CN116375756A - Preparation and application of anion type nano silicon dioxide hydrosol - Google Patents
Preparation and application of anion type nano silicon dioxide hydrosol Download PDFInfo
- Publication number
- CN116375756A CN116375756A CN202111652333.9A CN202111652333A CN116375756A CN 116375756 A CN116375756 A CN 116375756A CN 202111652333 A CN202111652333 A CN 202111652333A CN 116375756 A CN116375756 A CN 116375756A
- Authority
- CN
- China
- Prior art keywords
- silica
- hydrosol
- silicon dioxide
- anionic
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 73
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 150000001450 anions Chemical class 0.000 title description 20
- 125000000129 anionic group Chemical group 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 69
- 125000003277 amino group Chemical group 0.000 claims description 31
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 24
- 229940014800 succinic anhydride Drugs 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 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
- 239000002245 particle Substances 0.000 abstract description 39
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 description 16
- 238000012986 modification Methods 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- JGOICJFFICGNEJ-UHFFFAOYSA-M disodium;3-[dihydroxy(oxido)silyl]propanoate Chemical compound [Na+].[Na+].O[Si](O)([O-])CCC([O-])=O JGOICJFFICGNEJ-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008131 herbal destillate Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- MLUAJGRFXXHMQY-UHFFFAOYSA-N 2-cyanoethylsilicon Chemical compound [Si]CCC#N MLUAJGRFXXHMQY-UHFFFAOYSA-N 0.000 description 1
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 108090000623 proteins and genes Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- JIOGKDWMNMIDEY-UHFFFAOYSA-N triethoxy-(2-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1[Si](OCC)(OCC)OCC JIOGKDWMNMIDEY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
-
- 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
-
- 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
- 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
- C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
-
- 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)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to preparation and application of anionic nano silicon dioxide hydrosol. Wherein the structural formula of the anionic nano silicon dioxide is shown as the formula (1):
the nano silicon dioxide particles with the structure have great application potential in the field of nano materials. The preparation method provided by the invention is simple and easy to operate, the reaction conditions are mild and easy to control, the reaction solvent is water, and the green chemical idea is met.
Description
Technical Field
The invention belongs to the field of nano material preparation technology and oilfield application, and particularly relates to preparation of anionic nano silicon dioxide hydrosol and application of the anionic nano silicon dioxide hydrosol in the fields of scale prevention and oilfield tertiary oil recovery.
Background
The nano structure based on the silica nano particles has wide application in the fields of optoelectronic devices, MEMS devices, photonic crystals, chemical/biological sensors and the like. Various techniques such as electrostatic assembly, colloidal epitaxy, self-assembly by convection, physical adsorption to the surface Zhang Lijie, applied electric fields, etc. have been used to guide the assembly of nanoparticle surfaces, and in recent years covalent interactions have been used to bind nanoparticles to some organic molecules to produce functionalized nanoparticles, which require screening of the nanoparticles and organic molecules to provide the assembled functional nanoparticles with reactive groups, such as amino groups and genes, that are of interest for their better activity. Among them, the surface modification method is a common method for obtaining active groups on the surface of the nano silica particles, and most of the current surface modification documents are based on modification of the nano silica particles by a silane coupling agent so as to graft organic functional groups such as amino groups, vinyl groups, pyridine and the like on the silicon surface, wherein the amino groups are greatly concerned due to wide application in biomedicine, but the documents on carboxylic acid functionalized nano silica particles have relatively few reports, and in fact, the carboxylic acid functionalized nano silica has quite potential, for example, has wide application prospects in the fields of biomedicine, fingerprint manifestation, surfactants, enzyme immobilization carriers, scale prevention, tertiary oil recovery in oil fields and the like.
