CN106634923B - The nano silica and oil recovering nano-fluid of surface modification - Google Patents
The nano silica and oil recovering nano-fluid of surface modification Download PDFInfo
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- CN106634923B CN106634923B CN201610853302.2A CN201610853302A CN106634923B CN 106634923 B CN106634923 B CN 106634923B CN 201610853302 A CN201610853302 A CN 201610853302A CN 106634923 B CN106634923 B CN 106634923B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 75
- 239000012530 fluid Substances 0.000 title claims abstract description 40
- 230000004048 modification Effects 0.000 title claims abstract description 35
- 238000012986 modification Methods 0.000 title claims abstract description 35
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 claims description 4
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 claims description 4
- 235000015511 Liquidambar orientalis Nutrition 0.000 claims description 4
- 239000004870 Styrax Substances 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 3
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- VOLGAXAGEUPBDM-UHFFFAOYSA-N $l^{1}-oxidanylethane Chemical compound CC[O] VOLGAXAGEUPBDM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 60
- 239000002245 particle Substances 0.000 abstract description 38
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 33
- 238000011084 recovery Methods 0.000 abstract description 21
- 230000035699 permeability Effects 0.000 abstract description 17
- 238000012650 click reaction Methods 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000011435 rock Substances 0.000 description 17
- 238000006073 displacement reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 241000736148 Styrax Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000009096 changqing Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000004391 petroleum recovery Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a kind of nano silica of surface modification and oil recovering nano-fluids.The nano silica of surface modification, preparation method include the following steps: that 1) nano silica is reacted with hydrosulphonyl silane, obtain sulfhydrylation nano silica;2) sulfhydrylation nano silica made from step 1) and monounsaturated fatty acids is taken to carry out click-reaction to get the nano silica of monounsaturated fatty acids surface modification.Oil recovering nano-fluid: being dispersed in water to obtain dispersion liquid for the nano silica of the surface modification, adjust dispersion liquid pH value to 8 ~ 12 to get.The nanometer silicon dioxide particle of monounsaturated fatty acids surface modification of the invention can not add dispersing agent self-dispersing Yu Shuizhong.Nano-fluid preparation process of the invention is simple, dispersion is uniform, stability is good, is easy to extemporaneous preparation and large-scale application, can be improved Oil in Super-low Permeability Reservoirs recovery ratio.
Description
Technical field
The invention belongs to nano-functional materials and oil field chemical technical field, and in particular to a kind of nanometer of surface modification
Silica and oil recovering nano-fluid, the nano-fluid can be improved Oil in Super-low Permeability oil deposil erude petroleum recovery ratio.
Background technique
Petroleum has irreplaceable role as a kind of high efficient energy sources in national economy.With Chinese national economy
It increases rapidly, oil demand is continuously improved.With going deep into for oil-gas exploration and development, the ratio of Low Permeability Oil/gas resources exploration
Again will be increasing, the reserves for especially newly verifying extra-low-permeability reservoir in recent years are especially abundant, and such as middle petroleum Changqing oilfields are super
Nearly 1,000,000,000 tons of low-permeability oil deposit proved reserves, account for the 70% of Changqing oilfields petroleum proven reserve.But extra-low-permeability reservoir reservoir
Micro-nano pore throat is developed, the effective use rate of reserves is improved and faces the challenge.
In recent years, with the increase of the development of nanotechnology and oil-gas field development difficulty, nanotechnology is gradually applied to oil
Gas field development field.The nano-fluid displacement of reservoir oil is a kind of emerging oil recovery technique, it is formed in water using aqueous solution as transfer medium
Several hundred to tens even several nanometers of little particle has very big specific surface area and surface energy, greatly reduces grease
Interfacial tension, so that injection fluid during washing away hole, makes crude oil be easy to peel off into small oil droplet, and driven liquid displacement
Out.Nano-fluid drive has the characteristics that using concentration is lower, small investment, quick, oil displacement efficiency is obvious, will become has hair
" the improving water drive " of exhibition prospect improves the new technology of oil recovery factor and increasing injection.
