CN112322269B - Oil displacement sheet nano material - Google Patents
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- CN112322269B CN112322269B CN202011352669.9A CN202011352669A CN112322269B CN 112322269 B CN112322269 B CN 112322269B CN 202011352669 A CN202011352669 A CN 202011352669A CN 112322269 B CN112322269 B CN 112322269B
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- 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
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Abstract
The invention discloses a sheet nano material for oil displacement. According to the invention, 3-glycidol ether oxypropyl trimethoxysilane is selected to modify hectorite nano-particles to prepare flaky nano-particles with epoxy groups on two surfaces, then the particles are dispersed on an oil/water interface, hydrophobic modification is carried out on one surface of the particles by using a hydrophobic compound with amino groups, and hydrophilic modification is carried out on the other surface of the particles by using sodium bisulfite to prepare the asymmetric flaky nano-material. Tests show that the product has good dispersibility in simulated mineralized water; the product is added into an oil/water system, so that an interfacial film with certain strength can be formed, the fingering phenomenon in the displacement process is inhibited, and the oil displacement effect is improved; the product has obvious viscosity reducing effect on crude oil, and does not increase the difficulty of produced liquid treatment.
Description
Technical Field
The invention relates to a sheet nano material for oil displacement, belonging to the technical field of oilfield chemistry.
Background
Petroleum is one of indispensable non-renewable resources in modern society, and the exploitation and the utilization of the petroleum play an important role in the development of national economy. With the continuous progress of oil exploitation, at present, most of oil fields developed in China enter a high water cut period, and the yield can be stabilized only by a tertiary oil recovery technology, so that the crude oil recovery rate is improved. Chemical flooding is one of the main tertiary oil recovery technologies in China, and in the implementation process of chemical flooding, the mainly used chemical agent is a surfactant or a polymer. However, the two oil displacement agents still have a plurality of defects in the using process, and as for the surfactant, the surfactant is easily adsorbed by rock strata to cause concentration reduction, and the emulsifying action is too strong to cause difficulty in processing produced liquid; for polymers, the viscosity drops significantly under high temperature, high salt conditions, and mechanical and chemical degradation occurs during injection and migration. Therefore, the research and development of a novel oil displacement material with excellent comprehensive performance, wide application range and good long-term stability have important significance.
The nano material is used for improving chemical oil displacement due to a plurality of excellent properties, and the nano particles mainly improve the recovery ratio by: the oil-water interfacial tension and the contact angle are reduced, the wettability of oil layer rocks is changed, the viscous resistance of a pore channel to oil drops is reduced, and the crude oil is favorably peeled off and moved; the adsorption capacity of the surfactant on the surface of the rock is reduced, and the performance of reducing the oil-water interfacial tension and the contact angle is improved; improve the viscosity, temperature resistance and salt tolerance of the polymer solution. At present, commonly used oil displacement nano materials comprise nano SiO2TiO 2 nanoparticles2Nano ZrO 22Nano Al2O3And the like. The nano material does not have interfacial activity, and can achieve the effect of obviously improving the recovery ratio only by needing very high concentration in the using process. In recent years, researches show that the surface of a flaky nano material is subjected to asymmetric chemical modification, the hydrophilic and oleophilic properties of two sides of the material are accurately regulated and controlled, the material is endowed with excellent interfacial activity, the distribution of the material in an oil/water system is controlled, the oil displacement effect of the nano material can be obviously improved, the dosage of a medicament is reduced, and the treatment difficulty of produced liquid is reduced. Therefore, the asymmetric flaky nano material has good application prospect.
Disclosure of Invention
The invention aims to provide a sheet nano material for oil displacement.
The method for preparing the sheet nano material for oil displacement, which is provided by the invention, comprises the following steps:
1) ultrasonically dispersing the epoxy hectorite nano particles in water to obtain epoxy hectorite nano particle dispersion liquid;
2) uniformly mixing the hydrophobic compound and a nonpolar solvent to obtain a nonpolar solution of the hydrophobic compound;
3) adding the nonpolar solution of the hydrophobic compound in the step 2) into the epoxy group hectorite nanoparticle dispersion liquid in the step 1), stirring at 1200-1500 rpm for 15-60min, adding NaCl into a reaction system, and carrying out surface hydrophobic modification reaction at 20-60 ℃ for 12-60 h;
4) adding a sulfonating agent into the reaction system obtained in the step 3), and carrying out sulfonation reaction for 3-24h at 50-90 ℃.