The silica has the advantages of easily available raw materials and low cost, and the surface of the silica particles is rich in a large amount of hydroxyl groups, so that the silica particles have strong hydrophilicity, and in addition, the hydroxyl groups on the surfaces of the silica nanoparticles are easy to interact with silanol groups in the hydrolyzed organosilane coupling agent, so that different types of functional groups are grafted on the surfaces of the silica through chemical modification, and the silica is an ideal raw material for preparing the anionic nano silica. The following methods are generally used to prepare carboxylic acid functionalized nanosilica particles: cyanoethyl silane (TCES), a polymer coating (epoxy resin, isocyanate, polybutyl succinate, polypyrrole), glutaric anhydride or succinic anhydride are selected as the carboxylic acid source of the silicon surface, and then carboxylated silicon dioxide particles are obtained by different methods. For example, in the organic phase, to
The relatively monodisperse silica nanoparticle prepared by the method is used as a raw material, aminopropyl triethoxysilane (APTES) is used as a modifier, amino groups are introduced to the surface of silicon through silanization, then the aminated silica is added into DMF solution of succinic anhydride, and the amino groups on the surface of the silicon can enable the succinic anhydride to open a ring to form carboxyl groups, so that the carboxylic acid functionalized silica nanoparticle is prepared (Yanqing An., journal of Colloid and Interface Science (2007), 507-513). Anionic silica nanoparticles were prepared by a simple water-based one-pot process starting from commercial amorphous silicon powder, with iminodiacetic acid (PMIDA) which is readily soluble in water and contains two carboxyl groups per molecule as the carboxylic acid source (Peter majewski, applied Surface Science 257 (2011), 9282-9286). And, mesoporous silicon chip is taken as raw material, bis-triethoxysilyl benzene (BTEB) is added to prepare mesoporous Kong Ben silicon chip, then triblock copolymer P123 and KCl are taken as auxiliary agents, carboxyethylsilanetriol sodium salt (CES) is added, and carboxylic acid functionalized mesoporous silicon dioxide nano particles are obtained through co-condensation of BTEB and CES (Hao-YIang Wu., chem. Eur. J.2013,19, 6358-6367). In addition, CTAB is used as a structural template agent, TEOS is used as a precursor under the condition of alkali catalysis, and a sol-gel method is adopted to prepare the single-componentAnd adding cyanoethyl triethoxysilane to graft-CN on the silicon surface, and hydrolyzing-CN to-COOH under acidic condition to obtain anionic silica nanoparticle. However, when the anionic nano silicon dioxide is prepared by the method, the silicon dioxide raw material is firstly prepared, and the corresponding auxiliary agent, the structural template agent and the like are needed to be added, particularly when succinic anhydride is used as a carboxylic acid source, although the succinic anhydride can be easily converted into carboxyl under the condition of not needing high temperature or adding a catalyst, an organic reagent DMF is used in the experimental process, the whole preparation is complex due to the removal process, the cost is high, and the environmental protection risk exists; meanwhile, the anionic nano silicon dioxide particles prepared by certain methods have larger particle sizes, and the problem of larger particle sizes may exist in practical application.
Disclosure of Invention
In order to at least partially solve the technical problems in the prior art, the specific embodiment of the invention provides anionic nano silicon dioxide, which has simple preparation process and low cost and accords with the green chemical concept, wherein the particle size of the anionic nano silicon dioxide particles is smaller than 100nm.
As one aspect of the present invention, an anionic nanosilicon dioxide is provided, the structure of which is schematically shown as follows:
in at least one possible embodiment, the above-mentioned anionic nanosilica is present in the form of nanoparticles.
As another aspect of the invention, an anionic nanosilica hydrosol is provided.
As a further aspect, the present invention relates to a method for preparing the above hydrosol, comprising: (1) Under the condition of water phase, a silane coupling agent containing amino groups modifies the nano silica hydrosol to obtain silica hydrosol with the amino groups grafted on the surface of the silica; (2) And (3) adding anhydride for reaction to obtain the anionic nano silicon dioxide hydrosol.
In at least one possible embodiment, the reaction temperature of step (1) is from 35 to 45 ℃.
In at least one possible embodiment, in step (1), the silane coupling agent containing an amino group is added in an amount of 4% to 10%, preferably 8% to 10% by mass of silica.
