CN111574992B - Nano-phase permeability improver for acidizing and fracturing as well as preparation method and application of nano-phase permeability improver - Google Patents
Nano-phase permeability improver for acidizing and fracturing as well as preparation method and application of nano-phase permeability improver Download PDFInfo
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Abstract
The invention relates to a nano-phase permeability improver for acidizing and fracturing, a preparation method and application thereof, wherein the structural formula is shown as the following formula I:
Description
Technical Field
The invention relates to a nano-phase permeability improver for acidizing and fracturing, and a preparation method and application thereof, and belongs to the technical field of new materials.
Background
The phase permeation improver is a substance which can enter a stratum along with injected fluid and is adsorbed in a porous medium to cause unequal-proportion reduction of oil-water permeability of a reservoir. In recent years, the compact carbonate reservoir becomes an important reservoir type for oil and gas development of various countries and has high economic value. However, the pore throat structure of the compact carbonate rock is complex, the pore throat radius is small, micro/nano-scale pores and micro cracks are developed, the heterogeneity is strong, and the conventional production and development challenges are large. The acid fracturing is a production increasing measure widely adopted in the development of compact carbonate rock oil reservoirs at home and abroad at present, but for compact carbonate rock oil reservoirs with abundant development of bottom water, cracks formed after acid fracturing construction can become a circulation channel of injected water or bottom water, so that the problems of shortened effective period of production increase, sharp increase of water content and the like are caused, and the appearance of a phase permeation improver can solve the problems.
The polymer or polymer gel system is commonly used at home and abroad as a phase permeation improver to treat a production well with higher water content, and after the macromolecular substances are injected into a stratum, the macromolecular substances can be adsorbed on the wall surface of a rock pore canal, so that the polymer or polymer gel system has a selective control effect on the oil-water flow of a reservoir, and the unequal proportion reduction of the oil-water permeability of the reservoir is caused. However, for the acid fracturing development of compact carbonate rock, polymers and gels cannot exert a selective water control effect due to the problems of large molecular size, poor acid resistance and the like, and even the problems of overlarge pumping pressure and damage to a reservoir stratum can occur.
Chinese patent document CN103012667A discloses a synthesis method of a selective water shutoff agent for water control and sand control of an oil well, which takes acrylamide, sodium acrylate and N-methylene-bisacrylamide as raw materials, and reacts under the initiation of a redox initiator to obtain the selective water shutoff agent. The invention is beneficial to improving the sand prevention and water control effects of oil and water wells, and simultaneously, the productivity of the oil and water wells cannot be influenced due to the good oil passing effect of the oil and water wells. However, the selective water shutoff agent has a large molecular size, is only suitable for medium-high permeability reservoirs, does not have acid resistance, is easy to damage a network structure under an acidic condition, and is not suitable for acid fracturing development of compact carbonate rocks due to large difference between lithology of sandstone reservoirs and carbonate rocks.
Therefore, it is needed to develop an acid-resistant and reliable phase permeability improver for nano acid fracturing, which is used in the development operation of dense carbonate rock oil reservoirs with abundant bottom water development.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the problem that the existing phase permeation improver is not acid-resistant, the invention provides a nano phase permeation improver for acidizing and fracturing and a preparation method and application thereof.
The nano-phase permeability improver has good acid resistance and shear thickening property, can form a hydrophilic water control layer on the wall of a carbonate rock hole after entering a reservoir, and can play a selective water control effect in an acid fracturing oil well.
In order to solve the problems, the invention is realized by the following technical scheme:
a nano-phase permeability improver for acidizing and fracturing has a structural formula shown as the following formula I:
wherein the value range of n is 50000-55000, and the value range of X is 100-150.
According to the invention, the preferable nano-phase seepage improving agent for the acid fracturing is prepared by grafting polyacrylamide molecular chains on the surfaces of nano-silica particles through a silane coupling agent and then cationizing the grafted polyacrylamide molecular chains.
The invention also provides a preparation method of the nano-phase permeability improver for acidizing and fracturing.
