CN115058238A - Surface-modified nanoparticle high-temperature foam stabilizer and preparation method and application thereof - Google Patents
Surface-modified nanoparticle high-temperature foam stabilizer and preparation method and application thereof Download PDFInfo
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- CN115058238A CN115058238A CN202210698685.6A CN202210698685A CN115058238A CN 115058238 A CN115058238 A CN 115058238A CN 202210698685 A CN202210698685 A CN 202210698685A CN 115058238 A CN115058238 A CN 115058238A
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- 239000006260 foam Substances 0.000 title claims abstract description 193
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 116
- 239000003381 stabilizer Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000003607 modifier Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000004088 foaming agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000000391 magnesium silicate Substances 0.000 claims description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000004872 foam stabilizing agent Substances 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005187 foaming Methods 0.000 abstract description 10
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 19
- 239000007788 liquid Substances 0.000 description 18
- 230000000903 blocking effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 150000003973 alkyl amines Chemical class 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010793 Steam injection (oil industry) Methods 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 230000005465 channeling Effects 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 alkyl glycoside Chemical class 0.000 description 1
- 239000003876 biosurfactant Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
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- 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
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Abstract
The invention provides a surface modified nano-particle high-temperature foam stabilizer, and a preparation method and application thereof. The stabilizer is prepared from the following raw materials in percentage by mass: 1.0-2.0% of lithium magnesium silicate nano particles, 0.01-0.05% of surface modifier, 0.01-0.1% of interface synergist and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent. The surface-modified nano-particle high-temperature foam stabilizer prepared by the invention can greatly improve the stability of high-temperature foam, strengthen the plugging performance of the high-temperature foam and improve the profile control and yield increase effect of the foam under the condition of ensuring larger foaming volume; and has good temperature resistance and injection performance.
Description
Technical Field
The invention belongs to the technical field of oilfield chemistry, and particularly relates to a surface-modified nanoparticle high-temperature foam stabilizer, and a preparation method and application thereof.
Background
Steam injection is a main mode for exploiting thick oil, but due to the low density and low viscosity of steam and the ubiquitous heterogeneity of strata, the phenomenon of steam overtopping and steam channeling is very easy to occur in the steam injection process, the swept volume of the steam is reduced, and the development effect of the steam injection is influenced. The foam profile control agent has selective plugging capability of 'blocking large, not blocking small, blocking water and not blocking oil', can control steam fluidity while plugging a steam channeling channel, can greatly improve swept volume of injected steam, and further improves steam injection development effect. However, the foam belongs to a typical thermodynamically unstable system, and liquid drainage, disproportionation and coalescence processes are very easy to be carried out under the high-temperature condition, so that the foam is broken, and the profile control and flooding plugging capability of the foam is greatly reduced. The addition of foam stabilizer to the foaming agent is the main means for improving the foam stability, wherein low molecular alcohols and high molecular polymers are commonly used as foam stabilizers, which can improve the foam stability to some extent, but when the temperature is higher than 150 ℃, these low molecular alcohols and high molecular polymers are easily decomposed by heat, and the foam stabilizing effect does not exist.
Inorganic nanoparticles have good stable foam performance after modification due to excellent temperature resistance, and the nanoparticles are used as a high-temperature foam stabilizer to improve the high-temperature foam stability through more and more researches. Chinese patent document CN111253922A provides an in-situ authigenic nanoparticle stable foam system and its preparation and application; it is a nanoparticle foam stabilizing system consisting of silicate, biosurfactant alkyl glycoside and saline. The foaming volume of the system can reach about 1000 mL; however, the half-life of the solution is only a few minutes, the high-temperature foam is not stable enough, and the plugging capability needs to be improved. Chinese patent document CN104774603A provides a stable foam system based on nanoparticles and Gemini surfactant and a preparation method thereof; the foam material is a foam system consisting of nano silicon dioxide, a Gemini surfactant and water. The foaming volume of the system is less than 300mL, and the foaming volume is smaller; the stability of the high-temperature foam is not good enough. Chinese patent document CN112175600A discloses a novel foam stabilizer and a preparation method thereof. The foam stabilizer takes silane coupling agent KH550 and bromoalkane as raw materials, the silane coupling agent KH550 and the bromoalkane are adjusted to react to generate a coupling agent with hydrophobic groups, the hydrophilic groups of sodium chloroacetate and the previous step are subjected to quaternization reaction, and the hydrophilic groups and silicon dioxide are further coupled to generate modified particles with hydrophilic and hydrophobic groups. The modified particles prepared by the method have excellent dispersibility and wettability; however, the half-life of the solution is short, and the high-temperature foam is not stable enough.