In at least one possible embodiment, the silane coupling agent containing an amino group is a silane coupling agent containing a C1-C3 alkyl chain, and specifically, for example, may be one or a combination of several of γ -aminopropyl triethoxysilane (KH 550), N- (β -aminoethyl) - γ -aminopropyl trimethoxysilane (KH 792), N- (β -aminoethyl) - γ -aminopropyl methyldimethoxysilane (KH 602), and 3-aminopropyl methyldiethoxysilane (APDES).
In at least one possible embodiment, in step (2), the anhydride may specifically be, for example, one or a combination of several of succinic anhydride (succinic anhydride), glutaric anhydride, maleic anhydride (maleic anhydride).
In at least one possible embodiment, the anhydride is used in an amount of 5 to 10% by mass of the silica.
In at least one possible embodiment, in step (1), the nanosilica hydrosol has a ph=6 to 9 and a concentration of 20 to 30%.
As a further aspect of the invention, it relates to the use of the above-mentioned anionic nano-silica hydrosol for scale control and tertiary oil recovery in oil fields.
In the preparation method of the anionic nano silicon dioxide hydrosol, amino groups grafted on the silicon surface react with succinic anhydride after the amino-containing silane coupling agent modifies the nano silicon dioxide hydrosol, so that the anionic nano silicon dioxide hydrosol is obtained.
In the preparation method of the anionic nano silicon dioxide hydrosol, commercial nano silicon dioxide hydrosol is adopted as a raw material, and the particle size of nano silicon dioxide particles is less than 100nm. Because commercial nano silicon dioxide hydrosol is used, the preparation process of preparing the nano silicon sol by using a conventional sol-gel method is simplified, and the time is saved, so that the preparation process is simpler.
Firstly, under the condition of water phase, utilizing silane coupling agent containing amino group to modify nano silicon dioxide hydrosol, grafting amino group on the silicon dioxide surface, then adding proper quantity of succinic anhydride into the amino nano silicon dioxide hydrosol, and making succinic anhydride undergo the process of ring-opening reaction between amino group and succinic anhydride so as to make nano silicon dioxide particles be converted into carboxyl group from amino group functionalization so as to obtain the anionic nano silicon dioxide hydrosol.
The modification of the nano silicon dioxide hydrosol by the silane coupling agent containing amino groups is carried out under a mild water phase condition, and a simple water-based environment is used, so that the process is simple, the cost is low, and the nano silicon dioxide hydrosol is green and nontoxic.
The invention provides a preparation method of anion type nano silicon dioxide hydrosol, which utilizes silane coupling agent containing amino group to modify nano silicon dioxide hydrosol, then uses succinic anhydride as carboxylic acid source to prepare anion type nano silicon dioxide hydrosol, wherein the modification step is carried out in water phase, no other reagent, catalyst and the like are required to be added in the preparation process, wherein the reaction between amino grafted on the surface of silicon dioxide and added succinic anhydride is the key for preparing anion type nano silicon dioxide hydrosol.
The invention provides a preparation method of anionic nano silicon dioxide hydrosol, wherein the modification step of nano silicon dioxide particles in the hydrosol and the preparation process of the anionic nano silicon dioxide particles are both carried out on the surface of one silicon dioxide particle, the modification degree of the initial amino group-containing silane coupling agent on the nano silicon dioxide hydrosol determines the conversion rate of carboxyl on the silicon surface at the later stage, and meanwhile, the grafting rate of amino groups on the silicon surface can be regulated and controlled by changing the concentration of the nano silicon dioxide hydrosol and the dosage of the amino group-containing silane coupling agent;
the invention provides a preparation method of anion nano silicon dioxide hydrosol, which adopts silane coupling agent modified nano silicon dioxide hydrosol containing amino group because the amino group is chemically stable in water phase.
The invention provides a preparation method of anion nanometer silicon dioxide hydrosol, which adopts commercialized nanometer silicon dioxide hydrosol as raw material, not only simplifies the preparation process of nanometer silicon dioxide hydrosol, but also saves time and has lower cost.