A preparation method of a nano-phase permeability improver for acidizing and fracturing comprises the following steps:
(1) surface modifier and nano SiO 2 Adding the granules into an ethanol water solution, and uniformly dispersing the granules into the ethanol water solution by magnetic stirring; after the pH value of the solution is adjusted, heating, stirring and reacting for 3-5 hours, and then standing and reacting; after the reaction is finished, filtering, drying in vacuum and grinding to obtain a product KH570-SiO 2 ；
(2) KH570-SiO 2 Adding initiator and acrylamide into water, mixing, adjusting pH value, introducing nitrogen to remove oxygen, and initiating polymerization reaction in constant temperature water bath to obtain KH570-SiO 2 Mixing the solution;
(3) mixing KH570-SiO 2 Adjusting the pH value of the mixed solution, introducing nitrogen to remove oxygen, sequentially adding formaldehyde, diethanolamine and hydrochloric acid into the mixed solution at 50-65 DEG CStirring for reaction, evaporating, concentrating, cooling and drying the obtained product to obtain the nano-phase permeability improver for acid fracturing.
According to the invention, in the step (1), the nano SiO 2 The particle size of the particles is 10 to 500nm, and more preferably 15 to 25 nm.
According to the present invention, in the step (1), the surface modifier is a silane coupling agent KH 570.
According to the invention, in the step (1), the surface modifier is preferably mixed with the nano SiO 2 The mass ratio of the particles is (0.8-1.3): 1.5.
further preferably, the surface modifier is mixed with nano SiO 2 The mass ratio of the particles is (0.95-1.1): 1.5.
preferably, in the step (1), the volume concentration of the ethanol aqueous solution is 75-85%, and the nano SiO is 2 The mass-volume ratio of the particles to the ethanol aqueous solution is 1: (60 to 70), unit: g/mL; the magnetic stirring time is 25-35 min.
According to the preferable method, in the step (1), acetic acid is adopted to adjust the pH value to 3-6, the mixture is heated to 70-85 ℃, stirred and reacted for 3-5 hours at the speed of 500-700 r/min, and then kept stand and reacted for 8-12 hours.
Further preferably, in the step (1), the pH is adjusted to 4 by using acetic acid, the mixture is heated to 85 ℃, stirred and reacted for 4 hours at the speed of 600r/min, and then kept still for reaction for 12 hours.
Preferably, according to the invention, in step (2), KH570-SiO 2 The mass ratio of the initiator to the acrylamide is 1 (1.5-3.0) to 18-30.
Further preferably, in the step (2), KH570-SiO 2 The mass ratio of the initiator to the acrylamide is 1 (2.0-2.3) to (20-22).
Preferably, in step (2), the initiator is ammonium persulfate.
Preferably, according to the invention, in step (2), KH570-SiO 2 The mass ratio of the water to the water is 1: (90-160).
Preferably, according to the invention, in step (2), KH570-S is adjusted with acetic acid i O 2 The pH value of the solution is 4-6, the temperature of the constant-temperature water bath is 55-70 ℃, and the solution is stirred at the rotating speed of 300-400 r/min to initiate polymerization reaction for 3.5-5.5 h.
Preferably, in the step (2), the temperature of the water bath is 60 ℃, and the stirring speed is 350 r/min; the pH value of the adjusting system is 6; the polymerization time was 4 h.
According to a preferred embodiment of the invention, in step (3), KH570-SiO is adjusted with NaOH 2 The pH value of the mixed solution is 8-10, and the mixed solution is stirred and reacts for 1-3h at the temperature of 50-65 ℃.
According to the invention, in the step (3), the stirring speed is 200-400 r/min, the pH value of the adjusting system is 8, and the reaction temperature is 50 ℃; the reaction time is 2 h.
According to the invention, in step (3), KH570-SiO 2 The mass ratio of the mixed liquid to the formaldehyde to the diethanolamine to the hydrochloric acid is 1 (2.5-4.5): (3.8-6.4): (3.2-5.4), and the preferable ratio is 1 (3.5-4.2): (5.6-6.2): 4.0-4.5).
Preferably, in step (3), the temperature for evaporation and concentration is 80 ℃;
preferably, in step (3), the cooling is 0 ℃;
according to the invention, in the step (3), the drying is preferably carried out for 5-8 h under vacuum at 60-80 ℃.
The application of the nano-phase permeability improver for acidizing and fracturing is used as a selective water control agent for the exploitation of crude oil in a tight reservoir.