In conclusion, the existing nanoparticles are difficult to greatly improve the stability of high-temperature foam on the premise of maintaining the foaming volume, and the high-temperature blocking capability of the foam cannot be effectively improved. Therefore, the foam stabilizer which does not affect the foaming volume and can greatly improve the stability of the high-temperature foam is developed, and the foam stabilizer has great significance for improving the profile control and flooding effects of the high-temperature foam.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a surface modified nano-particle high-temperature foam stabilizer and a preparation method and application thereof. The surface-modified nano-particle high-temperature foam stabilizer prepared by the invention can greatly improve the stability of high-temperature foam, strengthen the plugging performance of the high-temperature foam and improve the profile control and yield increase effect of the foam under the condition of ensuring larger foaming volume; and has good temperature resistance and injection performance.
The technical scheme of the invention is as follows:
the surface-modified nanoparticle high-temperature foam stabilizer is prepared from the following raw materials in percentage by mass: 1.0-2.0% of lithium magnesium silicate nano particles, 0.01-0.05% of surface modifier, 0.01-0.1% of interface synergist and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
According to the invention, the stabilizer is preferably prepared from the following raw materials in percentage by mass: 1.0-1.5 percent of lithium magnesium silicate nano particles, 0.03-0.05 percent of surface modifier, 0.05-0.1 percent of interface synergist and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
According to the invention, the magnesium lithium silicate nano-particles have a trioctahedral layered structure, and the average particle size is 30-50 nm. The nanoparticles have excellent water dispersibility, viscosity enhancement and temperature resistance.
According to the invention, the surface modifier is preferably one or the combination of more than two of n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine or n-octylamine.
According to the invention, the interface synergist is preferably one or a combination of more than two of sodium hydroxide, sodium silicate, sodium phosphate, sodium carbonate or sodium metaborate.
The preparation method of the surface modified nano-particle high-temperature foam stabilizer comprises the following steps:
dispersing the magnesium lithium silicate nano particles in water to obtain a magnesium lithium silicate water dispersion system, adding a surface modifier, and uniformly dispersing; and then adding an interface synergist to adjust the pH value to 10.0-11.0, and carrying out full reaction and post-treatment to obtain the surface modified nanoparticle high-temperature foam stabilizer.
According to a preferred embodiment of the invention, the process for preparing the aqueous magnesium lithium silicate dispersion comprises the steps of: adding the magnesium lithium silicate nano particles into water, stirring for 4-6 h at the room temperature of 1000-2000 r/min, and standing for 12-24 h at the room temperature to obtain a uniformly dispersed magnesium lithium silicate water dispersion system.
According to the invention, the preferred dispersing conditions after the addition of the surface modifier are: stirring for 4-6 h at room temperature, wherein the stirring speed is 400-800 r/min.
According to the invention, preferably, after the surface modifier is added and dispersed uniformly, the interfacial synergist is added under the stirring condition of 400-800 r/min.
According to the invention, the reaction conditions are preferably: standing and reacting for 12-24 h at room temperature.
According to a preferred embodiment of the invention, the post-treatment method comprises the following steps: vacuum drying the reaction liquid obtained after the reaction at 50-80 ℃ for 12-24 h, and then sequentially cleaning with absolute ethyl alcohol and distilled water; repeating the process for 2-4 times, finally performing vacuum drying for 12-24 hours at the temperature of 50-80 ℃, and grinding into powder to obtain the surface modified nano-particle high-temperature foam stabilizer.
The surface modified nano-particle high-temperature foam stabilizer is applied to a high-temperature foam system as a foam stabilizer.
According to the invention, the foam system preferably comprises the following raw materials in percentage by mass: 1.0 to 1.5 percent of surface modified nano-particle high-temperature foam stabilizer, 0.5 to 1.0 percent of foaming agent and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
Preferably, the foaming agent is one or a combination of more than two of alpha-olefin sodium sulfonate, sodium dodecyl benzene sulfonate or sodium dodecyl sulfonate.