The invention provides a preparation method of anion nano silicon dioxide hydrosol, and nano silicon dioxide particles with the structure have great application potential in the field of nano materials. The preparation method provided by the invention is simple and easy to operate, the reaction conditions are mild and easy to control, the reaction solvent is water, and the green chemical idea is met.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
FIG. 1 is a schematic structural diagram of an anionic nano-silica particle prepared in example 1 of the present invention.
FIG. 2 is an infrared spectrum of the nano silica particles before and after the anion modification according to example 3 of the present invention and the nano silica particles in comparative examples 5 and 6.
FIG. 3 is a nuclear magnetic resonance carbon spectrum of nano silica particles before and after anion modification according to example 3 of the present invention.
FIG. 4 is a graph showing the particle diameter distribution of nano-silica particles before and after anion modification according to examples 1 to 4 of the present invention.
FIG. 5 is a graph showing the particle size distribution of silica nanoparticles before and after anion modification in example 5 of the present invention.
FIG. 6 is a graph showing the particle size distribution of silica nanoparticles before and after anion modification in example 6 of the present invention.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
Example 1
The invention provides a preparation method of anion nanometer silicon dioxide hydrosol, which is prepared through the following steps:
step one: 40g of a nano-silica hydrosol (SiO 2 Adding 30% of the mass fraction of the silica in the hydrosol, and pH=8) into a reaction bottle, then adding gamma-aminopropyl triethoxysilane (KH 550), controlling the addition amount to be 4% of the mass of the silica in the hydrosol, fully stirring for 4 hours in a water bath at 35 ℃, and finally standing for 3 days at room temperature to prepare the nano-silica hydrosol with amino groups grafted on the surface of the silica.
Step two: firstly, 1.2g of succinic anhydride is weighed and dissolved in 60mL of deionized water, then the solution is respectively mixed with the aminated nano silicon dioxide hydrosol in the first step, and the mixture is fully stirred at room temperature and reacts for 24 hours, so that the anionic nano silicon dioxide hydrosol with the particle size smaller than 100nm is prepared.
Example 2
The invention provides a preparation method of anion nanometer silicon dioxide hydrosol, which is prepared through the following steps:
step one: 40g of a nano-silica hydrosol (SiO 2 Adding 25% of the mass fraction of N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane (KH 602) into a reaction bottle, controlling the addition amount to be 10% of the mass of silicon dioxide in the hydrosol, fully stirring for 4h in a water bath at 40 ℃, and finally standing for 3d at room temperature to prepare the nano silicon dioxide hydrosol grafted with amino groups on the surface of the silicon dioxide.
Step two: firstly, 0.6g of succinic anhydride is weighed and dissolved in 60mL of deionized water, then the mixture is mixed with the aminated nano silicon dioxide hydrosol in the first step, and the mixture is fully stirred at room temperature and reacts for 24 hours, so that the anionic nano silicon dioxide hydrosol with the particle size smaller than 100nm is prepared.
Example 3
The invention provides a preparation method of anion nanometer silicon dioxide hydrosol, which is prepared through the following steps:
step one: 40g of a nano-silica hydrosol (SiO 2 The mass fraction of (2) is 20%, the pH=6.5), then gamma-aminopropyl triethoxysilane (KH 550) is added, the addition amount is controlled to be 8% of the mass of the silicon dioxide in the hydrosol, the mixture is fully stirred for 4 hours in a water bath at 40 ℃, and finally the mixture is placed for 3 days at room temperature, so that the nano silicon dioxide hydrosol with amino groups grafted on the surface of the silicon dioxide is prepared.
Step two: firstly, 0.7g of succinic anhydride is weighed and dissolved in 60mL of deionized water, then the mixture is mixed with the aminated nano silicon dioxide hydrosol in the first step, and the mixture is fully stirred at room temperature and reacts for 24 hours, so that the anionic nano silicon dioxide hydrosol with the particle size smaller than 100nm is prepared.