The nanophase permeation improver of the invention is nano S i O 2 The particles are used as a carrier, the hydrophilic cationic polymer is used as a surface modifier, the acid resistance is better, and the purpose of unequal proportional reduction of oil-water permeability of a reservoir is realized by depending on hydrophilic groups on polymer molecular chains through water absorption swelling and hydration.
The nano-phase seepage-improving particles can be firmly adsorbed on the wall of the carbonate rock pore to form a hydrophilic phase seepage-improving layer, the cationic polymer long chain grafted on the surface of the nano-particles forms a selective barrier in the pore channel, and the hydrophilic groups of the molecular chain can freely extend in water through water absorption expansion and hydration, so that frictional resistance is generated on flowing water, the flow of water is hindered, and the effective permeability of formation water is reduced. Due to the contraction and sliding effect of polymer molecular chains on the water control layer, the resistance of oil flow is reduced, and disproportionate permeability reduction effect is generated on crude oil and formation water in the rock core.
The principle of the invention is as follows:
1. the preparation principle of the nano-phase permeability improver for acidizing and fracturing comprises the following steps:
(1) the silane coupling agent KH570 undergoes hydrolysis reaction under acidic conditions to form a siloxane compound containing silicon hydroxyl bonds; the siloxane compound with low polymerization degree has silicon hydroxyl bond and nanometer SiO 2 Hydroxyl on the surface of the particle interacts to form a hydrogen bond; and finally, in the process of heating and curing, the covalent bond is formed by the action of the radical while dehydration reaction is carried out. The reaction equation is shown in the following formula II:
(2) the polymerization reaction between acrylamide generates polyacrylamide, acrylamide and nano SiO 2 The KH570-SiO is generated by the polymerization reaction between the double bonds of the silane grafted on the surface of the particle 2 PAM, the mechanism of both reactions belonging to the radical polymerization reaction, in view of the mode of action of the initiator and the reaction conditions. The reaction equation is shown in the following formula III:
(3) polyacrylamide reacts with formaldehyde aqueous solution, and the amido part is subjected to hydroxymethylation; reaction with a secondary amine to complete the alkylmethylation; reacting with hydrochloric acid to quaternize the tertiary amine. The structural formula is shown as the following formula I:
2. the principle of water control and oil stabilization:
after the nano-phase permeability improving particles are adsorbed on the surface of stratum rock due to the self small-size effect and the electrostatic force effect, the cationic polymer long chain grafted on the surfaces of the nano-particles forms a selective barrier in a pore channel, and hydrophilic groups of the long chain can freely extend in water through water absorption expansion and hydration effects to generate friction resistance to flowing water flow and block the flow of the water, so that the effective permeability of the stratum water is reduced; when crude oil flows through the pore channel, the molecular chain of the phase permeation improving nanoparticles is not oleophilic, the crude oil inhibits the free extension of the molecular chain of the cationic polymer, so that the molecular chain on the surface of the particles is contracted and deformed, and meanwhile, the nano phase permeation improving particles form a layer of hydrophilic film on the surface of rock, so that the crude oil cannot be diffused like on the surface of oleophilic rock. Instead, it converges to the middle of the tunnel and forms an outwardly spherical surface. In this way, the oil can be made to flow away from the hydrophilic rock. Therefore, the contact area of the oil flow and the hydrophilic pore walls is reduced, the resistance is relatively reduced, and the flow velocity on the surface of the oil flow nanoparticle layer is not zero. It increases uniformly at each point and increases overall. With the increase of the oil flow, the oil flow mode is changed from a parabolic velocity curve to a plug, the influence on the effective permeability of the oil in the pore canal is reduced, and therefore the infiltration improving agent solution shows the characteristic of obviously reducing the oil-water phase permeability in unequal proportion.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has wide raw material source, low price and easy realization of industrial production.
2. The invention does not increase the operation time, does not need additional field workers and has better economic benefit.
3. The particle size of the particles is in a nanometer range, and the particles cannot block the pore canal of the stratum, so that the permeability is reduced, and the damage to a reservoir or a crack is extremely small.