In the step 1) of ultrasonic dispersion, the time is 20-40 min; specifically 30 min; the temperature is normal temperature;
the mass ratio of the epoxy hectorite nanoparticles to the water is 1 (200-2000); specifically, the formula (1) is (600-1500); more specifically 1: 800-;
in the step 2), the nonpolar solvent is selected from at least one of kerosene, white oil, toluene and xylene;
the mass ratio of the hydrophobic compound to the nonpolar solvent is 1 (20-500); specifically 1, (50-300); more specifically 1:60 to 140 or 1: 90;
in the step 3), the mass ratio of the epoxy hectorite nanoparticles to the hydrophobic compound is 1 (2-30); specifically 1, (3.5-25); more specifically 1: 10;
the mass ratio of the epoxy hectorite nanoparticle dispersion liquid to NaCl is 1 (0.005-0.025); specifically 1, (0.005-0.012);
in the step of surface hydrophobic modification reaction, the temperature is 20-45 ℃; in particular 30-40 ℃; the time is 15-36 h; in particular 20-30 h; the stirring speed is 700-900 rpm;
in the step 4), the sulfonating agent is NaHSO with the mass percentage concentration of 4% -6%3An aqueous solution; in particular to 5 percent;
the mass ratio of the epoxy hectorite nanoparticles to the sulfonating agent is 1 (180-500); specifically 1, (250-400); more specifically 1: 300-;
in the step of sulfonation reaction, the temperature is 50-80 ℃; in particular 70-75 ℃; the time is 5-15 h; in particular 6-8 h; the stirring speed is 700-900 rpm.
In addition, the sheet-shaped nano material for oil displacement prepared by the method, the application of the sheet-shaped nano material for oil displacement in oil displacement and an oil displacement agent containing the sheet-shaped nano material for oil displacement also belong to the protection scope of the invention.
The invention also claims epoxy hectorite nanoparticles obtained by modifying hectorite with 3-glycidoxypropyltrimethoxysilane, which is one of raw materials used in the method for preparing the flaky nano material for oil displacement.
In the epoxy hectorite nanoparticles, the method for modifying hectorite by 3-glycidyl ether oxypropyl trimethoxysilane comprises the following steps:
ultrasonically dispersing hectorite in water, adjusting the pH value of a system to 7.5-9, adding the 3-glycidyl ether oxypropyl trimethoxysilane for surface condensation reaction, adding NaCl, centrifuging, and collecting precipitate to obtain the product;
specifically, in the ultrasonic dispersion step, the time is 20-40 min; specifically 30 min; the temperature is normal temperature;
the reagent for adjusting the pH value of the system is NaOH aqueous solution;
in the reaction step, the temperature is 40-90 ℃; specifically 55-70 ℃; more particularly 60-65 ℃; the time is 6-30 h; specifically 6-18 h; more specifically 7-10 h;
the mass ratio of the hectorite to the water to the 3-glycidyl ether oxypropyltrimethoxysilane is 1: (10-500): (0.1-5); specifically, 1: (20-250): (0.1 to 2.5); more specifically 1:50:1.5 or 1:150:0.9 or 1:50-150: 0.9-1.5;
the mass ratio of the water to the NaCl is 1 (0.005-0.035); specifically 1 (0.005-0.025).
The invention also claims a hydrophobic compound of formula Ia or Ib,
in the formulas Ia and Ib, R1Is H or-CH3；R2An alkyl group having 4 to 12 carbon atoms (more specifically, an alkyl group having 5 to 10 or 9 to 10 carbon atoms);
R3is H or-CH3；
a and b are 1-6 (specifically 3-5);
R4is an alkyl group having 1 to 9 carbon atoms (specifically, an alkyl group having 3 to 5 carbon atoms);
w：x：y：z＝(1～10):(3～20):(0.2～5):(0.5～5)。
specifically, w: x: y: z is (3 to 8), (6 to 20), (0.2 to 1) and (0.5 to 2).
