenon occurs, in addition, report
Nanometer wetting agent technology is directed to gas reservoir solution liquid lock, there is no for the nanometer wetting agent technology for changing reservoir wettability.Therefore, existing
Some nanometer wetting agents still have biggish improvement to promote leeway in technology and performance.And the nanometer wetting agent of function admirable is ground
Hair all undoubtedly can generate positive effect, and the economy and environmental benefit that finally show to existing waterflooding reservoir, all
It will have an important influence on.
Reservoir wettability is a key factor for controlling formation fluid regional location, distribution and flow behavior, special
Oil recovery factor is not improved by changing reservoir wettability there are in the case where a large amount of remaining oils in current waterflooding reservoir,
It is of great significance.
Summary of the invention
Existing nanometer wetting agent there are aiming at the problem that, it is living based on non-ionic surface that the purpose of the present invention is to provide one kind
Property agent modification nanometer wetting agent and its preparation method and application, by grafting phase after nano-silica surface coupling modifier
Surface active groups are answered, the nanometer wetting agent of stable structure is prepared, can effectively improve reservoir wettability, finally play and mention
The effect of high recovery rate.
To achieve the goals above, the first aspect of the present invention provides a kind of receiving based on nonionic surfactant modification
Rice wetting agent, this nanometer of wetting agent is the nano silica aggregate for being grafted with nonionic surfactant, the nano-silica
SiClx aggregate is coupling agent modified nano silica aggregate.
A preferred embodiment according to the present invention, the particle size of the nano silica aggregate are 10-
10000nm, preferably 10-100nm.
A preferred embodiment according to the present invention, the coupling agent are amino silicane coupling agent, preferably include γ-ammonia
Propyl-triethoxysilicane, γ-aminopropyltrimethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane,
N- β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane and γ-divinyl triammonium propyl
At least one of methyl dimethoxysilane.
A preferred embodiment according to the present invention, the nonionic surfactant include polyoxyethylene-type nonionic
Surfactant and/or polyol-based non-ionic surfactant；
The polyoxyethylene non-ionic surfactant is preferably alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxy second
At least one of alkene ether, polyoxyethylene carboxylate, fatty acid methyl ester ethoxylate；
The polyol-based non-ionic surfactant is preferably anhydrous sorbitol ester type non-ionic surfactant and/or alkyl
Alkylolamides type non-ionic surfactant.
The molar ratio of a preferred embodiment according to the present invention, anionic surfactant and coupling agent is 1:0.6-
2；The molar ratio of nanometer aggregate and coupling agent is 1:3-5.
The second aspect of the present invention provides the preparation method of above-mentioned nanometer wetting agent, method includes the following steps:
Step 1: preparing coupling agent modified nanometer aggregate
Under conditions of inert gas shielding and stirring, by washing to neutral nanometer aggregate, coupling agent and organic solvent
Aqueous solution contact and react, obtain coupling agent modified nanometer aggregate solution；
Step 2: link surfactant
Under conditions of inert gas shielding and stirring, by the coupling agent modified nanometer aggregate solution and nonionic table
Face active agent simultaneously reacts, and obtains the nanometer wetting agent mixed liquor of surface modification；
Step 3: separating-purifying
The nanometer wetting agent mixed liquor of the surface modification is centrifuged, the nanometer wetting of surface modification is obtained
Agent.
A preferred embodiment according to the present invention, the weight of the aqueous solution of nanometer aggregate and organic solvent in step 1
Than for 1:10-30；The organic solvent includes ethyl alcohol and/or isopropanol.When the organic solvent include more than above two it is molten
When agent, it can be mixed with arbitrary proportion.The aqueous solution of the organic solvent is preferably organic solvent and deionized water according to volume
The solution being formulated than the ratio for 1:1.
In the present invention, the reaction condition of step 1 includes: that temperature is 50-80 DEG C, time 1-2h；The reaction condition of step 2
Include: temperature be 50-80 DEG C, time 2-4h.
Heretofore described method further include: after mixing nanometer aggregate with the aqueous solution of organic solvent, stir 20-
30min, then ultrasonic vibration 20-30min, is uniformly mixed the two.Wherein, it is highly preferred that the revolving speed of stirring is 400-500
Turn/min.
In the preparation process in accordance with the present invention, the cleaning solution and washing times washed to lower part nano material can be by this
Skilled person carries out conventional selection and regulation.Preferably, successively surface is repaired with dehydrated alcohol and deionized water
Lower part nano material after decorations magnetic Nano material mixed liquor is centrifuged respectively is washed three times, be then dried in vacuo (such as
80 DEG C), obtain the surface finish nano wetting agent.
The third aspect of the present invention provides the wetting of nanometer made from the nanometer wetting agent and/or the preparation method
Agent is improving the application in oil recovery rate.
