WO2022048008A1 - 一种有机-无机杂化纳米材料及其制备方法、应用 - Google Patents
一种有机-无机杂化纳米材料及其制备方法、应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 44
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 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 abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 6
- 229940096992 potassium oleate Drugs 0.000 claims abstract description 5
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- WYPBVHPKMJYUEO-NBTZWHCOSA-M sodium;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Na+].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O WYPBVHPKMJYUEO-NBTZWHCOSA-M 0.000 claims abstract description 3
- 239000000295 fuel oil Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 230000003635 deoxygenating effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims 1
- 235000020778 linoleic acid Nutrition 0.000 claims 1
- 229960004232 linoleic acid Drugs 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000001603 reducing effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000003921 oil Substances 0.000 description 28
- 235000019198 oils Nutrition 0.000 description 28
- 230000000694 effects Effects 0.000 description 25
- 239000011259 mixed solution Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000010586 diagram Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002569 water oil cream Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000009671 shengli Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
-
- 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
Definitions
- the present application relates to an organic-inorganic hybrid nanomaterial, a preparation method and application thereof, and belongs to the field of viscosity reduction of heavy oil.
- the world's heavy oil resources are extremely rich, and its geological reserves far exceed conventional crude oil. More than 70 heavy oil fields have been discovered in 12 basins in my country, and their resources account for about 25% to 30% of the total oil resources. As the recoverable amount of light crude oil is less and less and the extraction technology continues to improve, the exploitation of heavy oil resources has attracted more and more attention from all over the world. However, high density, high freezing point, high viscosity and difficulty in flowing are the outstanding characteristics of heavy oil resources in my country. Therefore, reducing the viscosity of heavy oil and improving its fluidity are the keys to solving the problems of heavy oil extraction, gathering and refining.
- Nanomaterial viscosity reducer is a new type of viscosity reducer. It utilizes the characteristics of small nanoparticle size, large specific surface area and strong adsorption to play a viscosity reducing effect on heavy oil, especially high-wax heavy oil.
- the nano viscosity reducers used for heavy oil are mainly organic polymer type and organic-inorganic compound type.
- the organic polymer nano-viscosity reducer has problems such as poor temperature resistance, low viscosity-reducing performance, and complicated process, while the organic-inorganic compound nanoviscosity reducer has the problem of chromatographic separation, which affects the effect of on-site application.
- this application adopts cheap and readily available raw materials, uses inorganic lamellar nanomaterials as the matrix, and hydrophilic and hydrophobic monomers as grafts.
- the modifying reagent prepares an organic-inorganic hybrid nanomaterial through a one-step water-phase free radical polymerization method.
- the preparation method has a simple process, and solves the problem that the preparation process of the conventional modified nanometer material is complex and unsuitable for industrial production and application promotion.
- the organic-inorganic hybrid nanomaterial has good viscosity reduction effect for heavy oil.
- an organic-inorganic hybrid nanomaterial is provided, and the organic-inorganic hybrid nanomaterial has good water solubility.
- organic-inorganic hybrid nanomaterial characterized in that the organic-inorganic hybrid nanomaterial is composed of structural units represented by formula I, formula ii and formula iii;
- R 1 is a structural unit formed after the double bond of an organic hydrophobic monomer is opened, and the organic hydrophobic monomer is selected from sodium ⁇ -alkenyl sulfonate, sodium oleate, potassium oleate, and linseed oil. any one of sodium;
- R 2 is selected from -OH, -ONa or -NH 2 ;
- M is the structural unit of montmorillonite material
- x is the mass percentage content of the structural unit represented by formula i in the organic-inorganic hybrid nanomaterial
- y is the mass percentage content of the structural unit represented by formula ii in the organic-inorganic hybrid nanomaterial
- z is the mass percentage content of the structural unit represented by formula iii in the organic-inorganic hybrid nanomaterial
- the value range of x is 10% ⁇ x ⁇ 50%
- the value range of y is 30% ⁇ y ⁇ 90%
- the value range of z is 1% ⁇ z ⁇ 50%
- the particle size of the organic-inorganic hybrid nanomaterial is 150-500 nm.