The invention provides a method for preparing the hydrophobic compound shown in the formula Ia or Ib, which comprises the following steps:
uniformly mixing an initiator, a chain transfer agent, a monomer A, a monomer B, a monomer C, a monomer D and an organic solvent for polymerization reaction to obtain a hydrophobic compound shown as a formula Ia or a formula Ib;
monomer A is
Monomer B is
Wherein R is1Is H or-CH3，R2An alkyl group having 4 to 12 carbon atoms (more specifically, an alkyl group having 5 to 10 or 9 to 10 carbon atoms);
monomer C is
Wherein R is3Is H or-CH3(ii) a a and b are 1-6 (specifically 3-5);
monomer D is
Wherein R is4Is an alkyl group having 1 to 9 carbon atoms (specifically, an alkyl group having 3 to 5 carbon atoms).
In the above method, the organic solvent is dimethylformamide;
the initiator is azobisisobutyronitrile;
the chain transfer agent is mercaptoethylamine;
in the step of polymerization reaction, the temperature is 50-90 ℃; specifically 55-75 ℃; more particularly 65-70 ℃; the time is 1-24 h; specifically 3-10 h; more specifically 3.5-5 h;
the polymerization reaction is carried out in an inert atmosphere; the inert atmosphere is specifically nitrogen atmosphere;
the mass ratio of the chain transfer agent to the initiator is 1 (2-8); specifically 1, (2-5.5); more specifically 1:3 or 1: 4;
the molar ratio of the chain transfer agent to the monomer A to the monomer B to the monomer C to the monomer D is 1 (1-10) to 3-20 (0.2-5) to 0.5-5; specifically, 1 (3-8) (6-20) (0.2-1) (0.5-2);
the mass ratio of the total mass of the monomers A to D to the organic solvent is 1 (2-10); specifically 1, (3-7); more specifically 1: 4.4-6.
Hectorite: the product which is purchased in the market, namely the lithium magnesium silicate, is called as the Laponite in English, and is an artificially synthesized trioctahedral layered colloidal material. In aqueous solution, the hectorite particles are in a disc shape with good dispersibility, the thickness of the particles is about 1nm, and the diameter of the particles is about 20-50 nm. The hectorite particles have large specific surface area, and the surfaces of the hectorite particles contain a large number of hydroxyl groups, so that surface modification can be carried out.
The invention selects 3-glycidoxy propyl trimethoxy silane to modify hectorite nano particles to prepare flaky nano particles with epoxy groups on two surfaces, then the particles are dispersed on an oil/water interface, one surface of the particles is subjected to hydrophobic modification by using a hydrophobic compound with amino groups, and the other surface of the particles is subjected to hydrophilic modification by using sodium bisulfite to prepare the asymmetric flaky nano material. Tests show that the product has good dispersibility in simulated mineralized water; the product is added into an oil/water system, so that an interfacial film with certain strength can be formed, the fingering phenomenon in the displacement process is inhibited, and the oil displacement effect is improved; the product has obvious viscosity reducing effect on crude oil, and does not increase the difficulty of produced liquid treatment.
The invention has the following beneficial effects:
1. the invention has the advantages of easily obtained raw materials and safe preparation process, and is suitable for industrial production.
2. The product has an asymmetric flaky nano structure, tends to aggregate at an interface to form a film structure with certain strength in an oil/water system, and can remarkably improve the oil displacement effect.
3. The hydrophilic-lipophilic property of the product can be adjusted through the raw material proportion and the molecular weight of the hydrophobic compound, and aiming at different crude oils, the hydrophilic-lipophilic property of the product is controlled to promote the product to mainly gather at an interface, so that the utilization efficiency of the product is improved.
4. The product has amide, ester, phenyl, ether and other functional groups in the hydrophobic structure, has the function of dispersing colloid and asphaltene in the crude oil, and can reduce the viscosity of the crude oil.
5. The hydrophilic structure of the product has sulfonic acid groups and excellent water solubility, so that the product has good dispersion stability under oil reservoir conditions.
6. The product prepared by the invention is easy to store and convenient to transport, and meets the requirement of environmental protection.
Drawings
FIG. 1 shows structural confirmation data of the hydrophobic compound obtained in step 1) of example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Examples 1,
(1) Preparation of hydrophobic Compounds
3g (0.018mol) of azobisisobutyronitrile, 1g (0.01 mol) of azobisisobutyronitrile were added3mol) mercaptoethylamine, 4.5g (0.052mol) of monomer A, 20g (0.108mol) of monomer B (R)1Is H, R2N-octyl radical), 3.5g (0.006mol) of monomer C (C-1, a is 3), 1.5g (0.012mol) of monomer D (R)4N-propyl) and 180g of dimethylformamide are added into a four-neck glass bottle provided with a stirrer, a nitrogen introducing pipe, a spherical condensing pipe and a thermometer, after all raw materials are stirred to be dissolved, nitrogen is introduced for 30min, the polymerization temperature is controlled at 65 ℃, the polymerization reaction is carried out for 5h, the product is washed by ethanol/water mixed solution, and the reduced pressure distillation is carried out at 50 ℃ to remove volatile components, thus obtaining the hydrophobic compound;
the structure confirmation data of this compound are shown in fig. 1.