Preferably, the preparation method of the foam system comprises the following steps: dispersing the surface modified nano-particle high-temperature foam stabilizer in water, adding a foaming agent, and uniformly dispersing to obtain a foam system.
Further preferably, the preparation method of the foam system comprises the following steps: adding the surface modified nano-particle high-temperature foam stabilizer into water, stirring for 4-8 h at room temperature under the condition of 1000-2000 r/min, and then standing for 12-24 h at room temperature; and then adding a foaming agent under the stirring condition of 200-400 r/min, stirring and dispersing for 30-60 min at room temperature, and standing for 12-24 h at room temperature to obtain a foam system.
The invention has the following technical characteristics and beneficial effects:
1) the surface modified nano-particle high-temperature foam stabilizer provided by the invention takes magnesium lithium silicate inorganic nano-particles with excellent water dispersibility, viscosity increasing property and temperature resistance as materials, under the action of an interface synergist, short-chain alkylamine is adopted to generate neutralization action through electrostatic action and negative charges on the surfaces of the magnesium lithium silicate particles, molecular chains of the short-chain alkylamine can be directionally arranged through the electrostatic neutralization action, and a hydrophobic end faces to the outside, so that the hydrophilicity of the magnesium lithium silicate particles is reduced, and the aim of hydrophobic modification of the magnesium lithium silicate particles is fulfilled. Introducing a small amount of hydrophobic chains through the electrostatic adsorption effect of trace short-chain alkylamine, and changing the surface wettability of the nano particles from strong hydrophilic surfaces into weak hydrophilic surfaces (the contact angle is 60-70 degrees); the weak hydrophilic nano particles can form irreversible adsorption on a gas-liquid interface, so that the viscosity and interfacial viscoelasticity of a liquid film of the gas-liquid interface can be obviously improved, the mechanical strength of the interfacial liquid film is enhanced, and the stability of foam can be greatly improved. The modification method provided by the invention can avoid the over-strong flocculation effect of the nano particles after the cationic surfactant is modified and the adverse effects on the dispersion performance and the tackifying performance of the particles. The addition of the interface synergist is beneficial to the modification of the surface modifier on the surfaces of the magnesium lithium silicate particles and the promotion of the adsorption of the modified particles on a gas-liquid interface, so that the high-temperature stability and the profile control and flooding performance of foam are improved.
2) The surface-modified nano-particle high-temperature foam stabilizer provided by the invention has excellent foam stabilizing performance, and the half-life period of the high-temperature foam and the half-life period of the foam are obviously increased on the premise of hardly influencing the foaming capability of a foaming agent, so that the stability of the high-temperature foam is greatly improved. The stabilization principle is that the short-chain alkylamine surface modified magnesium lithium silicate nanoparticles can be firmly adsorbed on a gas-liquid interface to form a shell structure, so that the mechanical strength of a foam liquid film is greatly improved, meanwhile, the nanoparticles in a liquid phase are connected to form a three-dimensional network structure, the viscosity of the liquid phase is improved, the disproportionation and coalescence of foam are further prevented, and the stability of high-temperature foam is greatly improved.
3) The surface-modified nanoparticle high-temperature foam stabilizer provided by the invention has excellent temperature resistance and viscosity increasing performance, can greatly enhance the profile control and flooding performance of foam at a high temperature of more than 250 ℃, and can greatly improve the profile control and flooding seal channeling effect of steam foam; meanwhile, the average particle size of the surface-modified nano particles is 100-150 nm, and the nano particles can be suitable for high-temperature foam profile control and flooding of oil reservoirs with different permeability.
4) The surface modified nano-particle high-temperature foam stabilizer provided by the invention is simple in preparation method, strong in dispersibility of the modified nano-particles, easy to prepare a water dispersion system, capable of being used after modification, ready to use after preparation before production, and free from influence on foam stabilizing effect.
Drawings
FIG. 1 is an infrared spectrum of the surface-modified nanoparticle high temperature foam stabilizer (modified magnesium lithium silicate), the magnesium lithium silicate nanoparticles (magnesium lithium silicate) and the modifier n-butylamine (modifier) prepared in example 1.
FIG. 2 is a graph showing the contact angle changes before and after modification of the surface-modified nanoparticle high-temperature foam stabilizer (modified magnesium lithium silicate) and the magnesium lithium silicate nanoparticles (magnesium lithium silicate) prepared in example 1, i.e., magnesium lithium silicate.