Beneficial effects of the present invention:
1, nanometer wetting agent of the invention is to be made by surfactant in the link of the nanometer aggregate surface of coupling modifier
Its dilute aqueous solution has the ability for improving reservoir wettability, can make the present invention by using different surfactant and concentration
Surface finish nano wetting agent aqueous solution improvement reservoir wettability performance it is adjustable.
2, nanometer wetting agent of the invention can be configured to surfactant displacement liquid.The displacing fluid is of the invention receives
The aqueous solution of rice wetting agent can be nanometer wetting agent-aqueous dispersion of mass concentration 0.2-1%, be used for filling the water
Oil reservoir is developed, provided wetting agent can be effectively improved reservoir wettability, to play the effect for improving recovery ratio.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.Phase
Instead, these embodiments are provided so that the present invention is more thorough and complete, and can be by the scope of the present invention completely
It is communicated to those skilled in the art.
Embodiment 1:
(1) the earth silicon material 5g of 50nm is taken, deionized water is spare after washing to neutrality.
(2) 100mL ethanol water (volume ratio of ethyl alcohol and deionized water is 1:1) is packed into beaker, it then will be quasi-
The silica got ready is put into ultrasonator in being added to beaker, sonic oscillation 30min.It is transferred into three necks again
It in flask, is put on the magnetic stirring apparatus with water bath with thermostatic control, leads to nitrogen protection, add under the conditions of being stirred at room temperature into three-necked bottle
Enter the gamma-aminopropyl-triethoxy-silane of 18.25g, is warming up to 70 DEG C and isothermal reaction 2h under continuous stirring, obtains surface chain
Connect the nano silica mixed liquor of coupling agent.
(3) then at 70 DEG C and under conditions of stirring to the magnetic Nano titanium dioxide for holding the surface and linking coupling agent
The NP-10 (nonylphenol polyoxyethylene ether averagely contains 10 polyethoxy chains) of 11.65g is added in the three-necked bottle of silicon mixed liquor,
Lower isothermal reaction 4h is stirred, the nano silica mixed liquor of surface modification is obtained.
(4) the surface finish nano wetting agent mixed liquor is transferred in centrifugal bottle and is centrifuged, it is clear to discard top
Liquid, after lower part nano material is successively respectively washed three times with dehydrated alcohol and deionized water, then 80 DEG C of vacuum drying, obtain institute
State surface finish nano wetting agent NWND-1.
Embodiment 2:
(1) the earth silicon material 10g of 80nm is taken, deionized water is spare after washing to neutrality.
(2) 300mL ethanol water (ethyl alcohol is 1:1 with water volume ratio) is packed into beaker, then by ready two
Silica is put into ultrasonator in being added to beaker, sonic oscillation 30min.It is transferred into three-neck flask, puts again
Onto the magnetic stirring apparatus with water bath with thermostatic control, leads to nitrogen protection, 26.75g is added under the conditions of being stirred at room temperature into three-necked bottle
γ-aminopropyltrimethoxysilane, be warming up to 70 DEG C and isothermal reaction 2h under continuous stirring, obtain surface link coupling agent
Nano silica mixed liquor.
(3) to the nano silica mixed liquor for holding the surface link coupling agent at 70 DEG C and under conditions of stirring
Three-necked bottle in be added 12.50g paregal O (alkyl polyoxyethylene ether), isothermal reaction 4h, obtains surface modification under stiring
Nano silica mixed liquor.
(4) the surface finish nano wetting agent mixed liquor is transferred in centrifugal bottle and is centrifuged, it is clear to discard top
Liquid, after lower part nano material is successively respectively washed three times with dehydrated alcohol and deionized water, then 80 DEG C of vacuum drying, obtain institute
State surface finish nano wetting agent NWND-2.
Embodiment 3:
(1) the earth silicon material 5g of 50nm is taken, deionized water is spare after washing to neutrality.
(2) 300mL ethanol water (ethyl alcohol is 1:1 with water volume ratio) is packed into beaker, then by ready two
Silica is put into ultrasonator in being added to beaker, sonic oscillation 30min.It is transferred into three-neck flask, puts again
Onto the magnetic stirring apparatus with water bath with thermostatic control, leads to nitrogen protection, 17.25g is added under the conditions of being stirred at room temperature into three-necked bottle
γ-aminopropyltriethoxy diethoxy silane, be warming up to 70 DEG C and isothermal reaction 2h under continuous stirring, it is even to obtain surface link
Join the nano silica mixed liquor of agent.