Example 4
The invention provides a preparation method of anion nanometer silicon dioxide hydrosol, which is prepared through the following steps:
step one: 40g of a nano-silica hydrosol (SiO 2 The mass fraction of (2) is 30%, the pH=7.5), then gamma-aminopropyl triethoxysilane (KH 550) is added, the addition amount is controlled to be 6% of the mass of the silicon dioxide in the hydrosol, the mixture is fully stirred for 4 hours in a water bath at 40 ℃, and finally the mixture is placed for 3 days at room temperature, so that the nano silicon dioxide hydrosol with amino groups grafted on the surface of the silicon dioxide is prepared.
Step two: firstly, 1.1g of glutaric anhydride is weighed and dissolved in 60mL of deionized water, then the solution is mixed with the aminated nano silicon dioxide hydrosol in the first step, and the mixture is fully stirred at room temperature and reacts for 24 hours, so that the anionic nano silicon dioxide hydrosol with the particle size smaller than 100nm is prepared.
In the above embodiment, the anionic nano silica hydrosol is successfully prepared, wherein the particle size of the anionic nano silica particles is smaller than 100nm, the structural schematic diagram is shown in fig. 1, and the preparation method directly takes the commercial nano silica hydrosol as a raw material, so that the preparation process is simpler, the cost is lower, and in addition, the amino is chemically stable in a water phase and is easy to react with succinic anhydride, so that the anionic nano silica hydrosol plays an important role in the preparation of the anionic nano silica hydrosol.
Example 5
To demonstrate the successful preparation of anionic nanosilica hydrosols, control experiments were performed as follows:
1.2g of succinic anhydride was weighed out and dissolved in 60mL of deionized water, and then an aqueous solution of succinic anhydride was mixed with 40g of unmodified nanosilica hydrosol (SiO 2 30% by mass, ph=8), and the mixture was stirred well at room temperature and reacted for 24 hours. The particle size distribution test results show that in addition to particle distribution between <100nm, there is also particle distribution between 100-1000 nm.
Example 6
To demonstrate the successful preparation of anionic nanosilica hydrosols, control experiments were performed as follows:
1.2g succinic anhydride was weighed and dissolved in 60mL deionized water, and then a one-pot process was used to prepare a solution of silica sol (SiO 2 The mass fraction of (2) was 30%, and an aqueous solution of 8% gamma-aminopropyl triethoxysilane (KH 550) and succinic anhydride was added thereto at ph=8, followed by stirring at room temperature and reacting for 24 hours. The particle size distribution test results show that in addition to particle distribution between <100nm, there is also particle distribution between 100-1000 nm.
Application example 1
The anionic nanosilica hydrosol obtained in example 1 was subjected to measurement of Ca at a concentration of 50mg/L according to SYT5673-2020, general technical conditions for Scale inhibitor for oilfield 2+ The scale prevention rate of calcium carbonate scale in 132mg/L aqueous solution is 97.8%.
Application example 2
The core with gas permeability of 0.8mD was saturated with kerosene at 60℃and then injected with 20 volumes of pore volume water, and the cumulative oil production was determined. The anionic nano silica hydrosol obtained in example 4 was continuously injected at a concentration of 20 times the pore volume of 0.1%, and the newly increased cumulative oil recovery was measured. And then the core is put into an oven, water is removed at a constant temperature of 100 ℃, and the weight of the removed core is measured. Pyrolysis is carried out at 400 ℃ to remove oil, and dry rock core weight is weighed. The anionic nano silicon dioxide hydrosol obtained in the example 4 is calculated to improve the oil displacement recovery ratio by 3.5 percent.
The anionic nanosilica sample synthesized in example 3 above was characterized:
(1) Infrared spectrum characterization (FTIR)
Adding a small amount of KBr into agate mortar, grinding, tabletting into transparent sheet, and respectively subjecting unmodified nano-silica (unmodified SiO) to infrared spectrometer (Bruker Tensor 27, germany) 2 ) And anionic nanosilica (SiO) 2 -COOH) sample is subjected to infrared characterization, scanning range 4000cm -1 ～400cm -1 As a control, the samples of examples 5 and 6 were also infrared characterized and the results are shown in fig. 2.