FIG. 3 is a fluorescence confocal microscope image of the stabilized foam dyed by the surface-modified nanoparticle high-temperature foam stabilizer prepared in example 1.
Detailed Description
For the purpose of more clearly explaining the present invention, specific embodiments of the present invention will now be described in detail, but the scope of the present invention is not limited thereto.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The surface-modified nanoparticle high-temperature foam stabilizer is prepared from the following raw materials in percentage by mass: 1.0% of lithium magnesium silicate nano particles, 0.03% of surface modifier n-butylamine, 0.05% of interface synergist sodium hydroxide and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
The magnesium lithium silicate nano particles are of a trioctahedral layered structure, and the average particle size is 30-50 nm. The average particle size of the obtained surface modified nano-particle high-temperature foam stabilizer is 100-120 nm.
The preparation method of the surface modified nano-particle high-temperature foam stabilizer comprises the following steps:
at room temperature, 10g of magnesium lithium silicate nano particles are added into 990g of deionized water, stirred at a high speed of 1000r/min for 4h at a constant speed, and then kept stand for 12h to obtain a uniformly dispersed magnesium lithium silicate suspension. Adding 0.03g of n-butylamine surface modifier into 99.92g of magnesium silicate lithium suspension, stirring at a constant speed of 400r/min for 4h at room temperature, then adding 0.05g of sodium hydroxide interface synergist under the stirring condition of 400r/min to adjust the pH value to 10.0-11.0, and standing at room temperature for 12h to obtain the modified magnesium silicate lithium aqueous dispersion system. Drying the water dispersion system in a vacuum drying oven at 50 ℃ for 24 hours, and then sequentially cleaning with absolute ethyl alcohol and distilled water; repeating the process for 3 times, finally performing vacuum drying for 24 hours at 50 ℃, and grinding into powder by using an agate mortar to obtain the surface modified nano-particle high-temperature foam stabilizer.
The surface modified nano-particle high-temperature foam stabilizer is applied to a high-temperature foam system as a foam stabilizer.
The foam system comprises the following raw materials in percentage by mass: sodium alpha-olefin sulfonate (C) 16 ～C 18 ) Foaming agent, mass fraction 0.5%; the surface modified nano-particle high-temperature foam stabilizer accounts for 1.0 percent by mass; the balance is clear water with the mass fraction of 98.5%.
The preparation method of the foam system comprises the following steps:
10g of the surface-modified nanoparticle high-temperature foam stabilizer prepared in the embodiment is added into 990g of deionized water, stirred at a high speed of 1000r/min for 4 hours at room temperature and at a constant speed, and then kept stand at room temperature for 12 hours to obtain a uniformly dispersed modified magnesium lithium silicate aqueous dispersion system. Stirring at the rotating speed of 200r/min, 0.5g of alpha-olefin sodium sulfonate (C) 16 ～C 18 ) Adding 99.5g of modified magnesium lithium silicate aqueous dispersion system, stirring and dispersing for 30min at room temperature, and then fully standing for 12h at room temperature to obtain the high-temperature foam system.
FIG. 1 shows the surface-modified nanoparticles as high-temperature foam stabilizer (modified silicic acid) prepared in this exampleMagnesium lithium), magnesium lithium silicate nanoparticles (magnesium lithium silicate) and the surface modifier n-butylamine (modifier). As can be seen from FIG. 1, the infrared spectrum of the modified lithium magnesium silicate particles is 2870cm -1 The symmetric vibration absorption peak of methyl and methylene appears at 2934cm -1 At a position of 2960cm -1 Asymmetric vibration absorption peaks of methyl and methylene respectively appear at the two parts. The stretching vibration peak is also appeared in the infrared spectrum curve of the modifier, but the unmodified magnesium lithium silicate infrared spectrum curve is not appeared, which indicates that the modifier has adsorption effect on the surface of magnesium lithium silicate particles, so that the surface of the magnesium lithium silicate particles is partially hydrophobic and causes the magnesium lithium silicate particles to be weakly aggregated, and the adsorption of particle aggregates on a gas-liquid interface can be promoted.