Recovery efficiency technique is improved compared to traditional chemical displacement of reservoir oil, modified dispersions of nanoparticles has for oil field development
There is good effect of increasing production.2010, the Saudi Arabia tip A Mei company EXPEC research center utilized the fluid for carrying nanometer robot
Chemicals is sent into oil reservoir depths and carries out the displacement of reservoir oil, ASP flooding test is as a result, it has been found that the fluid has good stability and mobility.
" Energy fuels " the 1st phase " Enhanced Heavy Oil Recovery in Sandstone of volume 28 in 2014
Cores Using TiO2A Nanofluids " text reports a kind of nano titanium oxide dispersion and adopts for heavy oil raising
Yield, the results showed that recovery ratio can be increased to 80% from 49% by nano particle, and main function mechanism is wetability conversion, nanometer
Oil wet surface is converted to water-wet surface by titanium dioxide, and oil is stripped from wall surface, nano material interaction and adsorption mechanism pair
Wetability conversion plays key effect." Langmuir " " Dynamic Spreading of Nanofluids of volume 28 in 2012
On Solids. Part I:Experimental " and " Dynamic Spreading of Nanofluids on Solids
Two articles of Part II:Modeling " are reported respectively through laboratory experiment and sunykatuib analysis to dispersions of nanoparticles
The research for improving recovery ratio, since there are Brownian movements and interparticle electrostatic repulsion forces for nano particle, when particle size is enough
It is small, when quantity is enough, a stronger extension will be generated, and the electrostatic repulsion of the surface of solids exist it is uneven, thus
A wedge structure is self-assembly of in three-phase contact zone, the forward thrust that this wedge structure generates, what articulated system generated
It reduces capillary pressure, wettability reversal and mutually seeps and change the booster actions such as hysteresis effect, it can be by oil under rock surface removing
Come.
Chinese patent CN104531118A reports " a kind of preparation method of intelligent nano oil displacement agent ", by responsive to temperature type
Polymer and hydrophilic polymer, hydrophobic polymer are grafted to nanoparticle surface by covalent bond, prepare with temperature
The composite nanoparticle of sensitivity characteristic obtains the intelligent nano with temperature response characteristics then with alkali, surfactant compound
Oil displacement agent.
At present nanometer technology of reservoir sweep be mainly used for middle and high infiltration reservoir improve recovery ratio, and it is small by Oil in Super-low Permeability Reservoirs pore throat,
The limitation of the factors such as nano-fluid dispersion stabilization, there are no the nanometer streams that can be improved Oil in Super-low Permeability Reservoirs recovery ratio in the prior art
Body.
Summary of the invention
In order to solve the above-mentioned technical problem, a kind of nano silica of surface modification and containing its oil recovering with receiving
Meter Liu Ti, the nano-fluid can be improved Oil in Super-low Permeability oil deposil erude petroleum recovery ratio.
The nano-fluid is made of the nanometer silicon dioxide particle and alkaline aqueous solution of monounsaturated fatty acids surface modification.
The nano silica of monounsaturated fatty acids surface modification of the invention is successively repaired by hydrosulphonyl silane and monounsaturated fatty acids
It adorns nanometer silicon dioxide particle and is made.Monounsaturated fatty acids modification nanometer silicon dioxide particle is dispersed in water, 50 ~
At 100 DEG C, dispersion liquid pH value is adjusted to 8 ~ 12 with sodium hydroxide or potassium hydroxide solution, it is saturating that well dispersed clarification can be obtained
Bright shape nano-fluid.Monounsaturated fatty acids modifies nanometer silicon dioxide particle, and there are Brownian movements and interparticle electrostatic repulsion
Power, reduction capillary pressure that articulated system generates, wettability reversal and mutually seeps and changes the booster actions such as hysteresis effect, can will be oily
It is stripped down from rock surface, to improve Oil in Super-low Permeability oil recovery.The nano-fluid preparation process is simple, dispersion is uniform,
Stability is good, is easy to extemporaneous preparation and large-scale application.