4. The invention can obviously reduce the water content of the compact carbonate acidized fracturing oil well, has little influence on the permeability of stratum oil phase, and has obvious water control and oil stabilization effects.
5. The nanophase seepage improver has certain acid resistance, and has shear thickening property when added into a solution.
6. The nano-phase permeation improver can be firmly adsorbed on the wall of the carbonate rock pore and forms a hydrophilic phase permeation improving layer, so that the micro-morphology and the element composition of the wall of the carbonate rock pore are changed.
Drawings
FIG. 1 is a schematic representation of the effect of a nanophase permeability improver in acid fracturing of an oil well.
FIG. 2 is a schematic diagram of water control and oil stabilization of a nanophase permeation improver, wherein A is a schematic diagram of a nanophase permeation improver for reducing water phase permeability, and B is a schematic diagram of a nanophase permeation improver for stabilizing oil phase permeability.
FIG. 3 is a transmission electron micrograph of the nanophase contrast improver of example 1.
FIG. 4 is a graph showing the results of the acid resistance test of the aqueous permeability improvers of example 1 at different pH's.
FIG. 5 is a graph of the relative permeability of the core before and after the treatment with the permeability improver of example 1, Kro is the relative permeability of the oil phase before the treatment with the permeability improver, Kro1 is the relative permeability of the oil phase after the treatment with the permeability improver, Krw is the relative permeability of the water phase before the treatment with the permeability improver, and Krw1 is the relative permeability of the water phase after the treatment with the permeability improver.
FIG. 6 is a plot of the permeability of the core before and after the treatment with the permeability-improving agent of example 2, wherein Kro is the relative permeability of the oil phase before the treatment with the permeability-improving agent, Kro1 is the relative permeability of the oil phase after the treatment with the permeability-improving agent, Krw is the relative permeability of the water phase before the treatment with the permeability-improving agent, and Krw1 is the relative permeability of the water phase after the treatment with the permeability-improving agent.
Fig. 7 is a phase permeability curve of the core before and after the phase permeability improver treatment in example 3, Kro is the relative permeability of the oil phase before the phase permeability improver treatment, Kro1 is the relative permeability of the oil phase after the phase permeability improver treatment, Krw is the relative permeability of the water phase before the phase permeability improver treatment, and Krw1 is the relative permeability of the water phase after the phase permeability improver treatment.
FIG. 8 is a plot of the permeability of the core before and after the permeability-improving agent treatment of example 4, Kro being the relative permeability of the oil phase before the permeability-improving agent treatment, Kro1 being the relative permeability of the oil phase after the permeability-improving agent treatment, Krw being the relative permeability of the water phase before the permeability-improving agent treatment, and Krw1 being the relative permeability of the water phase after the permeability-improving agent treatment.
FIG. 9 is a graph of core displacement dynamics at different mass concentrations of the permeability-improving agent treatments of examples 1-4.
Detailed Description
The present invention is further illustrated by, but not limited to, the following specific examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of a nano-phase permeability improver for acidizing and fracturing comprises the following steps:
(1) 1.9g of silane coupling agent KH570 and 3g of nano SiO 2 Adding into 200mL 80% ethanol water solution, and magnetically stirring for 30min to uniformly disperse in the ethanol water solution; heating the solution to 85 ℃, and adjusting the pH to 4 with acetic acid; stirring at constant temperature of 600r/min for 4h, and standing for 12 h; after the reaction is finished, filtering, drying in vacuum and grinding to obtain the product KH570-SiO 2 ；
(2) Adding 2g of the product obtained in the step (1) into 250mL of water at the rotating speed of 500r/min, then slowly adding 36g of acrylamide and 4g of ammonium persulfate, and pouring the solution into a three-neck round-bottom flask; stirring in a thermostatic water bath at 60 ℃ and 350r/min, and adjusting KH570-SiO with acetic acid 2 The pH of the solution is 6; introducing nitrogen to remove oxygen for 1h, and then starting to initiate polymerization for 4h to obtain KH570-SiO 2 Mixing the solution;
(3) adjusting the pH value of the mixed solution in the step (2) to 8 by using NaOH, at the temperature of 50 ℃, introducing nitrogen to remove oxygen, sequentially dropwise adding 7g of formaldehyde, 11.2g of diethanolamine and 8g of hydrochloric acid, and respectively stirring for 2 hours at the rotating speed of 300 r/min; the product obtained is concentrated by evaporation and cooled to obtain the final product after cationization.