Fig. 2 is a graph showing contact angle changes before and after modification of the surface-modified nanoparticle high-temperature foam stabilizer (modified magnesium lithium silicate) and the magnesium lithium silicate nanoparticle (magnesium lithium silicate) prepared in this example, i.e., the magnesium lithium silicate. Contact angle test method: respectively preparing dried magnesium lithium silicate particles and modified magnesium lithium silicate particles into core tablets by using a hydraulic core machine under the pressure of 25MPa, placing the prepared core tablets on an observation table of a DSA video contact angle measuring instrument, slowly dripping a drop of distilled water after adjusting to a proper position, and recording and calculating the contact angle by using the DSA video contact angle measuring instrument. Fig. 2 illustrates that the adsorption of the surface modifier on the surface of the magnesium lithium silicate changes the contact angle of the magnesium lithium silicate from 18 ° to 66 °, which indicates that the wettability of the particle surface changes from strong hydrophilicity to weak hydrophilicity, and the particle has the ability to adsorb to the gas-liquid interface.
FIG. 3 is the fluorescence confocal microscope image of the stable foam obtained by dyeing the surface-modified nanoparticle high-temperature foam stabilizer prepared in this example. The test method is as follows: preparing a modified magnesium lithium silicate particle water dispersion system and a rhodamine B aqueous solution for later use, adding a trace amount of rhodamine B aqueous solution into the modified magnesium lithium silicate particle water dispersion system under the stirring condition, and stirring for 4 hours at room temperature to obtain a solution to be detected. And centrifuging, washing and drying the solution to be detected to obtain modified magnesium lithium silicate particles adsorbed with rhodamine B, preparing a foaming solution by using the obtained particles according to the method of the embodiment, and stirring the foaming solution for 60 seconds at a rotating speed of 3000r/min by using a Waring Blender high-speed stirring cup at room temperature to generate foam. A small amount of foam was placed on the slide with a sampling gun and the coverslip was slowly placed to prepare the sample. And (3) observing the prepared sample under a fluorescence confocal microscope, adjusting the multiple and the fluorescence intensity, and storing an experimental phenomenon image observed by a window. Fig. 3 further confirms the above conclusion that the dyed modified magnesium lithium silicate particles are distributed in the foam liquid film, which proves that the modified magnesium lithium silicate can be firmly adsorbed on the gas-liquid interface to form a structure, the strength of the gas-liquid film is enhanced, and the foam stability is greatly improved.
Example 2
The surface-modified nanoparticle high-temperature foam stabilizer is prepared from the following raw materials in percentage by mass: 1.2% of magnesium lithium silicate nano particles, 0.04% of modifier n-hexylamine, 0.08% of interface synergist sodium carbonate and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
The magnesium lithium silicate nano particles are of a trioctahedral layered structure, and the average particle size is 30-50 nm. The average particle size of the obtained surface modified nano-particle high-temperature foam stabilizer is 120-140 nm.
The preparation method of the surface modified nano-particle high-temperature foam stabilizer is the same as that of example 1.
The surface modified nano-particle high-temperature foam stabilizer is applied to a high-temperature foam system as a foam stabilizer.
The foam system comprises the following raw materials in percentage by mass: a sodium dodecyl benzene sulfonate foaming agent with the mass fraction of 0.8 percent; the surface modified nano-particle high-temperature foam stabilizer accounts for 1.2 percent by mass; the balance is clear water with the mass fraction of 98%.
The foam system was prepared as in example 1.
Example 3
The surface-modified nanoparticle high-temperature foam stabilizer is prepared from the following raw materials in percentage by mass: 1.5% of lithium magnesium silicate nano particles, 0.05% of n-octylamine serving as a surface modifier, 0.1% of sodium metaborate serving as an interface synergist and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
The magnesium lithium silicate nano particles are of a layered structure, and the average particle size is 30-50 nm; the average particle diameter of the obtained surface modified nano-particle high-temperature foam stabilizer is 130-150 nm.
The preparation method of the surface modified nanoparticle high temperature foam stabilizer is the same as that of example 1.
The surface modified nano-particle high-temperature foam stabilizer is applied to a high-temperature foam system as a foam stabilizer.
The foam system comprises the following raw materials in percentage by mass: sodium dodecyl sulfate foaming agent with the mass fraction of 1.0 percent; the surface modified nano-particle high-temperature foam stabilizer accounts for 1.5 percent by mass; the balance is prepared with clear water, and the mass fraction is 97.5%.
The foam system was prepared as in example 1.