The nano silica of surface modification provided by the invention, preparation method include the following steps:
1) nano silica is reacted with hydrosulphonyl silane, obtains sulfhydrylation nano silica;
2) sulfhydrylation nano silica made from step 1) and monounsaturated fatty acids is taken to carry out click-reaction to get list
The nano silica of unsaturated fatty acid surface modification.
Preferably, step 1) is that nano silica is taken to be scattered in organic solvent, addition hydrosulphonyl silane, at 30 ~ 80 DEG C
It is stirred to react, it is cooling, it is separated by solid-liquid separation, solid washing is dry, obtains sulfhydrylation nano silica;Wherein, the organic solvent
For the one of which or combinations thereof of methanol, ethyl alcohol, toluene or N,N-dimethylformamide.It is highly preferred that being stirred to react the time is 2
~8 h;Solid is washed 4 ~ 8 times with ethyl alcohol or N,N-dimethylformamide;24 ~ 48 h are dried in vacuo at 30 ~ 80 DEG C.
Preferably, step 2 is that the sulfhydrylation nano silica for taking step 1) to obtain is scattered in organic solvent, is added
Catalyst is added in monounsaturated fatty acids, stirring, and ultraviolet lighting reaction is separated by solid-liquid separation after completion of the reaction, and solid washing is dry
Obtain the nano silica of monounsaturated fatty acids surface modification;Wherein, the catalyst be styrax, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin isobutyl ether, dimethoxybenzoin, diphenylethan, benzophenone, 2,4 dihydroxyl benzophenone,
Michler's keton or triethylamine one of which or combinations thereof.Preferably, the mass ratio of monounsaturated fatty acids and catalyst are as follows: 1 ~ 40:
0.01~5;The ultraviolet lighting reaction time is 10 ~ 120 min;Solid is washed 4 ~ 8 times with ethyl alcohol or N,N-dimethylformamide;30~
24 ~ 48 h are dried in vacuo at 80 DEG C.
Preferably, the partial size of the nano silica is 7 ~ 15 nm, and specific surface area is 150 ~ 400 m2/g。
Preferably, the weight ratio of the nano silica, hydrosulphonyl silane and monounsaturated fatty acids are as follows: 1 ~ 10:1 ~
40:1 ~ 40(is with this ratio, it is ensured that each nanometer silicon dioxide particle is modified, so that well dispersed single insatiable hunger be made
With fatty acid modifying nanometer silicon dioxide particle).
Preferably, the hydrosulphonyl silane chemical formula is X3Si(CH2)nSH, X CH3O、CH3CH2O, Cl or Br, wherein 1≤
N≤30, n are integer;The monounsaturated fatty acids chemical formula is CH3(CH2)aHC=CH(CH2)bCOOH, wherein 1≤a≤50,
1≤b≤50, a and b are integer.
The present invention also provides a kind of oil recovering nano-fluids of nano silica containing above-mentioned surface modification:
The nano silica of the surface modification is dispersed in water to obtain dispersion liquid, adjust dispersion liquid pH value to 8 ~ 12 to get.
Preferably, the nano silica of surface modification mass percent shared in dispersion liquid be 0.001 ~
1%。
Preferably, pH is adjusted with the aqueous solution of alkali.
Preferably, dispersion liquid pH value is adjusted at 50 ~ 100 DEG C to 8 ~ 12.
Present invention has the advantage that:
The nanometer silicon dioxide particle of monounsaturated fatty acids surface modification of the invention can not add dispersing agent self-dispersing
Yu Shuizhong.
Nano-fluid preparation process of the invention is simple, dispersion is uniform, stability is good, is easy to extemporaneous preparation and answers on a large scale
With.
Nano-fluid of the invention can be improved Oil in Super-low Permeability Reservoirs oil recovery factor.
Detailed description of the invention
Fig. 1 is monounsaturated fatty acids surface finish nano silica dioxide granule preparation process schematic diagram.
Fig. 2 is monounsaturated fatty acids surface finish nano silica dioxide granule grain size distribution in nano-fluid.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be with
It better understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
As shown in Figure 1, the nano silica of monounsaturated fatty acids surface modification of the invention is by hydrosulphonyl silane and list
Unsaturated fatty acid is successively modified nanometer silicon dioxide particle and is made.Monounsaturated fatty acids surface modification of the invention is received
Rice silica is since the monounsaturated fatty acids on surface can form steric effect and electrostatic repulsion effect, so as to repair surface
The nanometer silicon dioxide particle of decorations is well dispersed in the nano-fluid.
The nano silica of surface modification of the invention is prepared via a method which:
(1) by 1 ~ 10 g partial size, 7 ~ 15 nm, 150 ~ 400 m of specific surface area2The nanometer silicon dioxide particle of/g is scattered in
In 100 ~ 1000 mL organic solvents, 1 ~ 40 g hydrosulphonyl silane is added, is stirred to react 2 ~ 8 h at 30 ~ 80 DEG C, is cooled to room temperature, from
The heart or filtering reaction product wash 24 ~ 48 h of vacuum drying at 4 ~ 8 times, 30 ~ 80 DEG C with ethyl alcohol or n,N-Dimethylformamide,
Obtain sulfhydrylation nanometer silicon dioxide particle;The organic solvent is its of methanol, ethyl alcohol, toluene or N,N-dimethylformamide
Middle one kind or combinations thereof can be such that nano silica is dispersed in wherein;
(2) it disperses above-mentioned sulfhydrylation nanometer silicon dioxide particle in 100 ~ 1000 mL organic solvents, 1 ~ 40 g is added
Monounsaturated fatty acids stirs 5 ~ 30 min, adds 0.01 ~ 5 g catalyst, 10 ~ 120 min, centrifugation are reacted under ultraviolet lighting
Or filtering reaction product, 24 ~ 48 h of vacuum drying at 4 ~ 8 times, 30 ~ 80 DEG C are washed with ethyl alcohol or n,N-Dimethylformamide, are obtained
Nanometer silicon dioxide particle is modified to monounsaturated fatty acids;
The organic solvent is methanol, ethyl alcohol, toluene or one of which of N,N-dimethylformamide or combinations thereof;It is described
Catalyst is styrax, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dimethoxybenzoin, diphenylethan, two
Benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton or one of which of triethylamine or combinations thereof.
Several embodiments are exemplified below so that invention is further explained:
Embodiment 1
By 2 g partial size, 10 nm, 200 m of specific surface area2The nanometer silicon dioxide particle of/g is scattered in 100 mL ethyl alcohol,
2 g (CH are added3CH2O)3SiCH2CH2SH is stirred to react 3 h at 60 DEG C, is cooled to room temperature, is centrifuged or filters reaction product, uses
24 h are dried in vacuo at ethanol washing 4 times, 50 DEG C, obtain sulfhydrylation nanometer silicon dioxide particle.
It disperses above-mentioned sulfhydrylation nanometer silicon dioxide particle in 100 mL ethyl alcohol, 2 g CH is added3(CH2)4HC=CH
(CH2)4COOH stirs 30 min, and 0.01 g dimethoxybenzoin is added as catalyst, reacts 20 min under ultraviolet lighting, from
The heart or filtering reaction product, are dried in vacuo 24 h at ethanol washing 4 times, 50 DEG C, obtain monounsaturated fatty acids surface modification
Nanometer silicon dioxide particle.
Embodiment 2
By 4 g partial size, 7 nm, 300 m of specific surface area2The nanometer silicon dioxide particle of/g is scattered in 200 mL N, N- diformazans
In base formamide, 4 g (CH are added3O)3SiCH2CH2SH is stirred to react 3 h at 60 DEG C, is cooled to room temperature, and is centrifuged or filters and is anti-
Product is answered, 24 h is dried in vacuo at ethanol washing 4 times, 50 DEG C, obtains sulfhydrylation nanometer silicon dioxide particle.
It disperses above-mentioned sulfhydrylation nanometer silicon dioxide particle in 200 mL n,N-Dimethylformamide, 2 g is added
CH3(CH2)10HC=CH(CH2)10COOH stirs 30 min, and 0.01 g diphenylethan is added as catalyst, under ultraviolet lighting
20 min, centrifugation or filtering reaction product are reacted, 24 h is dried in vacuo at ethanol washing 4 times, 50 DEG C, obtains single unsaturated lipid
Fat acid modifies nanometer silicon dioxide particle.
Embodiment 3
By 2 g partial size, 10 nm, 250 m of specific surface area2The nanometer silicon dioxide particle of/g is scattered in 200 mL N, N- bis-
In methylformamide, 2 g Cl are added3SiCH2CH2SH is stirred to react 3 h at 60 DEG C, is cooled to room temperature, is centrifuged or filters reaction
Product is dried in vacuo 24 h at ethanol washing 4 times, 50 DEG C, obtains sulfhydrylation nanometer silicon dioxide particle.
It disperses above-mentioned sulfhydrylation nanometer silicon dioxide particle in 200 mL n,N-Dimethylformamide, 2 g is added
CH3(CH2)15HC=CH(CH2)15COOH stirs 20 min, and 0.01 g triethylamine is added as catalyst, reacts under ultraviolet lighting
30 min, centrifugation or filtering reaction product, are dried in vacuo 24 h at ethanol washing 4 times, 50 DEG C, obtain monounsaturated fatty acids
Modify nanometer silicon dioxide particle.
Embodiment 4
Monounsaturated fatty acids surface finish nano silica dioxide granule made from 0.01 g embodiment 1 is weighed to be scattered in
It in 99.99 g water, is stirred under the conditions of 80 DEG C, dispersion liquid pH value is adjusted to 10, until list is not with 1 mol/L sodium hydroxide solution
Saturated fatty acid modification nanometer silicon dioxide particle clear shape is evenly dispersed, and the nano-fluid can be obtained.
Embodiment 5
It weighs the modification nanometer silicon dioxide particle of monounsaturated fatty acids made from 0.1 g embodiment 2 and is scattered in 99.9 g
It in water, is stirred under the conditions of 100 DEG C, dispersion liquid pH value is adjusted to 9, until single unsaturated lipid with 1 mol/L potassium hydroxide solution
Fat acid modification nanometer silicon dioxide particle clear shape is evenly dispersed, and the nano-fluid can be obtained.
Embodiment 6
It weighs the modification nanometer silicon dioxide particle of monounsaturated fatty acids made from 0.1 g embodiment 3 and is scattered in 99.9 g
It in water, is stirred under the conditions of 100 DEG C, dispersion liquid pH value is adjusted to 9, until single unsaturated lipid with 1 mol/L potassium hydroxide solution
Fat acid modification nanometer silicon dioxide particle clear shape is evenly dispersed, and the nano-fluid can be obtained.
Embodiment 7
Using nanometer silicon dioxide particle particle diameter distribution in laser particle size analyzer measurement nano-fluid, as shown in Figure 2: real
In the nano-fluid for applying example 4 ~ 6,7 ~ 25 nm of nanometer silicon dioxide particle particle size distribution range.
Embodiment 8
Taking a block length is 6 cm, diameter is 2.5 cm Oil in Super-low Permeability natural cores, cleans rock core, is dried in vacuo 24 at 90 DEG C
After h, gas permeability is 2.3 mD, saturation simulation oil (viscosity 3 mPas, 25 DEG C), after 24 h of aging, record saturation oil mass,
With the speed of 0.1 mL/min with 3% potassium chloride brine displacements rock core until outlet end is not fuel-displaced, record cumulative oil production, meter
Calculating primary recovery rate is 35.69%;Nano-fluid made from 0.3 PV embodiment 4 is injected to rock core with the speed of 0.1 mL/min
Slug records oil production;It is not fuel-displaced that secondary water is driven to rock core outlet end, records cumulative oil production, calculates secondary waterflood recovery efficiency factor
It is 45.78%, nano-fluid improves recovery ratio 10.09%.
Embodiment 9
Taking a block length is 6 cm, diameter is 2.5 cm Oil in Super-low Permeability natural cores, cleans rock core, is dried in vacuo 24 at 90 DEG C
After h, gas permeability is 1.9 mD, saturation simulation oil (viscosity 3 mPas, 25 DEG C), after 24 h of aging, record saturation oil mass,
With the speed of 0.1 mL/min with 3% potassium chloride brine displacements rock core until outlet end is not fuel-displaced, record cumulative oil production, meter
Calculating primary recovery rate is 32.18%;Nano-fluid made from 0.3 PV embodiment 5 is injected to rock core with the speed of 0.1 mL/min
Slug records oil production;It is not fuel-displaced that secondary water is driven to rock core outlet end, records cumulative oil production, calculates secondary waterflood recovery efficiency factor
It is 45.29%, nano-fluid improves recovery ratio 13.11%.
Embodiment 10
Taking a block length is 6 cm, diameter is 2.5 cm Oil in Super-low Permeability natural cores, cleans rock core, is dried in vacuo 24 at 90 DEG C
After h, gas permeability is 2.5 mD, saturation simulation oil (viscosity 3 mPas, 25 DEG C), after 24 h of aging, record saturation oil mass,
With the speed of 0.1 mL/min with 3% potassium chloride brine displacements rock core until outlet end is not fuel-displaced, record cumulative oil production, meter
Calculating primary recovery rate is 34.26%;Nano-fluid made from 0.3 PV embodiment 6 is injected to rock core with the speed of 0.1 mL/min
Slug records oil production;It is not fuel-displaced that secondary water is driven to rock core outlet end, records cumulative oil production, calculates secondary waterflood recovery efficiency factor
It is 44.29%, nano-fluid improves recovery ratio 10.03%.
Embodiment 11
Taking 5 block lengths is 6 cm, diameter is the similar Oil in Super-low Permeability natural core of 2.5 cm permeabilities, cleaning rock core, 90 DEG C
After 24 h of lower vacuum drying, gas permeability is divided into 3.3 mD, 3.1 mD, 3.4 mD, 2.9 mD and 3.7 mD, saturation simulation oil
(viscosity 3 mPas, 25 DEG C), after 24 h of aging, record saturation oil mass;Above-mentioned 5 blocks of rock cores are put into imbibition bottle, are soaked respectively
Bubble is concentration is 3wt% potassium chloride salt water, concentration is 0.1wt% neopelex surfactant solution, embodiment 4
In the nano-fluid of nano-fluid, the nano-fluid of embodiment 5 and embodiment 6,5 blocks of rock cores are recorded in different imbibition liquid at any time
Between oil drain quantity record final oil drain quantity until oil drain quantity no longer changes, the recovery ratio for calculating separately 5 kinds of imbibition liquid is respectively
13.2%, 18.6%, 30.1%, 30.0% and 29.8%, nano-fluid improves 10% or more compared to surfactant solution.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (7)
1. a kind of nano silica of surface modification, which is characterized in that preparation method includes the following steps:
1) it takes nano silica to be scattered in organic solvent, hydrosulphonyl silane is added, is stirred to react at 30 ~ 80 DEG C, cooling, solid-liquid
Separation, solid washing is dry, obtains sulfhydrylation nano silica;Wherein, the organic solvent be methanol, ethyl alcohol, toluene or
One of which of N,N-dimethylformamide or combinations thereof;
2) the sulfhydrylation nano silica for taking step 1) to obtain is scattered in organic solvent, and monounsaturated fatty acids is added, stirs
It mixes, catalyst is added, ultraviolet lighting reaction is separated by solid-liquid separation after completion of the reaction, and solid washing is dried to obtain monounsaturated fatty acids
The nano silica of surface modification;Wherein, the catalyst is styrax, benzoin ethyl ether, benzoin isopropyl ether, styrax
Butyl ether, dimethoxybenzoin, diphenylethan, benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton or triethylamine wherein one
Kind or combinations thereof;
The hydrosulphonyl silane chemical formula is X3Si(CH2)nSH, X CH3O、CH3CH2O, Cl or Br, wherein 1≤n≤30, n are whole
Number;The monounsaturated fatty acids chemical formula is CH3(CH2)aHC=CH(CH2)bCOOH, wherein 1≤a≤15,1≤b≤15, a
It is integer and equal with b.
2. the nano silica of surface modification according to claim 1, which is characterized in that the nano silica
Partial size is 7 ~ 15 nm, and specific surface area is 150 ~ 400 m2/g。
3. the nano silica of surface modification according to claim 1, which is characterized in that the nano silica,
The weight ratio of hydrosulphonyl silane and monounsaturated fatty acids are as follows: 1 ~ 10:1 ~ 40:1 ~ 40.
4. the oil recovering of nano silica of the one kind containing the described in any item surface modifications of claim 1 ~ 3 is flowed with nanometer
Body, which is characterized in that be dispersed in water to obtain dispersion liquid for the nano silica of the surface modification, adjust dispersion liquid pH value
To 8 ~ 12 to get.
5. oil recovering nano-fluid according to claim 4, which is characterized in that the nano-silica of the surface modification
SiClx mass percent shared in dispersion liquid is 0.001 ~ 1%.
6. oil recovering nano-fluid according to claim 4, which is characterized in that adjust pH with the aqueous solution of alkali.
7. oil recovering nano-fluid according to claim 4, which is characterized in that adjust dispersion liquid at 50 ~ 100 DEG C
PH value is to 8 ~ 12.
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CN112745987B (en) * | 2019-10-31 | 2022-07-08 | 中国石油化工股份有限公司 | Saturated fatty acid crystallization aid and preparation method thereof |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101735787A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Nano material-based water-based oil field injection agent and preparation method thereof |
CN102964881A (en) * | 2012-12-07 | 2013-03-13 | 北京彤程创展科技有限公司 | Amino/mercapto silane modified silica and preparation method thereof |
CN103739794A (en) * | 2013-12-24 | 2014-04-23 | 太原理工大学 | Preparation method of hyperbranched polymer-modified nano-silicon dioxide hybrid material |
CN103937478A (en) * | 2014-04-16 | 2014-07-23 | 东北石油大学 | Preparation method of nanofluid for improving oil recovery |
CN105001846A (en) * | 2015-07-01 | 2015-10-28 | 中国石油大学(华东) | Nano liquid for decompression and augmented injection of tight oil water-flooding and preparation method and application thereof |
-
2016
- 2016-09-27 CN CN201610853302.2A patent/CN106634923B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101735787A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Nano material-based water-based oil field injection agent and preparation method thereof |
CN102964881A (en) * | 2012-12-07 | 2013-03-13 | 北京彤程创展科技有限公司 | Amino/mercapto silane modified silica and preparation method thereof |
CN103739794A (en) * | 2013-12-24 | 2014-04-23 | 太原理工大学 | Preparation method of hyperbranched polymer-modified nano-silicon dioxide hybrid material |
CN103937478A (en) * | 2014-04-16 | 2014-07-23 | 东北石油大学 | Preparation method of nanofluid for improving oil recovery |
CN105001846A (en) * | 2015-07-01 | 2015-10-28 | 中国石油大学(华东) | Nano liquid for decompression and augmented injection of tight oil water-flooding and preparation method and application thereof |
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