- the particle size of the organic-inorganic hybrid nanomaterial is independently selected from 150 nm, 180 nm, 210 nm, 240 nm, 246 nm, 250 nm, 260 nm, 270 nm, 300 nm, 330 nm, 360 nm, 390 nm, 420 nm, 450 nm, 480 nm, Any value in 500nm or a range of values in between.
- M is the structural unit of montmorillonite material, and the concrete structure is as follows:
- Organic-inorganic hybrid nanomaterials are prepared by one-step aqueous free radical polymerization with inorganic sheet nanomaterials as matrix, hydrophilic and hydrophobic monomers as graft modification reagents.
- a method for preparing organic-inorganic hybrid nanomaterials comprising the steps of stirring and heating an aqueous solution containing coupled montmorillonite nanomaterials, organic hydrophobic monomers and organic hydrophilic monomer raw materials, and adding an initiator to form an aqueous solution of a reaction system, Through radical polymerization, the organic-inorganic hybrid nanomaterial is obtained;
- the organic hydrophobic monomer is selected from at least one of sodium ⁇ -alkenyl sulfonate, sodium oleate, potassium oleate and sodium linoleate;
- the organic hydrophilic monomer is selected from at least one of acrylamide, acrylic acid, and sodium acrylate.
- the concentration of the coupled montmorillonite nanomaterial is 0.1-5wt%
- the total concentration of the organic hydrophobic monomer and the organic hydrophilic monomer is 5-10 wt%.
- the concentration of coupled montmorillonite nanomaterials is independently selected from any value or any two of 0.1 wt %, 0.2 wt %, 0.5 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %. range between the values.
- the total concentration of organic hydrophobic monomer and organic hydrophilic monomer is independently selected from any value of 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% or a range between any two value.
- the mass ratio of the organic hydrophobic monomer to the organic hydrophilic monomer is 1:1-1:4.
- the mass ratio of the organic hydrophobic monomer and the organic hydrophilic monomer is independently selected from any value of 1:1, 1:2, 1:3, 1:4, or a range value between any two.
- the amount of coupling montmorillonite nanomaterial with organic hydrophobic monomer and organic hydrophilic monomer is not strictly limited.
- the rotational speed of the stirring is 150-500 rpm.
- the rotational speed of the stirring is independently selected from any value of 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, or a range value between any two.
- the heating temperature is 35-50°C.
- the temperature of the heating is independently selected from any value of 35°C, 38°C, 41°C, 44°C, 47°C, 50°C, or a range value between any two.
- the amount of the initiator is 0.1-2.0% of the total mass of the monomers.
- the amount of the initiator is 0.5-1.0% of the total mass of the monomers.
- the amount of the initiator is a percentage of the total mass of the monomers independently selected from any of 0.1%, 0.2%, 0.5%, 0.7%, 1.0%, 1.2%, 1.5%, 1.7%, and 2.0% value or a range of values in between.
- the initiator is selected from at least one of potassium persulfate, sodium persulfate, and ammonium persulfate.
- the conditions of the radical polymerization reaction are: the temperature is 70-85° C., and the reaction time is 2-8 h.
- the conditions of the radical polymerization reaction are: the temperature is 80° C. and the reaction time is 5h.
- the temperature of the free radical polymerization reaction is independently selected from any value of 70°C, 72°C, 75°C, 77°C, 80°C, 82°C, 85°C, or a range value between any two.
- the temperature of the free radical polymerization reaction is independently selected from any value of 2h, 3h, 4h, 5h, 6h, 7h, 8h, or a range value between any two.
- it includes at least:
- (1) will contain coupled montmorillonite nanomaterial, organic hydrophobic monomer and organic hydrophilic monomer raw material dissolved in water, deoxygenate, stir, heat, obtain mixture I;
- the concentration of the initiator is 0.05-2 wt%.