Comparative example 1
The unmodified lithium magnesium silicate reinforced foam system comprises the following raw materials in percentage by mass: sodium alpha-olefin sulfonate (C) 16 ～C 18 ) Foaming agent, mass fraction 0.5%; the stabilizer is unmodified magnesium lithium silicate nano particles, and the mass fraction of the stabilizer is 1.0 percent; the balance is clear water with the mass fraction of 98.5%.
The magnesium lithium silicate nano-particles are of a layered structure, and the average particle size is 30-50 nm.
The preparation method of the lithium magnesium silicate reinforced foam system is the same as that of example 1.
Comparative example 2
The foam stabilizer is prepared from the following raw materials in percentage by mass: 1.0% of lithium magnesium silicate nano particles, 0.03% of surface modifier cetyl trimethyl ammonium bromide, 0.05% of interface synergist sodium hydroxide and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
The magnesium lithium silicate nano-particles are of a layered structure, the average particle size is 30-50 nm, and the particle size of the obtained surface modified nano-particle high-temperature foam stabilizer is 1.0-1.5 microns.
The above foam stabilizer was prepared in the same manner as in example 1.
The foam stabilizer is applied to a high-temperature foam system as a foam stabilizer.
The foam system comprises the following raw materials in percentage by mass: foaming agent sodium alpha-olefin sulfonate (C) 16 ～C 18 ) 0.5 percent of mass fraction; the surface modified nano-particle high-temperature foam stabilizer accounts for 1.0 percent by mass; the balance is clear water with the mass fraction of 98.5%.
The foam system was prepared as in example 1.
Comparative example 3
The foam stabilizer is prepared from the following raw materials in percentage by mass: 1.0% of lithium magnesium silicate nano particles, 0.1% of surface modifier n-butylamine, 0.05% of interface synergist sodium hydroxide and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
The magnesium lithium silicate nano-particles are of a trioctahedral layered structure, the average particle size is 30-50 nm, and the average particle size of the obtained surface modified nano-particle high-temperature foam stabilizer is 800-1000 nm.
The above foam stabilizer was prepared in the same manner as in example 1.
The foam stabilizer is applied to a high-temperature foam system as a foam stabilizer.
The foam system comprises the following raw materials in percentage by mass: sodium alpha-olefin sulfonate (C) 16 ～C 18 ) Foaming agent, mass fraction 0.5%; the surface modified nano-particle high-temperature foam stabilizer accounts for 1.0 percent by mass; the balance is clear water with the mass fraction of 98.5%.
The foam system was prepared as in example 1.
Comparative example 4
The foam stabilizer is prepared from the following raw materials in percentage by mass: 1.0% of nano bentonite, 0.03% of surface modifier n-butylamine, 0.05% of interface synergist sodium hydroxide and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
The foam stabilizer was prepared in the same manner as in example 1.
The foam stabilizer is applied to a high-temperature foam system as a foam stabilizer.
The foam system comprises the following raw materials in percentage by mass: sodium alpha-olefin sulfonate (C) 16 ～C 18 ) Foaming agent, mass fraction 0.5%; the surface modified nano-particle high-temperature foam stabilizer accounts for 1.0 percent by mass; the balance is clear water with the mass fraction of 98.5%.
The foam system was prepared as in example 1.
Test example 1
Study subjects: foam stabilizers and foam systems prepared according to examples 1-3 and comparative examples 1-4.
(1) Evaluation of high temperature foam Properties: the surface-modified nanoparticle high-temperature foam stabilizers prepared in examples 1 to 3 and the stabilizers in comparative examples 1 to 4 were dispersed in water, respectively, to prepare an aqueous dispersion system having a mass concentration of 2.0%. Sealing the aqueous dispersion system in a high-temperature aging kettle, placing the kettle in a high-temperature roller heating furnace at 250 ℃ for heat aging treatment for 24 hours, taking out the kettle, and naturally cooling the kettle to room temperature. The foam system was prepared according to the preparation method of the foam systems of examples 1-3 and comparative examples 1-4 using the aged nanoparticles as the stabilizer, and the foam properties of the above system were evaluated by stirring at 3000r/min for 60s at room temperature using the Waring Blender stirring method, and the experimental results are shown in Table 1.