An electron micrograph of the nanophase permeation improver obtained in this example is shown in fig. 3, and it can be seen from fig. 3 that the nanophase permeation improver is granular and the surface thereof is coated with polymer molecular chains.
Acid resistance test of aqueous phase permeation improver solutions at different pH' s
Preparing 250mL of 2 wt% phase permeation improver fluid, and mixing acid liquor with pH values of 3, 3.4, 3.8, 4.2, 4.6, 5, 5.4, 5.8, 6.2, 6.6 and 7 according to a volume ratio of 1: 8 slowly adding phase permeation improving agent fluid, stirring, and stirring at 60 deg.C for 170s -1 The change in the viscosity of the mixture was measured at the rotation speed of (2).
The acid resistance of aqueous solutions of the permeability-improving agents at different pH values is shown in fig. 4.
The permeability curves of the cores before and after the treatment with the permeability-improving agent of example 1 are shown in fig. 5.
Example 2
A preparation method of a nano-phase permeability improver for acidizing and fracturing comprises the following steps:
(1) 1.9g of silane coupling agent KH570 and 3g of nano SiO 2 Adding into 200mL 80% ethanol water solution, and magnetically stirring for 30min to uniformly disperse in the ethanol water solution; heating the solution to 85 ℃, and adjusting the pH to 4 with acetic acid; stirring at constant temperature of 600r/min for 4h, and standing for 12 h; after the reaction is finished, filtering, drying in vacuum and grinding to obtain a product KH570-SiO 2 ；
(2) Adding 2g of the product in the step (1) into 250mL of water at the rotation speed of 500r/min, then slowly adding 40g of acrylamide and 4.2g of ammonium persulfate, and pouring the solution into a three-neck round-bottom flask; stirring in constant temperature water bath at 60 deg.C and 350r/min, and adjusting KH570-S with acetic acid i O 2 The pH value of the solution is 6; introducing nitrogen to remove oxygen for 1h, and initiating polymerization for 4h to obtain KH570-SiO 2 Mixing the solution;
(3) regulating the pH value of the mixed solution in the step (2) to 8 by using NaOH, at the temperature of 50 ℃, introducing nitrogen to remove oxygen, sequentially dropwise adding 7.6g of formaldehyde, 11.6g of diethanolamine and 8.3g of hydrochloric acid, and stirring for 2 hours at the rotating speed of 300 r/min; the obtained product is evaporated, concentrated and cooled to obtain the final product after cationization.
The permeability curves of the cores before and after the treatment with the permeability-improving agent of example 2 are shown in fig. 6.
Example 3
A preparation method of a nano-phase permeability improver for acidizing and fracturing comprises the following steps:
(1) 2g of silane coupling agent KH570 and 3g of nano SiO 2 Adding into 200mL 80% ethanol water solution, and magnetically stirring for 30min to disperse in ethanol water solution; heating the solution to 85 ℃, and adjusting the pH to 4 with acetic acid; stirring at constant temperature of 600r/min for 4h, and standing for 12 h; after the reaction is finished, filtering, drying in vacuum and grinding to obtain a product KH570-SiO 2 ；
(2) Adding 2.5g of the product obtained in the step (1) into 250mL of water at the rotating speed of 500r/min, then slowly adding 50g of acrylamide and 5g of ammonium persulfate, and pouring the solution into a three-neck round-bottom flask; stirring in a thermostatic water bath at 60 ℃ and 350r/min, and adjusting KH570-SiO with acetic acid 2 The pH value of the solution is 6; introducing nitrogen to remove oxygen for 1h, and then starting to initiate polymerization for 4h to obtain KH570-SiO 2 Mixing the solution;
(3) regulating the pH value of the mixed solution in the step (2) to 8 by using NaOH, at the temperature of 50 ℃, introducing nitrogen to remove oxygen, sequentially dropwise adding 10g of formaldehyde, 15g of diethanolamine and 10g of hydrochloric acid, and stirring for 2 hours at the rotating speed of 300r/min respectively; the product obtained is concentrated by evaporation and cooled to obtain the final product after cationization.