(3) to the nano silica mixed liquor for holding the surface link coupling agent at 70 DEG C and under conditions of stirring
Three-necked bottle in the TX-10 (octyl phenol polyoxyethylene ether, averagely contain 10 polyethoxy chains) of 20.25g is added, it is permanent under stiring
Temperature reaction 4h, obtains surface finish nano silica mixed solution.
(4) the surface finish nano wetting agent mixed liquor is transferred in centrifugal bottle and is centrifuged, it is clear to discard top
Liquid, after lower part nano material is successively respectively washed three times with dehydrated alcohol and deionized water, then 80 DEG C of vacuum drying, obtain institute
State the nanometer wetting agent NWSD-3 of surface modification.
Test case 1:
The nanometer wetting agent-of mass concentration 0.5% is respectively configured using nanometer wetting agent sample obtained by embodiment 1-3
Then aqueous dispersion carries out surface tension test to it.
Nanometer displacement agent-aqueous dispersion preparation method of the mass concentration 0.3% is the following steps are included: sample is claimed
It takes required amount in beaker, the desired amount of water is then added, be put into magnetic stir bar stirring (200 revs/min of revolving speed) 30min
Afterwards, beaker is moved into ultrasonator, sonic oscillation 30min obtains this nanometer of wetting agent-aqueous dispersion.
Using the K100 type surface and interface tension measuring device of German KRUSS company carry out to above-mentioned NWND-1, NWND-2,
Nanometer wetting agent-aqueous dispersion of the mass concentration 0.3% of NWND-3 configuration carries out surface tension performance test, the results are shown in Table
1 (room temperature condition).
The surface tension (room temperature condition) of 1 nanometer displacement agent of table
As can be seen from Table 1, nanometer wetting agent made from embodiment 1-3 has lower surface tension.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of nanometer wetting agent based on nonionic surfactant modification, which is characterized in that this nanometer of wetting agent is grafting
There is the nano silica aggregate of nonionic surfactant, the nano silica aggregate is coupling agent modified nanometer two
Silica aggregate.
2. according to claim 1 nanometer of wetting agent, wherein the particle size of the nano silica aggregate is 10-
10000nm, preferably 10-100nm.
3. according to claim 1 nanometer of wetting agent, wherein the coupling agent is amino silicane coupling agent, is preferably included
Gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxy
Silane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane and γ-divinyl three
At least one of aminopropyltriethoxy dimethoxysilane.
4. according to claim 1 nanometer of wetting agent, wherein the nonionic surfactant includes that polyoxyethylene-type is non-
Ionic surface active agent and/or polyol-based non-ionic surfactant；
The polyoxyethylene non-ionic surfactant is preferably alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene
At least one of ether, polyoxyethylene carboxylate, fatty acid methyl ester ethoxylate；
The polyol-based non-ionic surfactant is preferably anhydrous sorbitol ester type non-ionic surfactant and/or alkylol acyl
Amine type non-ionic surfactant.
5. according to claim 1 nanometer of wetting agent, wherein the molar ratio of nonionic surfactant and coupling agent is 1:
0.6-2；The molar ratio of nanometer aggregate and coupling agent is 1:3-5.
6. the preparation method of nanometer wetting agent described in any one of claim 1-5, which is characterized in that this method include with
Lower step:
Step 1: preparing coupling agent modified nanometer aggregate
Under conditions of inert gas shielding and stirring, by washing to neutral nanometer aggregate, the water of coupling agent and organic solvent
Solution is contacted and is reacted, and obtains coupling agent modified nanometer aggregate solution；
Step 2: link surfactant
It is under conditions of inert gas shielding and stirring, the coupling agent modified nanometer aggregate solution and non-ionic surface is living
Property agent is contacted and is reacted, and obtains the nanometer wetting agent mixed liquor of surface modification；
Step 3: separating-purifying
The nanometer wetting agent mixed liquor of the surface modification is centrifuged, the nanometer wetting agent of surface modification is obtained.
7. preparation method according to claim 6, wherein the weight of the aqueous solution of nanometer aggregate and organic solvent in step 1
Amount is than being 1:10-30；The organic solvent includes ethyl alcohol and/or isopropanol.
8. preparation method according to claim 6, wherein the reaction condition of step 1 includes: that temperature is 50-80 DEG C, the time
For 1-2h；The reaction condition of step 2 includes: that temperature is 50-80 DEG C, time 2-4h.
9. preparation method according to claim 6, wherein this method further include: by the water of nanometer aggregate and organic solvent
After solution mixing, 20-30min is stirred, then ultrasonic vibration 20-30min, is uniformly mixed the two.
10. described in any one of nanometer wetting agent and/or claim 6-9 described in any one of claim 1-5
Nanometer wetting agent made from preparation method is improving the application in oil recovery rate.
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