(2) Evaluating the high-temperature plugging performance of the foam system: the blocking performance of the foam system is evaluated by taking the resistance factor as an index, and the higher the resistance factor is, the better the blocking performance of the foam is. A sand-filled pipe model with the inner diameter of 25mm, the length of 30cm and the permeability of 3000mD is used for simulating a stratum at the experiment temperature of 250 ℃. And (3) resistance factor determination: at a rate of 1 mL/min -1 Simultaneously injecting water and nitrogen, and recording the pressure; simultaneously injecting a foam system solution and nitrogen in a gas-liquid volume ratio of 1:1, and recording the pressure; the resistance factor is the ratio of foam flooding pressure difference to gas-water mixed injection pressure difference, and is calculated. The results are shown in Table 1.
TABLE 1 high temperature foam Properties and high temperature blocking Properties of the stabilizers in examples 1 to 3 and comparative examples 1 to 4
| Sample(s) | Bubbling volume/mL | Half life of liquid separation/min | Half foam life/h | Resistance factor |
| Example 1 | 635 | 278 | 26 | 60.3 |
| Example 2 | 620 | 336 | 33 | 71.4 |
| Example 3 | 605 | 384 | 39 | 85.6 |
| Comparative example 1 | 620 | 76 | 18 | 42.6 |
| Comparative example 2 | 615 | 61 | 16 | 35.9 |
| Comparative example 3 | 580 | 58 | 20 | 36.4 |
| Comparative example 4 | 610 | 41 | 15 | 27.3 |
By comparing the foam parameters in examples 1-3 and comparative examples 1-4, it is found that compared with unmodified magnesium lithium silicate in comparative example 1, after the surfaces of the magnesium lithium silicate nanoparticles are modified by short-chain alkylamine in examples 1-3, the liquid precipitation half-life of a high-temperature foam system is greatly improved by 5-9 times, which indicates that the strongly hydrophilic magnesium lithium silicate particles are modified to become partially hydrophobic and cause weak aggregation of the magnesium lithium particles, so that irreversible adsorption of particle aggregates on a gas-liquid interface can be promoted, the mechanical strength of a foam liquid film is greatly increased, the disproportionation and coalescence of foam are effectively prevented, and the high-temperature foam stability is remarkably improved; meanwhile, as can be seen from the data of the foam high-temperature resistance factors in the table 1, the resistance factors of the foam systems in the examples 1 to 3 at 250 ℃ are obviously greater than those of the foam systems in the comparative examples 1 to 4, so that the foam with stable magnesium lithium silicate particles modified at the optimal concentration has excellent high-temperature plugging performance under the synergistic action of the surface modifier and the interface synergist, and can generate obvious plugging effect on high-temperature steam; the surface-modified lithium magnesium silicate high-temperature foam stabilizer provided by the invention can greatly improve the stability of foam under a high-temperature condition and can strengthen the high-temperature foam profile control, flooding and plugging capability.
And comparative example 2 adopts a cationic surfactant cetyl trimethyl ammonium bromide to modify the surface of the magnesium silicate lithium nanoparticle, although the cationic surfactant cetyl trimethyl ammonium bromide can be adsorbed on the surface of the magnesium silicate lithium nanoparticle through electrostatic action, the optimal foam stabilizing contact angle of 60-70 degrees cannot be achieved, the stability of the nanoparticle in comparative example 2 to foam is also reduced, and after the cationic surfactant adsorbs negatively charged magnesium silicate lithium particles, the nanoparticle is easy to flocculate, so that the particle size is rapidly increased, and the injection capacity of the nanoparticle is limited. The comparative example 3 adopts a modifier with higher concentration to modify the magnesium lithium silicate nano particles, and the result shows that the stability of the modified nano particles to the foam is sharply reduced, the particle size is sharply increased, and the high-temperature blocking capability of the foam is also sharply reduced. Comparative example 4 adopts surface modified nano bentonite as high temperature foam stabilizer, and the foam stabilizing effect and the adjusting, driving and plugging effect are obviously poor.
Therefore, the surface modified nano particles composed of the lithium magnesium silicate particles, the surface modifier and the interface synergist are the best high-temperature foam stabilizer, can obviously improve the high-temperature stability and the high-temperature profile control and plugging capability of a foam system, and have better application prospect in improving the profile control and flooding effect of high-temperature foam.