The permeability curves of the cores before and after the treatment with the permeability-improving agent of example 3 are shown in fig. 7.
Example 4
A preparation method of a nano-phase permeability improver for acidizing and fracturing comprises the following steps:
(1) 2g of silane coupling agent KH570 and 3g of nano SiO 2 Adding into 200mL 80% ethanol water solution, and magnetically stirring for 30min to uniformly disperse in the ethanol water solution; heating the solution to 85 ℃, and adjusting the pH to 4 with acetic acid; stirring at constant temperature of 600r/min for 4h, and standing for 12 h; after the reaction is finished, filtering, drying in vacuum and grinding to obtain a product KH570-SiO 2 ；
(2) Adding 2.5g of the product obtained in the step (1) into 250mL of water at the rotating speed of 500r/min, then slowly adding 62g of acrylamide and 6.5g of ammonium persulfate, and pouring the solution into a three-neck round-bottom flask; stirring in a thermostatic water bath at 60 ℃ and 350r/min, and adjusting KH570-SiO with acetic acid 2 The pH of the solution is 6; introducing nitrogen to remove oxygen for 1h, and then starting to initiate polymerization for 4h to obtain KH570-SiO 2 Mixing the solution;
(3) regulating the pH value of the mixed solution in the step (2) to 8 by using NaOH, at the temperature of 50 ℃, introducing nitrogen to remove oxygen, sequentially dropwise adding 12g of formaldehyde, 18.2g of diethanolamine and 12.4g of hydrochloric acid, and stirring for 2 hours at the rotating speed of 300r/min respectively; the product obtained is concentrated by evaporation and cooled to obtain the final product after cationization.
The permeability curves of the cores before and after the treatment with the permeability-improving agent of example 4 are shown in fig. 8.
Comparative example 1
A method for preparing a nanophase permeation improver as described in example 1, except that in the step (1), the reaction temperature is adjusted to 55 ℃, and other conditions are not changed, to obtain the nanophase permeation improver.
Comparative example 2
A method for preparing a nanophase permeation improver as described in example 2, except that in the step (2), the pH of the system is adjusted to 4, and other conditions are not changed, to obtain the nanophase permeation improver.
Comparative example 3
A method for preparing a nanophase-permeation improver as described in example 3, except that in the step (2), the polymerization reaction time of the system is adjusted to 2 hours, and other conditions are not changed, to obtain the nanophase-permeation improver.
Examples of the experiments
The nano-phase permeability improving agents prepared in the examples 1 to 4 and the comparative examples 1 to 3 are respectively prepared into a phase permeability improving aqueous solution with the mass concentration of 2 wt% for carrying out a rock core displacement experiment, and the method comprises the following steps:
taking a rock core with the length of 9cm and the diameter of 2.5cm, cleaning the rock core, drying the rock core in vacuum for 24 hours, vacuumizing the rock core, saturating water, calculating the porosity of the rock core by using a weighing method, and measuring the water-logging absolute permeability k of the rock core at the experimental temperature of 60 ℃ (thermostat temperature control); injecting oil into the rock core at a constant speed until the outlet end of the rock core does not produce water any more, establishing the saturation of the bound water of the rock core, recording the displacement fluid production amount of the experiment and the pressure difference between the inlet and the outlet of the rock core, and calculating the effective permeability k of the oil phase under the bound water of the rock core o (ii) a Constant rate of injection into coreWater, recording the pressure difference delta P (t) at two ends of the core and the accumulated oil production Q at each time t o (t) cumulative Water yield Q w (t) calculating the effective permeability k of the water phase under the residual oil of the rock core until the outlet end of the rock core does not produce oil any more w (ii) a Reversely injecting a phase permeation improver fluid, keeping the temperature at 60 ℃ for 24 hours, and repeating the steps 3 and 4; and (4) sorting and calculating the experimental data, and drawing a relative permeability curve of the rock core. The results are shown in Table 1.
TABLE 1
It can be observed from table 1 that, after the injection of the phase permeation improving solution, the relative permeability of the water phase and the permeability of the water phase are both greatly reduced, the permeability of the water phase is both reduced by more than 60%, while the relative permeability of the oil phase is slightly increased, the permeability of the oil phase is reduced, but the reduction range is not large, and both are less than 15%. The selective water control effect of the nanophase permeation improver obtained by changing the reaction temperature and the reaction time or changing the pH of the reaction system of the invention is deteriorated.
Claims (9)
1. A nano-phase permeability improver for acidizing and fracturing has a structural formula shown as the following formula I:
formula I
Wherein the value range of n is 50000-55000, and the value range of X is 100-150;
the nano-phase permeability improver for acidizing and fracturing is prepared by the following method:
(1) surface modifier and nano SiO 2 Adding the particles into an ethanol water solution, and uniformly dispersing the particles in the ethanol water solution by magnetic stirring; after the pH value of the solution is adjusted, heating, stirring and reacting for 3-5 hours, and then standing and reacting; after the reaction is finished, filtering, drying in vacuum and grinding to obtain the product KH570-SiO 2 ；
(2) Mixing KH570-SiO 2 Adding initiator and acrylamide into water, mixing, adjusting pH value, introducing nitrogen to remove oxygen, and initiating polymerization reaction in constant temperature water bath to obtain KH570-SiO 2 Mixing the solution;
(3) mixing KH570-SiO 2 And adjusting the pH value of the mixed solution, introducing nitrogen to remove oxygen, sequentially adding formaldehyde, diethanolamine and hydrochloric acid into the mixed solution, stirring and reacting at 50-65 ℃, and evaporating, concentrating, cooling and drying the obtained product to obtain the nano-phase permeability improver for acid fracturing.
2. The nanophase penetration improver for acid fracturing as claimed in claim 1, wherein in the step (1), the surface modifier is a silane coupling agent KH 570.
3. The nanophase penetration enhancer for acid fracturing as claimed in claim 1, wherein in step (1), the surface modifier is mixed with nano SiO 2 The mass ratio of the particles is (0.95-1.1): 1.5.
4. the nanophase permeation improver for acidizing and fracturing, according to claim 1, wherein in the step (1), the volume concentration of the ethanol aqueous solution is 75 to 85%, and the nano SiO is 2 The mass-to-volume ratio of the particles to the ethanol aqueous solution is 1: (60 to 70), unit: g/mL; the magnetic stirring time is 25-35 min;
adjusting the pH value to 3-6 by adopting acetic acid, heating to 70-85 ℃, stirring at the speed of 500-700 r/min for reaction for 3-5 h, and then standing for reaction for 8-12 h.
5. The nanophase penetration enhancer for acid fracturing as claimed in claim 1, wherein in the step (2), KH570-SiO 2 The mass ratio of the initiator to the acrylamide is 1 (2.0-2.3) to (20-22).
6. The nanophase permeation improver for acid fracturing as set forth in claim 1, whereinCharacterized in that in the step (2), the initiator is ammonium persulfate; KH570-SiO 2 The mass ratio of the water to the water is 1: (90-160); adjusting KH570-S with acetic acid i O 2 The pH value of the solution is 4-6, the temperature of the constant-temperature water bath is 55-70 ℃, and the solution is stirred at the rotating speed of 300-400 r/min to initiate polymerization reaction for 3.5-5.5 h; the water bath temperature is 60 ℃, and the stirring speed is 350 r/min; the pH value of the adjusting system is 6; the polymerization time was 4 h.
7. The nanophase permeation improver for acid fracturing as claimed in claim 1, wherein in the step (3), KH570-SiO is adjusted with NaOH 2 The pH value of the mixed solution is 8-10, and the mixed solution is stirred and reacts for 1-3h at the temperature of 50-65 ℃; the stirring speed is 200-400 r/min, the pH value of the adjusting system is 8, and the reaction temperature is 50 ℃; the reaction time was 2 h.
8. The nanophase penetration enhancer for acid fracturing as claimed in claim 1, wherein in the step (3), KH570-SiO 2 The mass ratio of the mixed liquid to the formaldehyde to the diethanolamine to the hydrochloric acid is 1 (3.5-4.2) to (5.6-6.2) to (4.0-4.5).
9. The application of the nano-phase permeability improver for acid fracturing as claimed in claim 1 as a selective water control agent for tight reservoir crude oil extraction.
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