As can be seen from the figure, the product has a correct structure and is the target product.
(2) Preparation of epoxy hectorite nanoparticles
Adding 1g of hectorite into 50g of deionized water, carrying out ultrasonic dispersion for 30min, adjusting the pH value of the system to 7.5-9 by using NaOH, adding 1.5g of 3-glycidyl ether oxypropyl trimethoxysilane into the system, controlling the reaction temperature at 60 ℃, reacting for 10h, adding 1g of NaCl, centrifuging, and drying the precipitate to obtain epoxy hectorite nanoparticles;
(3) modification of epoxy hectorite nanoparticles
Adding 0.5g of epoxy hectorite nano-particles into 500g of deionized water, and performing ultrasonic dispersion for 30min to obtain epoxy hectorite nano-particle dispersion liquid; 5g of hydrophobic compound is added into 450g of kerosene, and the mixture is stirred and dissolved to obtain hydrophobic compound kerosene solution; adding a hydrophobic compound kerosene solution into the epoxy hectorite nanoparticle dispersion liquid, stirring at the speed of 1200-1500 rpm for 15min, adding 4g of NaCl into the system, controlling the stirring speed at 700-900 rpm, controlling the reaction temperature at 30 ℃, and reacting for 30 h; 150g of NaHSO with the mass fraction of 5 percent3Adding the aqueous solution into a system, controlling the stirring speed at 700-900 rpm, controlling the reaction temperature at 75 ℃, and reacting for 8 hours; and centrifuging, washing and drying the product to obtain the asymmetric flaky nano material.
Example 2:
as described in example 1, except that the amount of azobisisobutyronitrile added in step (1) was 4 g.
Example 3:
the procedure is as described in example 1, except that in step (1) the amount of monomer A added is 7 g.
Example 4:
as described in example 1, except that R in the monomer B in step (1)1is-CH3，R2Is n-butyl.
Example 5:
as described in example 1, except that R in the monomer B in step (1)1Is H, R2Is n-decyl.
Example 6:
the procedure is as described in example 1, except that the amount of monomer B added in step (1) is 30 g.
Example 7:
as described in example 1, except that in step (1) the monomer C is C-2, wherein R is3Is H, and b is 5.
Example 8:
the procedure is as in example 1, except that in step (1) the amount of monomer C added is 2.2 g.
Example 9:
as described in example 1, except that R in the monomer D in step (1)4Is n-pentyl.
Example 10:
the procedure is as in example 1, except that in step (1) the amount of monomer D added is 2.5 g.
Example 11:
as described in example 1, except that the amount of dimethylformamide added in step (1) was 130 g.
Example 12:
the procedure is as described in example 1, except that the polymer temperature in step (1) is 70 ℃ and the time is 3.5 hours.
Example 13:
the procedure is as described in example 1, except that in step (2), 150g of deionized water and 0.9g of 3-glycidoxypropyltrimethoxysilane were added.
Example 14:
the procedure is as described in example 1, except that the reaction temperature in step (2) is 65 ℃ and the reaction time is 7 hours.
Example 15:
except that 400g of deionized water was added to formulate the hectorite epoxy nanoparticle dispersion in step (3), as described in example 1.
Example 16:
except that the hydrophobic compound kerosene solution was prepared in step (3), as described in example 1, in an amount of 700g of kerosene was added.
Example 17:
except that 3g of the hydrophobic compound was added in the preparation of the hydrophobic compound kerosene solution in the step (3) as described in example 1.
Example 18:
except that the hydrophobic compound was added in an amount of 7.5g in the preparation of the hydrophobic compound kerosene solution in the step (3) as described in example 1.
Example 19:
as described in example 1, except that NaHSO is used in step (3)3The amount of the aqueous solution added was 180 g.
Example 20:
as described in example 1, except that the hydrophobic compound was reacted with the epoxy hectorite nanoparticles in step (3) at a temperature of 40 ℃ for 20 hours, NaHSO3When the epoxy hectorite nano-particles react with the epoxy hectorite nano-particles, the temperature is 70 ℃, and the reaction time is 6 hours.