Claims (10)
1. The surface-modified nanoparticle high-temperature foam stabilizer is characterized by being prepared from the following raw materials in percentage by mass: 1.0-2.0% of lithium magnesium silicate nano particles, 0.01-0.05% of surface modifier, 0.01-0.1% of interface synergist and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
2. The surface-modified nanoparticle high-temperature foam stabilizer according to claim 1, which is prepared from the following raw materials in percentage by mass: 1.0-1.5 percent of lithium magnesium silicate nano particles, 0.03-0.05 percent of surface modifier, 0.05-0.1 percent of interface synergist and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
3. The surface-modified nanoparticle high-temperature foam stabilizer according to claim 1, wherein the magnesium lithium silicate nanoparticles have a trioctahedral layered structure and an average particle size of 30-50 nm.
4. The surface-modified nanoparticle high-temperature foam stabilizer according to claim 1, wherein the surface modifier is one or a combination of two or more of n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine or n-octylamine.
5. The surface-modified nanoparticle high-temperature foam stabilizer according to claim 1, wherein the interfacial synergist is one or a combination of two or more of sodium hydroxide, sodium silicate, sodium phosphate, sodium carbonate or sodium metaborate.
6. The process for preparing the surface-modified nanoparticle high-temperature foam stabilizer according to any one of claims 1 to 5, comprising the steps of:
dispersing the magnesium lithium silicate nano particles in water to obtain a magnesium lithium silicate water dispersion system, adding a surface modifier, and uniformly dispersing; and then adding an interface synergist to adjust the pH value to 10.0-11.0, and carrying out full reaction and post-treatment to obtain the surface modified nano-particle high-temperature foam stabilizer.
7. The method of claim 6, wherein the method comprises one or more of the following conditions:
i. the preparation method of the magnesium silicate lithium water dispersion system comprises the following steps: adding the magnesium lithium silicate nano particles into water, stirring for 4-6 h at the room temperature of 1000-2000 r/min, and standing for 12-24 h at the room temperature to obtain a uniformly dispersed magnesium lithium silicate water dispersion system;
ii. The dispersion conditions after adding the surfactant are as follows: stirring for 4-6 h at room temperature, wherein the stirring speed is 400-800 r/min;
iii, adding the surface modifier, dispersing uniformly, and adding the interface synergist under the stirring condition of 400-800 r/min;
iv, the reaction conditions are as follows: standing and reacting for 12-24 h at room temperature;
v, the post-processing method comprises the following steps: vacuum drying the reaction liquid obtained after the reaction at 50-80 ℃ for 12-24 h, and then sequentially cleaning with absolute ethyl alcohol and distilled water; repeating the process for 2-4 times, finally performing vacuum drying for 12-24 hours at 50-80 ℃, and grinding into powder to obtain the surface modified nano-particle high-temperature foam stabilizer.
8. The use of the surface-modified nanoparticles as claimed in any of claims 1 to 5 as foam stabilizers for high-temperature foam systems.
9. The use of the surface-modified nanoparticle high-temperature foam stabilizer according to claim 8, wherein the foam system comprises the following raw materials in percentage by mass: 1.0 to 1.5 percent of surface modified nano-particle high-temperature foam stabilizer, 0.5 to 1.0 percent of foaming agent and the balance of water; the sum of the mass percentages of the raw materials is one hundred percent.
10. Use of the surface-modified nanoparticle high temperature foam stabilizer according to claim 9, characterized by comprising one or more of the following conditions:
i. the foaming agent is one or the combination of more than two of alpha-olefin sodium sulfonate, sodium dodecyl benzene sulfonate or sodium dodecyl sulfonate;
ii. The preparation method of the foam system comprises the following steps: dispersing the surface modified nano-particle high-temperature foam stabilizer in water, adding a foaming agent, and uniformly dispersing to obtain a foam system;
further preferably, the preparation method of the foam system comprises the following steps: adding the surface modified nano-particle high-temperature foam stabilizer into water, stirring for 4-8 h at room temperature under the condition of 1000-2000 r/min, and then standing for 12-24 h at room temperature; and then adding a foaming agent under the stirring condition of 200-400 r/min, stirring and dispersing for 30-60 min at room temperature, and standing for 12-24 h at room temperature to obtain a foam system.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285935A (en) * | 2023-05-11 | 2023-06-23 | 智慧猫(东营)智能科技有限公司 | Foam stabilizing surfactant and preparation method thereof |
| CN116285935B (en) * | 2023-05-11 | 2023-12-01 | 广州芯联化工产品有限公司 | Foam stabilizing surfactant and preparation method thereof |
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