3460cm in unmodified nano-silica infrared spectrum -1 And 1642cm -1 The position is a symmetrical telescopic vibration and bending vibration absorption peak of Si-OH on the surface of silicon dioxide and physically adsorbing the-OH in water, 1112cm -1 ， 803cm -1 And 470cm -1 The positions are respectively attributed to asymmetric stretching vibration, symmetric stretching vibration and bending vibration absorption peaks of Si-O-Si. After anionic modification, in SiO 2 1557cm in the infrared spectrum of-COOH -11 And 1730cm -1 Two new absorption peaks, respectively characteristic absorption peaks of C=O in amide bond and carboxylic acid, are appeared at 2990-2830cm -1 The absorption peaks at the positions are asymmetric stretching vibration and symmetric stretching vibration peaks of C-H in KH550 and succinic anhydride, and the two are connected through an amide bond so that the characteristic absorption peaks of methylene are overlapped. Furthermore, the infrared spectrum of the control experiment showed that the characteristic peaks of silica and 2990-2830cm were excluded -1 Outside the C-H absorption peak, no characteristic absorption peak of carboxyl or amide appears.
(2) Nuclear magnetic characterization (NMR)
Using a Bruker, germany company VARIAN III MHz nuclear magnetic resonance spectrometer (NMR)) The anionic nanosilica particles (SiO) in example 3 were subjected to the following method using TMS as an internal standard 2 -COOH) sample 13 C NMR characterization, results are shown in FIG. 3.
After the modification of the anions, the modified anions, 13 a new absorption peak appears in the C NMR spectrum, the peak appearing at 185ppm is attributed to the signal peak of carbon in-COOH, and the signal peak of carbon in paraffin appears at 37ppm, since succinic anhydride and KH550 are linked by an amide bond to lengthen the alkyl chain, the signal peak at this point is-CH in both 2 -the result of the overlap. The combination of infrared spectrum proves that the anionic nano silicon dioxide hydrosol is successfully prepared.
(3) Dynamic light scattering particle size analyzer (DLS)
The size and distribution of the nano-silica particles before and after the anionic modification was analyzed by DLS (Malvern Instrument Zetasizer Nano ZS) and the results are shown in fig. 4.
After anion modification is carried out on the nano silicon dioxide hydrosol, the particle size is increased, for example, the particle size is increased from 22nm to about 30nm, the particle size distribution is narrower, and better monodispersity is presented.
Fig. 5 and 6 correspond to the particle size test results of example 5 and example 6, respectively. The samples prepared by example 5 or example 6 had more large size particles between 100-1000 nm. This is mainly because the unmodified nano-silica hydrosol cannot react with the modifier under the conditions of example 5 or example 6, and the modifier allows the unmodified nano-silica hydrosol to aggregate among particles, so that there are many large-sized particles.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (13)
1. The anionic nano silica is characterized in that the structural formula is shown as formula (1):
2. the anionic nanosilica of claim 1, wherein the anionic nanosilica is present in a nanoparticle state.
3. An anionic nano-silica hydrosol, characterized in that it comprises the anionic nano-silica according to any one of claims 1 or 2.
4. A method for preparing an anionic nanosilica hydrosol comprising: (1) Under the condition of water phase, a silane coupling agent containing amino groups modifies the nano silica hydrosol to obtain silica hydrosol with the amino groups grafted on the surface of the silica; (2) And (3) adding anhydride for reaction to obtain the anionic nano silicon dioxide hydrosol.
5. The process of claim 4, wherein the reaction temperature in step (1) is from 35℃to 45 ℃.
6. The method according to claim 4, wherein in the step (1), the silane coupling agent having an amino group is added in an amount of 4 to 10% by mass of the silica.
7. The method according to claim 6, wherein in the step (1), the silane coupling agent having an amino group is added in an amount of preferably 8 to 10% by mass of the silica.
8. The method according to claim 4, wherein in the step (1), the silane coupling agent having an amino group is a silane coupling agent having a C1-C3 alkyl chain.