- the concentration of the initiator is 0.25-0.5 wt %.
- the concentration of the initiator is independently selected from 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, Any value of 0.5 wt %, 0.7 wt %, 0.9 wt %, 1 wt %, 1.2 wt %, 1.5 wt %, 1.7 wt %, 2 wt %, or a range value between any two.
- a nano-viscosity reducing agent is provided.
- a nano-viscosity reducing agent contains at least one of the above-mentioned organic-inorganic hybrid nanomaterials and the organic-inorganic hybrid nanomaterials prepared according to the above-mentioned preparation method.
- an application of a nano-viscosity reducing agent in viscosity reduction of heavy oil is provided.
- the surface of the nano-viscosity reducer is rich in hydrophobic and hydrophilic segments, the hydrophobic segments are inserted into the oil phase, and the hydrophilic segments are inserted into the water phase, thereby forming an oil/water emulsion to achieve emulsification and viscosity reduction of heavy oil.
- the nanomatrix connecting the hydrophobic and hydrophilic segments is distributed at the oil-water interface, which improves the interfacial film stability of the oil/water emulsion interface and realizes the efficient viscosity reduction of heavy oil.
- the concentration of the nano-viscosity reducing agent is 0.1-1.0 wt% when applied to the viscosity reduction of heavy oil.
- the experimental method for evaluating the viscosity reduction effect of heavy oil refers to the China Petroleum and Natural Gas Industry Standard Q/SH0055-2007 "Technical Requirements for Viscosity Reducing Agents for Heavy Oil”.
- the dilution water is 3wt% NaCl+0.3wt% CaCl 2 oil field simulated mineralized water.
- 0.1-1.0 wt% of organic-inorganic hybrid nanomaterials has a viscosity reduction effect of 85-98% on heavy oil with a viscosity of 200-40000 mPa ⁇ s.
- the data ranges given are selected from any value in the range and include the endpoints of the range.
- the organic-inorganic hybrid nanomaterial provided by this application has a small particle size and a narrow particle size distribution, and has good performance in pure water and oil field simulated mineralized water at normal temperature (25°C) and high temperature of 80°C. Dispersion stability, no precipitation or precipitation, so it has good temperature and salt resistance.
- the preparation process is simple, the scale-up production is easy, the raw material sources are wide, and it is suitable for industrial production and application promotion.
- As a water-soluble nano viscosity reducer it has obvious viscosity reduction effect on both ordinary heavy oil and extra heavy oil at lower concentration.
- 0.1-1.0 wt% of organic-inorganic hybrid nanomaterials has a viscosity reduction effect of 85-98% on heavy oil with a viscosity of 200-40000 mPa ⁇ s.
- the nano-viscosity reducer requires very little disturbance during emulsification and viscosity reduction, and can realize the emulsification of heavy oil under static or low-perturbation conditions, and the oil-water emulsion has a long stability time.
- FIG. 1 is a schematic structural diagram of the organic-inorganic hybrid nanomaterial of the present application.
- FIG. 2 is a schematic diagram of the reaction for preparing organic-inorganic hybrid nanomaterials in the present application.
- FIG. 3 is a Fourier transform infrared spectrometer characterization diagram of sample 3# prepared in Example 3 and coupled montmorillonite nanomaterials.
- FIG. 4 is the particle size characterization diagram of the sample 3# prepared in Example 3 and the coupled montmorillonite nanomaterial.
- the raw materials in the examples of this application are all purchased through commercial channels.
- the test method adopts the conventional method, and the instrument setting adopts the setting recommended by the manufacturer.
- Coupling montmorillonite nanomaterials purchased from NANOCOR company, specification 50 ⁇ 300nm.
- the molecular structure characteristics of the organic-inorganic hybrid nanomaterials were tested and analyzed by Fourier transform infrared spectrometer (FTIR), and the analytical instrument was Nicolet iS50 Fourier transform infrared spectrometer produced by ThermoFisher Company.
- FTIR Fourier transform infrared spectrometer
- the particle size of the organic-inorganic hybrid nanomaterials was characterized by a Zetasizer Nano ZSE nanoparticle size potentiometer produced by Malvern Company.
- the apparent viscosity of the system was measured with a DV2TLV viscometer produced by Brookfield, and the test temperature was 50°C.
- the experimental procedure is as follows:
- Step (1) add the purchased industrial-grade coupled montmorillonite nanomaterials, organic hydrophilic monomers, and organic hydrophobic monomers into a round-bottomed flask, add an appropriate amount of water, stir and dissolve, and pass nitrogen to remove oxygen;
- Step (2) adding the initiator into the beaker, adding an appropriate amount of water, stirring and dissolving, and deoxidizing with nitrogen;
- Step (3) the round-bottomed flask in (1) is placed in an oil bath, mechanically stirred and heated;
- Step (4) add the solution in step (2) into the dropping funnel on the round-bottomed flask in step (3), and drop the solution in step (2) into the round-bottomed flask in step (3), After heating and reacting for a period of time, organic-inorganic hybrid nanomaterials are obtained.
- step (1) the masses of the raw materials coupled with montmorillonite nanomaterials, organic hydrophilic monomers, and organic hydrophobic monomers are respectively 0.10-5.00g, 3.00-9.00g, 1.00-5.00g, and the total mass of the raw materials 10.00g, water 80g, deoxygenation for 20-40 minutes;
- the initiator in the step (2) is a kind of potassium persulfate, sodium persulfate, and ammonium persulfate, the quality of the initiator is 0.005-0.2g, the water is 10g, and the oxygen is removed for 20-40 minutes;
- step (3) the stirring speed is 150-500 rpm, and the temperature is 35-50 °C;
- step (4) the dropwise addition time is 5-10 minutes, the temperature is 70-85°C, and the reaction time is 2-8h.
- Step (a) preparing oilfield simulated mineralized water
- Step (b) taking an appropriate amount of organic-inorganic hybrid nanomaterials, and diluting with the simulated mineralized water in step (1);
- Step (c) weighs the heavy oil sample of 21g in a beaker, adds the diluent in the step (2) of 9g;
- Step (d) put the beaker in step (c) into a constant temperature water bath at 50°C for 1 hour, and stir for 2 to 3 minutes;
- step (e) the apparent viscosity of the sample in step (d) at 50° C. was measured using a DV2TLV viscometer produced by Brookfield.
- the salinity of the mineralized water in step (a) is 3wt%NaCl+0.3wt% CaCl2 ;
- the mass concentration of the organic-inorganic hybrid nanomaterial in step (b) is 0.1-1.0 wt%
- step (e) the No. 0 rotor is selected for the apparent viscosity measurement, and the rotating speed is 6 rpm.
- ⁇ 0 Viscosity of heavy oil sample at 50°C, mPa ⁇ s;
- ⁇ Viscosity of the thick oil emulsion system after adding the sample solution at 50°C, mPa ⁇ s.
- FIG. 1 is a schematic structural diagram of the organic-inorganic hybrid nanomaterial of the present application
- FIG. 2 is a schematic diagram of the reaction for preparing the organic-inorganic hybrid nanomaterial of the present application. It should be noted that what is given is only a schematic diagram of the structure of organic-inorganic hybrid nanomaterials, and because during the polymerization process, each structural unit may be randomly polymerized, the order of z, x, y is not in the schematic diagram Do limit.
- the samples prepared in the above examples were characterized by particle size. Taking sample 3# as a typical example, the particle size test chart is shown in Figure 4. In the figure, a and b are respectively unmodified coupled montmorillonite nanomaterials and Particle size distribution diagram of final product sample 3#. It can be seen from the comparison that the particle size of the modified organic-inorganic hybrid nanomaterials increases to 246 nm.
- the viscosity reduction effect in heavy oil was evaluated for the samples prepared in the above examples and comparative examples.
- the heavy oil used is Xinjiang Karamay heavy oil, CNOOC Qinhuangdao heavy oil, Shengli Chenjiazhuang heavy oil, and the viscosity range is 200-40000mPa ⁇ s.
- the viscosities of the three heavy oil samples at 50 °C are shown in Table 1.
- Oilfield simulated mineralized water with a salinity of 3wt%NaCl+0.3wt% CaCl2 was prepared, and the samples in Examples or Comparative Examples were diluted to a concentration of 0.5wt%.
- the nano-viscosity reducer with an organic-inorganic hybrid nanomaterial content of 0.5 wt% has a viscosity reduction effect of 85-98% on heavy oil with a viscosity of 200-40000 mPa ⁇ s.
- samples 1#, 2#, 3#, 4#, and 5# in the examples all have obvious viscosity reduction effect, and the viscosity reduction rate is >85%, while the viscosity reduction rate of sample 6# Just below 85%.
- the viscosity reduction rate of sample 3# is as high as 96.2%, so the matching between sample 3# and oil sample 1# is the best, followed by others.
- samples 1#, 2#, and 3# in the examples all have obvious viscosity reduction effect, and the viscosity reduction rate is >85%, while the viscosity reduction rate of samples 4#, 5#, and 6# Just below 85%.
- the viscosity reduction rates of samples 1# and 3# to oil sample 2# are similar, both are about 90%, and the matching is similar.
- the viscosity reduction effect of samples 4#, 5# and 6# is slightly lower for this heavy oil, which may be due to the concentration boundary.
- the nano-viscosity reducer with an organic-inorganic hybrid nanomaterial content of 0.1-1.0 wt% has a viscosity-reducing effect of 85-98% on heavy oil with a viscosity of 200-40000 mPa ⁇ s.
- samples 1#, 2#, 5# can achieve effective viscosity reduction when the concentration is ⁇ 0.5wt%, sample 3# can achieve viscosity reduction rate >85% when the concentration is 0.1wt%, sample 4 #Although the viscosity reduction rate of >85% can be achieved at a concentration of 0.2wt%, the overall viscosity reduction rate is low. Sample 6# can achieve a viscosity reduction rate of >85% at a concentration of 1.0wt%. Therefore, sample 3# has the best viscosity reduction effect on oil sample 1#, with low dosage and high viscosity reduction rate.
- sample 2# can achieve effective viscosity reduction when the concentration is greater than or equal to 0.5wt%, and samples 4#, 5#, and 6# can achieve effective viscosity reduction when the concentration is >0.5wt%.
- the matching of sample 2# is relatively poor.
- Samples 1# and 3# can effectively reduce the viscosity of the heavy oil at a low concentration of 0.1-0.2wt%, but the dosage of 1# is relatively lower, and the viscosity reduction rate is slightly higher. Therefore, sample 1# has the best match with oil sample 2#.
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Abstract
Description
稠油编号 | 稠油类型 | 粘度,mPa·s |
油样1# | 新疆克拉玛依稠油 | 512 |
油样2# | 中海油秦皇岛稠油 | 1727 |
油样3# | 胜利陈家庄稠油 | 38352 |
稠油编号 | 样品编号 | 油水乳液的粘度,mPa·s | 降粘率,% |
1# | 1# | 74.2 | 85.5 |
2# | 59.4 | 88.4 | |
3# | 19.4 | 96.2 | |
4# | 64.5 | 87.4 | |
5# | 72.7 | 85.8 | |
6# | 104 | 79.7 | |
D1# | 301 | 41.2 | |
D2# | 238 | 53.4 | |
2# | 1# | 126 | 92.7 |
2# | 219 | 87.3 | |
3# | 148 | 91.4 | |
4# | 271 | 84.3 | |
5# | 305 | 82.3 | |
6# | 339 | 80.4 | |
D1# | 851 | 50.7 | |
D2# | 1366 | 20.9 | |
3# | 1# | 5215 | 86.4 |
2# | 8590 | 77.6 | |
3# | 4448 | 88.4 | |
4# | 6404 | 83.3 | |
5# | 1023 | 97.3 | |
6# | 13241 | 65.5 | |
D1# | 28188 | 26.5 | |
D2# | 15072 | 60.7 |
Claims (12)
- 一种有机-无机杂化纳米材料,其特征在于,所述有机-无机杂化纳米材料由式ⅰ、式ⅱ和式ⅲ表示的结构单元构成;其中,在式ⅰ中,R 1为有机疏水单体双键打开后所形成的结构单元,所述有机疏水单体来自α-烯基磺酸钠、油酸钠、油酸钾、亚油酸钠中的任一种;在式ⅱ中,R 2选自-OH、-ONa或-NH 2;在式ⅱi中,M为蒙脱土材料的结构单元;x为式ⅰ表示的结构单元在所述有机-无机杂化纳米材料中的质量百分含量;y为式iⅰ表示的结构单元在所述有机-无机杂化纳米材料中的质量百分含量;z为式ⅰii表示的结构单元在所述有机-无机杂化纳米材料中的质量百分含量;x的取值范围为10%≤x≤50%;y的取值范围为30%≤y≤90%;z的取值范围为1%≤z≤50%;50%≤x+y≤99%,x+y+z=100%。
- 根据权利要求1所述的有机-无机杂化纳米材料,其特征在于,所述有机-无机杂化纳米材料的粒径为150~500nm。
- 一种有机-无机杂化纳米材料的制备方法,其特征在于,将含有偶联蒙脱土纳米材料、有机疏水单体和有机亲水单体原料的水溶液,搅拌,加热,加入引发剂,形成反应体系水溶液,经自由基聚合反应,得到所述有机-无机杂化纳米材料;所述有机疏水单体选自α-烯基磺酸钠、油酸钠、油酸钾、亚油酸钠中的至少一种;所述有机亲水单体选自丙烯酰胺、丙烯酸、丙烯酸钠中的至少一种。
- 根据权利要求3所述的有机-无机杂化纳米材料的制备方法,其特征在于,所述反应体系水溶液中,偶联蒙脱土纳米材料的浓度为0.1~5wt%;有机疏水单体和有机亲水单体的总浓度为5~10wt%。
- 根据权利要求3所述的有机-无机杂化纳米材料的制备方法,其特征在于,有机疏水单体和有机亲水单体的质量比为1:1~1:4。
- 根据权利要求3所述的有机-无机杂化纳米材料的制备方法,其特征在于,所述引发剂的用量为单体质量总和的0.1~2.0%。
- 根据权利要求3所述的有机-无机杂化纳米材料的制备方法,其特征在于,所述引发剂选自过硫酸钾、过硫酸钠、过硫酸铵中的至 少一种。
- 根据权利要求3所述的有机-无机杂化纳米材料的制备方法,其特征在于,所述自由基聚合反应的条件为:温度为70~85℃,反应时间为2~8h。
- 根据权利要求3所述的有机-无机杂化纳米材料的制备方法,其特征在于,至少包括:(1)将含有偶联蒙脱土纳米材料、有机疏水单体和有机亲水单体原料溶解水中,除氧,搅拌,加热,得混合物I;(2)将含有引发剂的物质溶解水中,除氧,得混合物II;(3)将混合物II滴加到混合物I中,加热反应,得到所述有机-无机杂化纳米材料。
- 一种纳米降粘剂,其特征在于,含有权利要求1至2任一项所述的有机-无机杂化纳米材料、根据权利要求3至9任一项所述的制备方法制备的有机-无机杂化纳米材料中的至少一种。
- 权利要求10所述的纳米降粘剂在稠油降粘中的应用。
- 根据权利要求11所述的应用,其特征在于,所述纳米降粘剂在应用于稠油降粘时的浓度为0.1~1.0wt%。
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