Comparative example 1:
hydrophilic nano SiO produced by Jiangsu Tianxing new material Co., Ltd2(TSP-C05)。
Comparative example 2:
self-made amphiphilic nano SiO2The preparation method is as follows.
10g of TSP-C05 was added to 200mL of H2Stirring in O/ethanol (volume ratio of 9.5/0.5) to disperse fully, and adjusting pH of the system to about 8 with triethylamine; adding 0.5g of n-octyl triethoxysilane, and reacting for 1.5h at 80 ℃; then, 0.25g of aminopropyltriethoxysilane is added for reaction for 2 hours at 80 ℃; filtering, and drying the filter cake at 80 deg.C to obtainAmphiphilic nano SiO2。
Evaluation of Performance
(1) Evaluation of viscosity-reducing Properties
The viscosity reducing effect of the products in the comparative examples and the examples 1-20 on the Bohai sea oil field thick oil sample is evaluated, and the test method comprises the following steps:
the preparation is prepared into 2000mg/L dispersion in simulated formation water (Table 1), 50mL crude oil and 50mL solution of the preparation are poured into a beaker and stirred by a stirrer at 1500r/min for 5min to obtain an oil-water mixture. The viscosity of the crude oil and the viscosity of the oil-water mixture are measured by a Brookfield DV-3 type rotary viscometer, the torque ratio is fixed at 50% by adjusting the rotating speed, the testing temperature is 65 ℃, and the viscosity of the crude oil is 285 mPas. After the viscosity test was completed, the emulsion was allowed to stand at room temperature for 6 hours, and the volume of the separated aqueous phase was measured. The results of the viscosity reducing performance evaluation are shown in Table 2.
TABLE 1 ion composition of simulated formation water
| Ion species | Na+ | K+ | Ca2+ | Mg2+ | HCO3 - | SO4 2- | Cl- | TDS |
| Concentration (mg/L) | 2323.52 | 26.57 | 115.53 | 52.29 | 619.22 | 11.16 | 3689.88 | 6838.17 |
TABLE 2 results of viscosity-reducing Performance evaluation
In table 2, the water volume ratio (%) is defined as follows:
wherein, the volume of the water phase is mL after the V-oil-water mixture is kept stand for 6 hours;
the viscosity reduction (%) is defined as follows:
wherein eta is the viscosity of the oil-water mixture, mPas.
As can be seen from the data in the table, the invention is relative to the hydrophilic nano materialThe prepared flaky nano material has a good viscosity reducing effect; amphiphilic nano SiO with hydrophilic and hydrophobic non-return distribution relative to surface2The oil-water mixture formed by the sheet-shaped nano material prepared by the method is easy to separate oil from water under the condition of standing, and the produced liquid is convenient to treat.
(2) Evaluation of oil displacing Performance
Three layers of heterogeneous artificial square core (size 4.5X 30cm, permeability 0.5/1.0/3.0 μm) were used2) And (5) carrying out an oil displacement experiment.
Experimental oil: the viscosity of crude oil is 285 mPa.s at 65 ℃; the concentrations of the experimental medicines are all 2000 mg/L.
Water for experiment: simulated mineralized water (shown in table 1 above).
The specific experimental procedure is as follows.
The formation water is saturated at a certain flow rate at 65 ℃ and the permeability is calculated.
Secondly, the crude oil after saturated aging at a certain flow rate at 65 ℃ is recorded with the saturated oil amount; the model was aged at 65 ℃ for 72 h.
Thirdly, water is driven at the flow rate of 1mL/min until the water content is more than 95 percent; 0.3PV of the drug solution was transfused at a flow rate of 0.5 mL/min; water is driven at the flow rate of 1mL/min until the water content is more than 98 percent.
And fourthly, calculating the water drive recovery rate and the medicament recovery rate.
The oil displacement performance evaluation results are shown in table 3.
TABLE 3 evaluation results of oil displacing Performance
As can be seen from the results in the table, SiO is relatively hydrophilic to the nanometer2Amphiphilic nano SiO with no return to surface2The sheet nano material prepared by the invention has the advantages of small dosage and excellent oil displacement effect.
Claims (14)
1. A method for preparing a flaky nano material for oil displacement comprises the following steps:
1) ultrasonically dispersing epoxy group hectorite nano particles in water to obtain epoxy group hectorite nano particle dispersion liquid;
the epoxy hectorite nanoparticles are obtained by modifying hectorite with 3-glycidyl ether oxypropyl trimethoxy silane;
2) uniformly mixing a hydrophobic compound and a nonpolar solvent to obtain a nonpolar solution of the hydrophobic compound;
the hydrophobic compound is shown in a formula Ia or a formula Ib,
in the formulas Ia and Ib, R1Is H or-CH3；R2Is an alkyl group with 4-12 carbon atoms;
R3is H or-CH3；
a and b are 1-6;
R4is an alkyl group having 1 to 9 carbon atoms;
w：x：y：z＝(1～10):(3～20):(0.2～5):(0.5～5)；
3) adding the nonpolar solution of the hydrophobic compound in the step 2) into the epoxy group hectorite nanoparticle dispersion liquid in the step 1), stirring at 1200-1500 rpm for 15-60min, adding NaCl into a reaction system, and carrying out surface hydrophobic modification reaction at 20-60 ℃ for 12-60 h;
4) adding a sulfonating agent into the reaction system obtained in the step 3), and carrying out sulfonation reaction for 3-24h at 50-90 ℃.
2. The method of claim 1, wherein: in the step 1), the ultrasonic dispersion step is carried out for 20-40 min; the temperature is normal temperature;
the mass ratio of the epoxy hectorite nanoparticles to the water is 1 (200-2000);
in the step 2), the nonpolar solvent is selected from at least one of kerosene, white oil, toluene and xylene;
the mass ratio of the hydrophobic compound to the nonpolar solvent is 1 (20-500);
in the step 3), the mass ratio of the epoxy hectorite nanoparticles to the hydrophobic compound is 1 (2-30);
the mass ratio of the epoxy hectorite nanoparticle dispersion liquid to NaCl is 1 (0.005-0.025);
in the step of surface hydrophobic modification reaction, the temperature is 20-45 ℃; the time is 15-36 h; the stirring speed is 700-900 rpm;
in the step 4), the sulfonating agent is NaHSO with the mass percentage concentration of 4% -6%3An aqueous solution;
the mass ratio of the epoxy hectorite nanoparticles to the sulfonating agent is 1 (180-500);
in the step of sulfonation reaction, the temperature is 50-80 ℃; the time is 5-15 h; the stirring speed is 700-900 rpm.
3. The method of claim 2, wherein: in the step 1), ultrasonic dispersion is carried out for 30 min;
the mass ratio of the epoxy hectorite nanoparticles to the water is 1 (600-1500);
the mass ratio of the hydrophobic compound to the nonpolar solvent is 1 (50-300);
in the step 3), the mass ratio of the epoxy hectorite nanoparticles to the hydrophobic compound is 1 (3.5-25);
the mass ratio of the epoxy hectorite nanoparticle dispersion liquid to NaCl is 1 (0.005-0.012);
in the step of surface hydrophobic modification reaction, the temperature is 30-40 ℃; the time is 20-30 h;
in the step 4), the sulfonating agent is NaHSO with the mass percentage concentration of 5%3An aqueous solution;
the mass ratio of the epoxy hectorite nanoparticles to the sulfonating agent is 1 (250-400);
in the sulfonation reaction step, the temperature is 70-75 ℃; the time is 6-8 h.
4. The method of claim 3, wherein: the mass ratio of the epoxy hectorite nanoparticles to the water is 1: 800-1000;
the mass ratio of the hydrophobic compound to the nonpolar solvent is 1: 60-140;
in the step 3), the mass ratio of the epoxy hectorite nanoparticles to the hydrophobic compound is 1: 10;
the mass ratio of the epoxy hectorite nanoparticles to the sulfonating agent is 1: 300-360.
5. The nano material prepared by the method of any one of claims 1 to 4.
6. The use of the oil-displacing sheet nanomaterial of claim 5 in oil displacement.
7. An oil-displacing agent comprising the oil-displacing sheet-like nanomaterial according to claim 5.
And 8.3-glycidol ether oxypropyl trimethoxy silane modified hectorite to obtain epoxy hectorite nanoparticles.
9. The hectorite-epoxy nanoparticles of claim 8, wherein: the method for modifying the hectorite by using the 3-glycidoxypropyltrimethoxysilane comprises the following steps:
ultrasonically dispersing hectorite in water, adjusting the pH value of a system to 7.5-9, adding the 3-glycidyl ether oxypropyl trimethoxysilane for surface condensation reaction, adding NaCl, centrifuging, and collecting precipitate to obtain the product;
in the ultrasonic dispersion step, the time is 20-40 min; the temperature is normal temperature;
the reagent for adjusting the pH value of the system is NaOH aqueous solution;
in the reaction step, the temperature is 40-90 ℃; the time is 6-30 h;
the mass ratio of the hectorite to the water to the 3-glycidyl ether oxypropyltrimethoxysilane is 1: (10-500): (0.1-5);
the mass ratio of the water to the NaCl is 1 (0.005-0.035).
10. The laponite epoxy nanoparticles of claim 9, wherein: in the ultrasonic dispersion step, the time is 30 min;
in the reaction step, the temperature is 55-70 ℃; the time is 6-18 h;
the mass ratio of the hectorite to the water to the 3-glycidyl ether oxypropyltrimethoxysilane is 1: (20-250): (0.1 to 2.5);
the mass ratio of the water to the NaCl is 1 (0.005-0.025).
11. A hydrophobic compound of formula Ia or Ib,
in the formulas Ia and Ib, R1Is H or-CH3；R2Is an alkyl group with 4-12 carbon atoms;
R3is H or-CH3；
a and b are 1-6;
R4is an alkyl group having 1 to 9 carbon atoms;
w：x：y：z＝(1～10):(3～20):(0.2～5):(0.5～5)。
12. a process for preparing the hydrophobic compound of formula Ia or formula Ib according to claim 11, comprising:
uniformly mixing an initiator, a chain transfer agent, a monomer A, a monomer B, a monomer C, a monomer D and an organic solvent for polymerization reaction to obtain a hydrophobic compound shown as a formula Ia or a formula Ib;
monomer A is
Monomer B is
Wherein R is1Is H or-CH3，R2Is an alkyl group with 4-12 carbon atoms;
monomer C is
Wherein R is3Is H or-CH3(ii) a a and b are 1-6;
monomer D is
Wherein R is4Is an alkyl group having 1 to 9 carbon atoms.
13. The method of claim 12, wherein: the organic solvent is dimethylformamide;
the initiator is azobisisobutyronitrile;
the chain transfer agent is mercaptoethylamine;
in the step of polymerization reaction, the temperature is 50-90 ℃; the time is 1-24 h;
the polymerization reaction is carried out in an inert atmosphere;
the mass ratio of the chain transfer agent to the initiator is 1 (2-8);
the molar ratio of the chain transfer agent to the monomer A to the monomer B to the monomer C to the monomer D is 1 (1-10) to 3-20 (0.2-5) to 0.5-5;
the mass ratio of the total mass of the monomers A to D to the organic solvent is 1 (2-10).
14. The method of claim 13, wherein: in the step of polymerization reaction, the temperature is 55-75 ℃; the time is 3-10 h;
the inert atmosphere is nitrogen atmosphere;
the mass ratio of the chain transfer agent to the initiator is 1 (2-5.5);
the molar ratio of the chain transfer agent to the monomer A to the monomer B to the monomer C to the monomer D is 1 (3-8): 6-20): 0.2-1): 0.5-2;
the mass ratio of the total mass of the monomers A to D to the organic solvent is 1 (3-7).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016021899A1 (en) * | 2014-08-04 | 2016-02-11 | 주식회사 엘지화학 | Surface-modified nanoclay for preparing superabsorbent resin, and neutralization solution for preparing superabsorbent resin |
| CN109045305A (en) * | 2018-07-31 | 2018-12-21 | 东华大学 | A kind of preparation method of the hectorite nano particle of TPGS modification |
| CN111333792A (en) * | 2020-04-07 | 2020-06-26 | 中国石油大学(华东) | Modified nano hectorite and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016021899A1 (en) * | 2014-08-04 | 2016-02-11 | 주식회사 엘지화학 | Surface-modified nanoclay for preparing superabsorbent resin, and neutralization solution for preparing superabsorbent resin |
| CN109045305A (en) * | 2018-07-31 | 2018-12-21 | 东华大学 | A kind of preparation method of the hectorite nano particle of TPGS modification |
| CN111333792A (en) * | 2020-04-07 | 2020-06-26 | 中国石油大学(华东) | Modified nano hectorite and preparation method and application thereof |
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