9. The method of claim 8, wherein in step (1), the silane coupling agent containing an amino group is one or a combination of several of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl methyldimethoxysilane, and 3-aminopropyl methyldiethoxysilane.
10. The method of claim 4, wherein the anhydride is one or a combination of succinic anhydride, glutaric anhydride, maleic anhydride.
11. The method according to claim 10, wherein the anhydride is used in an amount of 5 to 10% by mass of silica.
12. The method of claim 4, wherein in step (1), the nano silica hydrosol has a ph=6 to 9 and a concentration of 20 to 30%.
13. Use of the anionic nano-silica hydrosol prepared by the method of any one of claims 4-13 in the fields of scale control and oilfield tertiary oil recovery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111652333.9A CN116375756A (en) | 2021-12-30 | 2021-12-30 | Preparation and application of anion type nano silicon dioxide hydrosol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111652333.9A CN116375756A (en) | 2021-12-30 | 2021-12-30 | Preparation and application of anion type nano silicon dioxide hydrosol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116375756A true CN116375756A (en) | 2023-07-04 |
Family
ID=86960204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111652333.9A Pending CN116375756A (en) | 2021-12-30 | 2021-12-30 | Preparation and application of anion type nano silicon dioxide hydrosol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116375756A (en) |
-
2021
- 2021-12-30 CN CN202111652333.9A patent/CN116375756A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rahman et al. | Synthesis of organo-functionalized nanosilica via a co-condensation modification using γ-aminopropyltriethoxysilane (APTES) | |
| US5013585A (en) | Method for the preparation of surface-modified silica particles | |
| Kotsyuda et al. | Bifunctional silica nanospheres with 3-aminopropyl and phenyl groups. Synthesis approach and prospects of their applications | |
| CA3058469A1 (en) | Brine resistant silica sol | |
| Okhrimenko et al. | Hydrolytic stability of 3-aminopropylsilane coupling agent on silica and silicate surfaces at elevated temperatures | |
| EP2556021B1 (en) | Silica particle manufacturing process | |
| CN102863823A (en) | Preparation method of modified nano silicon dioxide | |
| Barabanova et al. | Anhydride modified silica nanoparticles: Preparation and characterization | |
| Greenwood et al. | Aqueous silane modified silica sols: theory and preparation | |
| Yan et al. | Hydrophobic modification on the surface of SiO2 nanoparticle: wettability control | |
| CN102757790B (en) | Surface-modified fluorescent quantum dot/silica composite microspheres, preparation method thereof, and application thereof | |
| An et al. | A new route to synthesis of surface hydrophobic silica with long-chain alcohols in water phase | |
| Zhou et al. | Magnetic nanoparticles for the affinity adsorption of maltose binding protein (MBP) fusion enzymes | |
| Idris et al. | Investigation on particle properties and extent of functionalization of silica nanoparticles | |
| CN109248790A (en) | Huge surfactant and preparation method thereof for mineral floating | |
| Durães et al. | Exploring the versatile surface chemistry of silica aerogels for multipurpose application | |
| El-Soad et al. | Insights into grafting of (3-Mercaptopropyl) trimethoxy silane on halloysite nanotubes surface | |
| Yu et al. | Modification of nanosilica particles with hydrophobic modifier bis [3-(triethoxysilyl) propyl] tetrasulfide by using micro-injection in aqueous solutions | |
| JPH0798655B2 (en) | Method for producing surface-modified silica | |
| CN111422877A (en) | Preparation method and surface modification method of nano silicon dioxide | |
| CN104629494A (en) | Polycarboxyl silicon dioxide nanoparticles and preparation method thereof | |
| Oh et al. | Facile synthesis of PEG–silica hybrid particles using one-step sol–gel reaction in aqueous solution | |
| CN116375756A (en) | Preparation and application of anion type nano silicon dioxide hydrosol | |
| Laird et al. | Sol–gel processing of polyhedral oligomeric silsesquioxanes: Nanohybrid materials incorporating T 8 and T 10 cages | |
| CN113000035B (en) | Cerium ion imprinted magnetic nano material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |