CN114106806B - Temperature-resistant salt-resistant nano imbibition agent and synthetic method and application thereof - Google Patents
Temperature-resistant salt-resistant nano imbibition agent and synthetic method and application thereof Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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Abstract
The invention provides a temperature-resistant and heat-resistant alloyA salt nano imbibition agent and a synthesis method and application thereof belong to the technical field of oil exploitation, transportation and chemical engineering. The invention provides a temperature-resistant and salt-resistant nano imbibition agent which is BrCH2CH2OSi(OCH2CH3)3N-methylimidazole, RO (CH)2CH2O)n‑1CH2CH2OH、BrCH2COONa is prepared by the step-by-step reaction of raw materials, and the excellent imbibition oil production effect can still be exerted in an ultra-low permeability reservoir stratum with the temperature less than or equal to 150 ℃ and the total mineralization degree less than or equal to 32868 mg/L.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, transportation and chemical engineering, and relates to a temperature-resistant and salt-resistant nano imbibition agent, and a synthesis method and application thereof.
Background
The low-permeability oil reservoir has the defects of compact structure of an oil-bearing stratum, low air permeability, fine pore throat and difficult imbibition and seepage, and the conditions of high injection pressure, small injection amount, fast water injection efficiency reduction and the like are shown in the water injection development process, so that the normal injection allocation can not be carried out, and the poor exploitation effect is caused. The development of shale oil gas and compact oil gas also has the technical problems of low porosity, low permeability, fine matrix pore throat, mainly nano-micron and the like.
Conventional enhanced shale oil and gas and tight oil and gas recovery is achieved by means of "pressing" or "flooding". The volume fracturing of the horizontal well is injected into the stratum through 'square sand and square liquid' with high pressure and large discharge to form a complex seam network, an oil gas flowing highway is built, the oil drainage area is increased, the single well control degree is improved, or the energy increasing throughput is realized through injecting 'water' and 'gas', and the 'source power' for efficient development of shale oil gas and compact oil gas is enhanced. Whether the 'pressing' and 'driving' are combined or not can complete the fracturing and crack making, meanwhile, the effects of supplementing formation energy and efficiently replacing oil and water are achieved, and the method becomes a new development concept.
The prior art discloses a novel nano imbibition agent synthesis and pressure flooding process research (Zhang waves, etc.; applied chemical industry [ J ], Shanxi extended oil (group) research institute of GmbH, 2021), wherein the recorded nano imbibition agent contains ester group in molecular structure, and is easy to hydrolyze at high temperature to cause chemical decomposition of the nano imbibition agent, and is difficult to penetrate into a low-permeability oil reservoir to exert imbibition oil production effect. The preparation of the silicon dioxide nanofluid and the research on the imbibition and oil drainage rules of the silicon dioxide nanofluid in an ultra-low permeability oil reservoir are also disclosed (Wangchen, Master's academic paper [ J ], China Petroleum university, 2018), the silicon dioxide nanofluid is compounded by modified nano silicon dioxide and a surfactant, and because covalent bonds do not exist between the modified nano silicon dioxide and the surfactant, the interaction between the modified nano silicon dioxide and the surfactant is easy to damage in the operation process of a stratum, so that nano particles are agglomerated, the particle size is far beyond the nano level, and the imbibition and oil drainage performance is difficult to be cooperatively exerted in the low permeability oil reservoir. Therefore, the nano imbibition agent has better temperature resistance and salt resistance, smaller particle size and narrower particle size range, and imbibes and discharges oil, and has important significance for further improving the recovery ratio of the low-permeability reservoir.
Disclosure of Invention
The invention provides synthesis and application of a temperature-resistant and salt-resistant nano imbibition agent, wherein the nano imbibition agent can still play an excellent oil imbibition and discharge effect in a low-permeability stratum with the temperature of less than or equal to 150 ℃ and the mineralization degree of less than or equal to 32868 mg/L.
In order to achieve the aim, the invention provides a synthesis method of a temperature-resistant and salt-resistant nano imbibition agent, which comprises the following steps:
mixing raw material BrCH2CH2OSi(OCH2CH3)3Adding the N-methylimidazole and N-methylimidazole into a closed reactor which is provided with a thermometer and a condensation reflux device and is filled with an organic solvent 1, introducing nitrogen to remove oxygen, heating to 50-60 ℃, carrying out reflux reaction for 2-3h, and evaporating to remove the solvent to obtain an intermediate 1;
the structural formula of the intermediate 1 is as follows:
intermediate 1, RO (CH)2CH2O)n-1CH2CH2Sequentially adding OH into another reactor containing an organic solvent 2, adding alkali liquor into a reaction system after the OH is fully dissolved, adjusting the pH of the system to be 8-10, and carrying out vacuum pumping reaction for 2-3h at the reaction temperature of 60-70 ℃ to obtain an intermediate 2;
the structural formula of the intermediate 2 is as follows:
intermediate 2 and BrCH2And sequentially adding COONa into a reactor containing an organic solvent 3, adding ionic liquid into the system, fully dissolving, reacting at the reaction temperature of 70-80 ℃ for 5-6h, and evaporating the solvent again to obtain the temperature-resistant salt-resistant nano imbibing agent.
The structural formula of the temperature-resistant and salt-resistant nano imbibition agent is as follows:
the reaction mechanism of the synthesis method is as follows:
preferably, the material BrCH2CH2OSi(OCH2CH3)3The mass ratio of the N-methylimidazole to the organic solvent 1 is (1.5-2.0): (0.5-1.0): 5.0. It is understood that the mass ratio of the above reaction raw materials may be 1.5:0.5:5.0, 1.5:0.8:5.0, 1.5:1.0:5.0, 1.7:0.5:5.0, 1.8:0.8:5.0, 1.9:1.0:5.0, 2.0:0.5:5.0, 2.0:0.8:5.0, 2.0:1.0:5.0, or any ratio within the above range. Here, it should be noted that the reaction raw material is determined to be BrCH due to the requirement of the oil field chemicals for organic chlorine and the further reduction of the production cost2CH2OSi(OCH2CH3)3And N-methylimidazole.
Preferably, intermediate 1, RO (CH)2CH2O)n-1CH2CH2The mass ratio of OH to the organic solvent 2 is (1.0-1.5): 1.5-2.0): 6.0, wherein, considering that the temperature-resistant and salt-resistant nano imbibition agent has typical surface/interface activity and good water solubility, RO (CH)2CH2O)n-1CH2CH2The value range of n in OH is 2-5, and specifically can be 2, 3, 4 and 5; r is straight-chain alkane with 4-8 carbon atoms. It is understood that the mass ratio of the above reaction raw materials may be 1.0:1.5:6.0, 1.0:1.8:6.0, 1.0:2.0:6.0, 1.2:1.5:6.0, 1.2:1.8:6.0, 1.2:2.0:6.0, 1.5:1.5:6.0, 1.5:1.7:6.0, 1.5:2.0:6.0, or any ratio within the above range. In addition, it is considered that the pressure reduction operation is advantageous to promote the reaction forward and increase the reaction conversion rate during the second-step reversible reaction.
Preferably, the alkaline solution added is selected from one or more of NaOH solution, KOH solution or ammonia water. It is understood that as the concentration of the alkali solution increases, the nucleophilic attack on the silicon nucleus from the less sterically hindered side due to the smaller OH-radius of the anion will charge the silicon nucleus negatively and cause the electron cloud to shift towards the OR group on the other side, such that the Si-O bond of the group is weakened and eventually breaks off the OR.
Preferably, the reaction raw material BrCH2The mass ratio of COONa, the intermediate 2 and the organic solvent 3 is (1.0-1.5): (2.5-3.0): 4.0. It is understood that the mass ratio of the above reaction raw materials may be 1.0:2.5:4.0, 1.0:2.7:4.0, 1.0:3.0:4.0, 1.2:2.5:4.0, 1.2:2.8:4.0, 1.2:3.0:4.0, 1.5:2.5:4.0, 1.5:2.7:4.0, 1.5:3.0:4.0, or any ratio within the above range.
Preferably, the ionic liquid added is selected from [ Bmim ]]BF4、[Bmim]PF6、[C3OHmim]BF4、[Bmim][CF3SO3]And [ Bmim ]][Tf2N]At least one of (1). It can be understood that the ionic liquid can be used as a solvent for preparing the nano particles, and the ionic liquid is beneficial to obviously reducing and thinning the particle size of the nano imbibition agent. In addition, the ionic liquid can also effectively prevent the agglomeration among the nanoparticles, so that the nanoparticles have good dispersibility and stability in the ionic liquid.
Preferably, the organic solvent 1, the organic solvent 2 and the organic solvent 3 are selected from at least one of toluene, ethanol, acetonitrile, tetrahydrofuran and dimethylsulfoxide.
Preferably, the mass of the added ionic liquid accounts for 0.3-0.5 per mill of the total mass of the reaction system.
The invention provides a temperature-resistant and salt-resistant nano imbibition agent prepared by the synthesis method according to any one technical scheme.
The invention provides an application of the temperature-resistant and salt-resistant nano imbibition agent in the technical scheme in the exploitation of an ultra-low permeability oil field with the temperature of less than or equal to 150 ℃ and the mineralization degree of less than or equal to 32868 mg/L.
Preferably, when the method is applied, after the temperature-resistant and salt-resistant nano imbibing agent with the concentration of 200ppm is added into the victory III type water solution with the temperature of 150 ℃ and the concentration of 32868mg/L, the median value of the particle diameter of the solution is less than or equal to 49nm, the capillary self-priming height is more than or equal to 20mm, and the interfacial tension is less than or equal to 8.17 multiplied by 10-3mN/m, surface tension less than or equal to 24.168 mN/m.
Preferably, when the application of the temperature-resistant salt-resistant nano imbibition agent is simulated in a victory III type aqueous solution at 90 ℃ and 32868mg/L, the imbibition recovery ratio is more than or equal to 63.79 percent after the temperature-resistant salt-resistant nano imbibition agent with the concentration of 200ppm is added. Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention provides a temperature-resistant and salt-resistant nano imbibition agent which is BrCH2CH2OSi(OCH2CH3)3N-methylimidazole, RO (CH)2CH2O)n-1CH2CH2OH、BrCH2COONa is prepared by the step-by-step reaction of raw materials, because of RO (CH) participating in the second step reaction2CH2O)n-1CH2CH2O-The group structure is larger, (CH)2CH2O)n-1CH2CH2O-And the silicon-based nano-porous material is only combined with Si at a position with small steric hindrance, so that the prepared nano-porous material has few byproducts.
2. The invention provides a synthesis method of a temperature-resistant and salt-resistant nano imbibition agent, under the alkaline condition, BrCH2CH2OSi(OCH2CH3)3Hydrolysis for preparing SiO with small grain diameter2In the particle process, respectively with RO (CH)2CH2O)n-1CH2CH2OH、BrCH2COONa is combined in sequence to form a covalent bond (it should be noted here that the order of addition of the two materials cannot be adjusted, if the two materials are first combined with BrCH2COONa is combined, the formed intermediate after reaction has larger steric hindrance, and is difficult to further combine with RO (CH) under the experimental condition2CH2O)n-1CH2CH2OH is combined to obtain a target product), so that the steric hindrance of the nano imbibition agent is larger, the nano particles are not easy to agglomerate, and the dispersibility and the stability are better; the ionic liquid is introduced as a solvent for preparing the nano imbibition agent, so that the particle size is further reduced, and the dispersion stability of the nano imbibition agent is enhanced. Furthermore, by RO (CH)2CH2O)n-1CH2CH2OH、BrCH2COONa modifies silicon dioxide nano particles, in a nano imbibition agent molecular structure, surfactant molecules and the nano particles act together, the oleophylic surface of a rock core becomes hydrophilic, and capillary force is changed into power from imbibition resistance, so that residual crude oil in a low-permeability and ultra-low-permeability oil reservoir is easier to transport and discharge.
3. The temperature-resistant and salt-resistant nano imbibition agent provided by the invention has the advantages that the capillary has high self-absorption rate, can effectively reduce the oil-water interfacial tension at high temperature and high mineralization degree, particularly in a stratum with high calcium and magnesium ion concentration, and has good surface activity and the effect of changing the rock wettability; the saturation and imbibition experiments of the on-site ultra-low permeability core verify that the oil-water-based porous polymer has a good imbibition oil production effect under an extremely low concentration.
Drawings
FIG. 1 is a schematic view of the particle size distribution of the NMSXQ-1 nano-sized imbibition agent provided by the invention;
FIG. 2 is a schematic view of the particle size distribution of the NMSXQ-2 nano-sized imbibition agent provided by the invention;
FIG. 3 is a schematic view of the particle size distribution of the NMSXQ-3 nanoimbibition agent provided by the invention;
FIG. 4 is a schematic view of the particle size distribution of the NMSXQ-4 nano-sized imbibition agent provided by the invention;
FIG. 5 is a schematic view of the NMSXQ-5 nano-sized imbibition agent particle size distribution provided by the invention;
FIG. 6 is a schematic view of the particle size distribution of the NMSXQ-6 nanoimbibition agent provided by the invention;
FIG. 7 is a schematic view of the NMSXQ-7 nanoimbibition agent particle size distribution provided by the invention;
FIG. 8 is a schematic view of the particle size distribution of the NMSXQ-8 nano imbibition agent provided by the invention.
Detailed Description
In order to more clearly and specifically describe the synthesis method and the application of the temperature-resistant and salt-tolerant nano imbibition agent provided by the embodiment of the invention, the technical scheme in the embodiment of the invention will be clearly and completely described below, and it is obvious that the described embodiment is only a part of the embodiment of the invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preparation of victory type III brine: a clean 5L jar was placed on a balance, 4831.75g of deionized water was added, the solution was vortexed by placing it in a magnetic stirrer, and the following reagents were added in order: 9.7144g of anhydrous calcium chloride, 7.3442g of magnesium chloride hexahydrate and 151.1887g of sodium chloride. Each reagent is added until it is completely dissolved before the other reagent is added. Stirring was continued until complete dissolution. The prepared saline water should be homogeneous and transparent, and has no precipitation phenomenon, and the effective period is 7 days.
The method for measuring the product performance comprises the following steps:
1 capillary self-priming height
1.1 preparation of oleophilic capillaries
1.1.1 capillary gauge: the inner diameter of the standard capillary tube is 0.5 mm, and carbon tetrachloride and benzene are sequentially used: acetone: performing ultrasonic treatment on ethanol =7:1.5:1.5 (volume ratio) for 30min to remove surface organic substances;
1.1.2, sequentially carrying out ultrasonic treatment on the surface of the capillary tube by using a dilute hydrochloric acid solution (1: 10) and a hydrofluoric acid solution (10%), and carrying out rough and activation on the surface of the capillary tube for 30 min; ultrasonic cleaning with deionized water to remove residual acid until pH is greater than 6.5, and oven drying at 105 deg.C;
1.1.3 preparing aging oil according to the proportion, wherein the aging oil comprises crude oil: aviation kerosene: 90# asphalt =2:5: 3; completely immersing the treated capillary tube in aging oil, and aging for 2-4 weeks at the temperature of 60 ℃;
1.1.4 taking out the capillary, soaking the capillary for 2 min by using kerosene to clean asphalt deposited on the inner wall and the outer wall of the capillary, wherein the observation is not influenced; and (3) blowing kerosene outside the tube by using nitrogen, placing the tube in a closed environment at 60 ℃ for drying to obtain an oil-wet capillary tube, and storing the tube for later use.
1.2 test sample preparation
1.2.1 preparing 200ppm solution to be detected by using victory III type saline, adding a drop of blue ink, keeping the temperature of the solution at 25 +/-0.2 ℃, pouring the solution to be detected into a cuvette to the boundary of the top end, and tightly attaching a ruler to the rear wall to stand behind;
1.2.2 vertically placing the processed three capillaries in a cuvette, keeping the inclination angles of all the capillaries for testing consistent by using a glass slide, reading the height difference between the liquid level in the recording tube and the boundary at the top end of the cuvette, respectively recording the liquid level height of the capillaries when the capillaries are immersed in the liquid level for 10min, and taking the arithmetic mean value as the measurement result.
2 surface tension
Preparing 200ppm sample solution by using the Shengli III type saline, measuring the surface tension value of the prepared fracturing fluid imbibition agent solution by using a surface tensiometer at the temperature of 25 ℃, continuously measuring for three times, and taking the average value.
3 interfacial tension
Preparing 200ppm sample solution with Shengli III type saline water, taking the prepared fracturing fluid imbibition agent solution, measuring the interfacial tension value of the fracturing fluid imbibition agent solution by a rotating drop method specified in SY/T5370-1999 3.3 at 70 ℃ by taking kerosene as a low-density phase, continuously measuring for three times, and taking the average value.
4 temperature resistance
200g of sample solution with 200ppm is prepared by using Shengli III type saline, the sample solution is sealed and placed in a drying oven with the temperature of 150 ℃ for aging for 15d, then the sample is taken out and is respectively measured according to the methods 1, 2 and 3, and the values of the self-priming height, the surface tension and the interfacial tension after high-temperature aging are recorded, wherein the self-priming height is the liquid level height when the capillary tube is immersed in the liquid level for 10 min.
5 imbibition recovery ratio
5.1 oil displacing agent solution of experimental sample: the preparation solution is prepared from Shengli III type saline and 200ppm nano imbibition agent; crude oil sample: taking stratum crude oil from an oil field site, and performing high-temperature dehydration and separation to obtain the crude oil; core sample: from a natural core column of 25 mm diameter, taken on site, with a permeability rating of 0.1 mD.
5.2 Experimental conditions experimental temperatures: 90 ℃; experiment pressure: atmospheric pressure.
5.3 test methods
5.3.1 saturated crude oil: vacuumizing and pressurizing the core to saturate the formation crude oil, and aging in a thermostat at 90 ℃ for more than 24 hours after saturation;
5.3.2 after saturation, winding copper wires on the core, then hanging the core wound with the fine copper wires on a hook under the balance of the infiltration experiment device, placing beakers filled with different water samples on a lifting table under the core, and ensuring that the core is positioned in the middle of liquid in the beakers and does not contact with the walls of the beakers during experiments by adjusting the copper wires and the lifting table;
5.3.3 the self-priming experiment was started by adjusting the height of the beaker to the appropriate height with the lift table to completely submerge the core in the liquid. And recording the self-absorption time and the change condition of the core mass in the experiment until no oil is separated out to show that the core mass is constant, and ending the experiment. And (3) calculating the imbibition recovery ratio R of the rock core according to the formula (1).
In the formula:
r-soaking spontaneous imbibition recovery ratio, decimal;
Vo-total saturated oil volume in core, mL;
delta m represents the mass difference, g, of the rock core in the oil displacement agent solution;
ρw、ρooil displacing agent solution density, oil density, g/cm3。
6 median diameter
6.1 preparing nano imbibition agent with concentration of 200ppm by using Shengli III type water, and placing the nano imbibition agent in a 150 ℃ oven by using a high-temperature aging tank for keeping the temperature for 72 hours.
6.2 cooling to room temperature, opening a Microtrac S3500 laser particle size analyzer for preheating for 30min, simultaneously ultrasonically dispersing the emulsion polymer in an ultrasonic cleaner for 5min, and measuring the median particle size (D50) on a laser particle distribution measuring instrument according to the operation steps.
Example 1
150g of BrCH2CH2OSi(OCH2CH3)3Respectively adding 50g N-methylimidazole and the tetrahydrofuran into a 1000mL closed reactor filled with 500g of tetrahydrofuran, arranging a thermometer and a condensation reflux device in the closed reactor, introducing nitrogen to remove oxygen, heating to 50 ℃, carrying out reflux reaction for 2 hours, and evaporating the solvent by a rotary evaporator to obtain an intermediate 1;
70g of intermediate 1, 105g C4H9OCH2CH2OCH2CH2OH is sequentially added into a 1000mL four-neck flask filled with 420g of acetonitrile, after the acetonitrile is fully dissolved, 11.9g of KOH solution with the mass concentration of 30 percent is added into the reaction system, the pH value of the system is adjusted to be 8, and the reaction temperature is 60 DEG CCarrying out vacuum pumping reaction for 2h under reduced pressure to obtain an intermediate 2;
150g of intermediate 2, 60g of BrCH2COONa was added to 240g of tetrahydrofuran in this order, and 0.135g of ionic liquid [ Bmim ] was added to the system]BF4After the nano-size nanometer porous material is fully dissolved, the reaction is carried out for 5 hours at the reaction temperature of 70 ℃, and the solvent is evaporated again by a rotary evaporator, so that the temperature-resistant and salt-resistant nano-size imbibing agent NMSXQ-1 can be prepared, wherein the particle size distribution is shown in figure 1.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-1 as follows:
example 2
150g of BrCH2CH2OSi(OCH2CH3)3Adding 75g N-methylimidazole and 75g of dimethyl sulfoxide into a 1000mL closed reactor filled with 375g of dimethyl sulfoxide respectively, arranging a thermometer and a condensation reflux device in the closed reactor, introducing nitrogen to remove oxygen, heating to 60 ℃, carrying out reflux reaction for 3 hours, and evaporating a solvent by using a rotary evaporator to obtain an intermediate 1;
75g of intermediate 1, 100g C8H17O(CH2CH2O)4CH2CH2Sequentially adding OH into a 1000mL four-neck flask filled with 300g of toluene, adding 11.6g of ammonia water solution with the mass concentration of 30% into a reaction system after the OH is fully dissolved, adjusting the pH value of the system to 9, and carrying out vacuum pumping reaction for 3 hours at the reaction temperature of 70 ℃ to obtain an intermediate 2;
150g of intermediate 2, 75g of BrCH2COONa was sequentially added to 200g of acetonitrile, and 0.2125g of ionic liquid [ Bmim ] was added to the system][CF3SO3]After the nano-size nanometer imbibition agent NMSXQ-2 is fully dissolved, the reaction is carried out for 6 hours at the reaction temperature of 80 ℃, and the solvent is evaporated again by a rotary evaporator, so that the temperature-resistant and salt-resistant nano-size imbibition agent NMSXQ-2 can be prepared, wherein the particle size distribution is shown in figure 2.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-2 as follows:
example 3
150g of BrCH2CH2OSi(OCH2CH3)3Adding 80g N-methylimidazole and the mixture into a 1000mL closed reactor filled with 500g of absolute ethyl alcohol respectively, arranging a thermometer and a condensation reflux device in the closed reactor, introducing nitrogen to remove oxygen, heating to 55 ℃, carrying out reflux reaction for 2.5h, and evaporating a solvent by using a rotary evaporator to obtain an intermediate 1;
70g of intermediate 1, 126g C6H13O(CH2CH2O)2CH2CH2Sequentially adding OH into a 1000mL four-neck flask filled with 420g of dimethyl sulfoxide, adding 10.5g of NaOH solution with the mass concentration of 30% into a reaction system after the OH is fully dissolved, adjusting the pH value of the system to 10, and carrying out vacuum pumping reaction for 2.5h at the reaction temperature of 65 ℃ to obtain an intermediate 2;
168g of intermediate 2, 60g of BrCH2COONa was added to 240g of anhydrous ethanol in sequence, and 0.1872g of ionic liquid [ Bmim ] was added to the system]PF6After the nano-size nanometer imbibition agent NMSXQ-3 is fully dissolved, the reaction is carried out for 5.5h at the reaction temperature of 75 ℃, and the solvent is evaporated again by a rotary evaporator, so as to prepare the temperature-resistant and salt-resistant nano-size imbibition agent NMSXQ-3 with the particle size distribution shown in figure 3.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-3 as follows:
example 4
150g of BrCH2CH2OSi(OCH2CH3)3Adding 84.375g N-methylimidazole respectively into a 1000mL closed reactor filled with 468.75g of acetonitrile, arranging a thermometer and a condensation reflux device in the closed reactor, introducing nitrogen to remove oxygen, heating to 57 ℃, carrying out reflux reaction for 3h, and evaporating the solvent by a rotary evaporator to obtain an intermediate 1;
70g of intermediate 1, 90g C4H9OCH2CH2OCH2CH2Sequentially adding OH into a 1000mL four-neck flask filled with 300g of absolute ethyl alcohol, after the OH is fully dissolved, adding 13.2g of KOH solution with the mass concentration of 30% into a reaction system, adjusting the pH value of the system to be 10, and carrying out vacuum pumping reaction at the reaction temperature of 68 ℃ for 2.6 hours to obtain an intermediate 2;
150g of intermediate 2, 80.769g of BrCH2COONa was added to 230.769g of tetrahydrofuran in sequence, and 0.1615g of ionic liquid [ Bmim ] was added to the system][Tf2N]After the nano-size nanometer imbibition agent NMSXQ-4 is fully dissolved, the reaction is carried out for 5.6h at the reaction temperature of 77 ℃, and the solvent is evaporated again by a rotary evaporator, so as to prepare the temperature-resistant and salt-resistant nano-size imbibition agent NMSXQ-4 with the particle size distribution shown in figure 4.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-4 as follows:
example 5
150g of BrCH2CH2OSi(OCH2CH3)3Adding 52.5g N-methylimidazole and dimethyl sulfoxide (500 g) into a 1000mL closed reactor filled with dimethyl sulfoxide, respectively, arranging a thermometer and a condensation reflux device in the closed reactor, introducing nitrogen to remove oxygen, heating to 52 ℃, carrying out reflux reaction for 2.3h, and evaporating a solvent by using a rotary evaporator to obtain an intermediate 1;
70g of intermediate 1, 112g C4H9OCH2CH2OCH2CH2Sequentially adding OH into a 1000mL four-neck flask filled with 420g of acetonitrile, adding 10.7g of ammonia water solution with the mass concentration of 30% into a reaction system after the OH is fully dissolved, adjusting the pH value of the system to be 8, and carrying out vacuum pumping reaction at the reaction temperature of 63 ℃ for 2.4 hours to obtain an intermediate 2;
150g of intermediate 2, 78g of BrCH2COONa was sequentially added to 240g of tetrahydrofuran, and 0.2106g of an ionic liquid [ C ] was added to the system3OHmim]BF4After the sodium chloride is fully dissolved, the mixture reacts for 5.6 hours at the reaction temperature of 72 ℃, and the solvent is evaporated again by a rotary evaporator, so that the temperature-resistant and salt-resistant sodium chloride can be preparedThe rice imbibition agent NMSXQ-5 has a particle size distribution shown in FIG. 5.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-5 as follows:
comparative example 1
150g of BrCH2CH2OSi(OCH2CH3)3Respectively adding 50g N-methylimidazole and the tetrahydrofuran into a 1000mL closed reactor filled with 500g of tetrahydrofuran, arranging a thermometer and a condensation reflux device in the closed reactor, introducing nitrogen to remove oxygen, heating to 50 ℃, carrying out reflux reaction for 2 hours, and evaporating the solvent by a rotary evaporator to obtain an intermediate 1;
70g of intermediate 1, 105g C4H9OCH2CH2OCH2CH2Sequentially adding OH into a 1000mL four-neck flask filled with 420g of acetonitrile, adding 11.9g of KOH solution with the mass concentration of 30% into a reaction system after the OH is fully dissolved, adjusting the pH value of the system to be 8, and carrying out vacuum pumping reaction for 2 hours at the reaction temperature of 60 ℃ to obtain an intermediate 2;
150g of intermediate 2, 60g of BrCH2COONa is sequentially added into 240g of tetrahydrofuran, and after the COONa is fully dissolved, the mixture reacts for 5 hours at the reaction temperature of 70 ℃, and after the solvent is removed again by a rotary evaporator, the temperature-resistant and salt-resistant nano imbibing agent NMSXQ-6 can be prepared, wherein the particle size distribution of the agent is shown in figure 6.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-6 as follows:
comparative example 2
150g of BrCH2CH2OSi(OCH2CH3)3Adding 75g N-methylimidazole respectively into 1000mL sealed reactor containing 375g dimethyl sulfoxide, arranging thermometer and condensing reflux device in the sealed reactor, introducing nitrogen to remove oxygen, heating to 60 deg.C, reflux reacting for 3 hr, and rotatingEvaporating the solvent by a rotary evaporator to obtain an intermediate 1;
75g of intermediate 1, 100g C10H21O(CH2CH2O)5CH2CH2Sequentially adding OH into a 1000mL four-neck flask filled with 300g of toluene, adding 11.6g of ammonia water solution with the mass concentration of 30% into a reaction system after the OH is fully dissolved, adjusting the pH value of the system to 9, and carrying out vacuum pumping reaction for 3 hours at the reaction temperature of 70 ℃ to obtain an intermediate 2;
150g of intermediate 2, 75g of BrCH2COONa was sequentially added to 200g of acetonitrile, and 0.2125g of ionic liquid [ Bmim ] was added to the system][CF3SO3]After the nano-size nanometer imbibition agent NMSXQ-7 is fully dissolved, the reaction is carried out for 6 hours at the reaction temperature of 80 ℃, and the solvent is evaporated again by a rotary evaporator, so that the temperature-resistant and salt-resistant nano-size imbibition agent NMSXQ-7 can be prepared, wherein the particle size distribution is shown in figure 7.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-7 as follows:
comparative example 3
150g of BrCH2CH2OSi(OCH2CH3)3Adding 84.375g N-methylimidazole respectively into a 1000mL closed reactor filled with 468.75g of acetonitrile, arranging a thermometer and a condensation reflux device in the closed reactor, introducing nitrogen to remove oxygen, heating to 57 ℃, carrying out reflux reaction for 3h, and evaporating the solvent by a rotary evaporator to obtain an intermediate 1;
70g of intermediate 1, 90g C4H9OCH2CH2OCH2CH2Sequentially adding OH into a 1000mL four-neck flask filled with 300g of absolute ethyl alcohol, and after the OH is fully dissolved, carrying out vacuum pumping reaction for 2.6h at the reaction temperature of 68 ℃ to obtain an intermediate 2;
150g of intermediate 2, 80.769g of BrCH2COONa was added to 230.769g of tetrahydrofuran in sequence, and 0.1615g of ionic liquid [ Bmim ] was added to the system][Tf2N]After being fully dissolved, the mixture is reacted at the reaction temperature of 77 DEG CAfter 5.6h, the solvent is evaporated again by the rotary evaporator, and the temperature-resistant and salt-resistant nano imbibition agent NMSXQ-8 can be prepared, wherein the particle size distribution is shown in figure 8.
The temperature-resistant and salt-resistant nano infiltration and absorption agent has the structural formula NMSXQ-8 as follows:
TABLE 1 series of technical indexes of small-scale nano-grade imbibition agent
As can be seen from the above table, the technical indexes of NMSXQ-1, NMSXQ-2, NMSXQ-3, NMSXQ-4 and NMSXQ-5 in the examples are obviously higher than the technical requirements of the comparative examples NMSXQ-6, NMSXQ-7 and NMSXQ-8, which indicates that BrCH is used as the reference2CH2OSi(OCH2CH3)3N-methylimidazole, RO (CH)2CH2O)n-1CH2CH2OH and BrCH2COONa is used as a reaction raw material, the temperature-resistant and salt-resistant nano infiltration and absorption agent synthesized by three steps of reactions has good surface activity and can effectively reduce the interfacial tension under the condition of an extremely low concentration of 200ppm, the capillary wettability is changed, the capillary self-absorption height is over 20mm, and the core technical indexes of the NMSXQ-1, NMSXQ-2, NMSXQ-3, NMSXQ-4 and NMSXQ-5 are that the capillary self-absorption height is more than or equal to the technical requirement of 20mm specified in Q/SLCG 0403 and 2021 infiltration and extraction agent for fracturing fluid on the premise of lower concentration, higher mineralization degree and longer aging time. In addition, under a certain temperature and mineralization degree, the particle size range of the nano imbibition agent can still reach a lower nano level, and a good imbibition oil production effect can be exerted in low-permeability and ultra-low-permeability oil reservoirs.
It is understood that the third reaction step of comparative example 1 is the reaction of example 1 without adding the ionic liquid [ Bmim ]]BF4Since the solvent prepared from the ionic liquid nano-particles is helpful for obviously reducing and thinning the particle size of the nano-imbibition agent, the embodimentThe median 49nm of the particle size of the 1 NMSXQ-1 is obviously smaller than the median 570nm of the particle size of the 1 NMSXQ-6 in the comparative example, and the NMSXQ-1 has smaller size, so that the NMSXQ-1 can easily enter fine pore throats, remove blockage and water lock in rock stratums, change the wettability of rocks, increase the imbibition and diversion capacity and fully realize the imbibition and oil recovery effect in an ultra-low permeability reservoir; in addition, the ionic liquid can also effectively prevent the agglomeration among the nanoparticles, so that the nanoparticles have good dispersibility and stability in the ionic liquid. The particle size distribution range of the NMSXQ-1 in the example 1 is 39 nm-73 nm, while the particle size distribution range of the NMSXQ-6 in the comparative example 1 is 94 nm-2.536 mu m, which is far beyond the average air permeability of an ultra-low permeability reservoir stratum and is less than 10 multiplied by 10-3μm2Therefore, NMSXQ-6 cannot be applied to ultra-low permeability reservoirs in combination with nano-imbibition agent particle size distribution (fig. 1 and fig. 6), and it can be seen that the particle size dispersion and stability of example 1 NMSXQ-1 are significantly better than those of comparative example 1 NMSXQ-6.
Comparative example 2 the second step starting material from example 2C4H9OCH2CH2OCH2CH2OH for C of equal mass10H21O(CH2CH2O)5CH2CH2OH, starting material C participating in the second reaction step in comparative example 210H21O(CH2CH2O)5CH2CH2OH has large steric hindrance, and is still difficult to combine with a silicon atom to form a covalent bond (marked by a dotted line in a structural formula) even from the side with the minimum steric hindrance under experimental conditions. In addition, in comparative example 2, the second step reacted the raw material C10H21O(CH2CH2O)5CH2CH2Due to the introduction of OH, the lipophilicity of the system is enhanced because the carbon chain is obviously increased, the oleophilic-hydrophilic balance of the NMSXQ-2 in the embodiment 2 is destroyed, the oil-water interfacial tension is difficult to be obviously reduced, the wettability of rock is difficult to be changed, and the imbibition oil extraction effect is poor. Therefore, the imbibition recovery of NMSXQ-7 was only 21.57%, which is much lower than the imbibition recovery of 63.85% for NMSXQ-2 of example 2.
In comparative example 3, the second reaction step is that in example 4, no 30% KOH solution is added to adjust the pH to 10, and the second reaction mechanism is a nucleophilic substitution reaction, wherein the nucleophilic substitution reaction is that under alkaline conditions, the anion OH-radius is smaller, the silicon nucleus is subjected to nucleophilic attack from the side with smaller steric hindrance, the silicon nucleus is charged with negative electricity, and the electron cloud is shifted to the OR group on the other side, so that the Si-O bond of the group is weakened and finally is broken to separate from the OR. Therefore, comparative example 3 does not have the conditions for the second step reaction to occur, and it is difficult to successfully modify the nanoparticles to obtain the nano imbibition agent NMSXQ-8 (the covalent bond is marked by a dotted line).
In summary, RO (CH)2CH2O)n-1CH2CH2The addition of OH is beneficial to modifying nano particles to form covalent bonds, so that the prepared nano imbibition agent keeps oleophylic-hydrophilic balance, effectively changes the wettability of rocks and exerts the imbibition oil extraction effect. The introduction of the ionic liquid enables the particle size of the nano imbibition agent to be smaller, the dispersibility and the stability to be better, and the nano imbibition agent can more easily go deep into the fine pore throat to play a role. The introduction of NaOH solution, KOH solution or ammonia water and other alkali liquids makes nucleophilic substitution reaction in alkaline environment to obtain target product, which plays a role in ultra-low permeability storage.
Claims (5)
1. The synthesis method of the temperature-resistant and salt-resistant nano imbibition agent is characterized by comprising the following steps:
mixing raw material BrCH2CH2OSi(OCH2CH3)3Adding the N-methylimidazole into a closed reactor which is provided with a thermometer and a condensation reflux device and is filled with an organic solvent 1, introducing nitrogen to remove oxygen, heating to 50-60 ℃, carrying out reflux reaction for 2-3h, and evaporating to remove the solvent to obtain an intermediate 1, wherein the structural formula is as follows:
intermediate 1, RO (CH)2CH2O)n-1CH2CH2Sequentially adding OH into another reactor containing organic solvent 2, adding alkali solution into the reaction system after completely dissolving, adjusting pH to 8-10, and reacting at 60-70 deg.CCarrying out vacuum pumping reaction for 2-3h under reduced pressure to obtain an intermediate 2, wherein the structural formula is as follows:
intermediate 2 and BrCH2Sequentially adding COONa into a reactor containing an organic solvent 3, adding ionic liquid into the system, fully dissolving, reacting at 70-80 ℃ for 5-6h, and evaporating to remove the solvent again to obtain the temperature-resistant and salt-resistant nano imbibition agent;
wherein, the added organic solvent 1, organic solvent 2 and organic solvent 3 are all selected from at least one of toluene, ethanol, acetonitrile, tetrahydrofuran and dimethyl sulfoxide;
the added ionic liquid is selected from [ Bmim ]]BF4、[Bmim]PF6、[C3OHmim]BF4、[Bmim][CF3SO3]And [ Bmim ]][Tf2N]At least one of the above-mentioned (B) is added in an amount of 0.3-0.5 per mill of the total mass of the reaction system;
BrCH added2CH2OSi(OCH2CH3)3The mass ratio of the N-methylimidazole to the organic solvent 1 is (1.5-2.0): (0.5-1.0): 5.0; intermediate 1, RO (CH)2CH2O)n-1CH2CH2The mass ratio of OH to the organic solvent 2 is (1.0-1.5): (1.5-2.0): 6.0;
wherein, the value range of n is 2-5, and R is straight-chain alkane with 4-8 carbon atoms; BrCH2The mass ratio of COONa, the intermediate 2 and the organic solvent 3 is (1.0-1.5): (2.5-3.0): 4.0.
2. The synthesis method according to claim 1, wherein the alkaline solution added is at least one selected from NaOH solution, KOH solution or ammonia water.
3. The temperature-resistant and salt-resistant nano imbibition agent prepared by the synthesis method according to claim 1 or 2.
4. The temperature-resistant and salt-tolerant nano imbibition agent as claimed in claim 3, which is applied to ultra-low permeability oilfield exploitation with the temperature of less than or equal to 150 ℃ and the mineralization degree of less than or equal to 32868 mg/L.
5. The application of claim 4, wherein after the temperature-resistant and salt-resistant nano imbibing agent with the concentration of 200ppm is added into the victory III type aqueous solution with the temperature of 150 ℃ and the concentration of 32868mg/L, the median value of the particle diameter is less than or equal to 49nm, the self-priming height of the capillary is more than or equal to 20mm, the surface tension is less than or equal to 24.168mN/m, and the interfacial tension is less than or equal to 8.17 x 10-3mN/m。
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