CN117402299A - Micro-nano spherical modified silica acid liquid gelatinizer and preparation method and application thereof - Google Patents

Micro-nano spherical modified silica acid liquid gelatinizer and preparation method and application thereof Download PDF

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CN117402299A
CN117402299A CN202210799342.9A CN202210799342A CN117402299A CN 117402299 A CN117402299 A CN 117402299A CN 202210799342 A CN202210799342 A CN 202210799342A CN 117402299 A CN117402299 A CN 117402299A
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nano
micro
solvent
acid liquid
drying
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刘云峰
刘雨舟
马晨洮
唐永帆
张燕
张倩
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to PCT/CN2023/096216 priority patent/WO2024007759A1/en
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    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
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    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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    • C09K8/62—Compositions for forming crevices or fractures
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Abstract

The invention provides a micro-nano spherical modified silica acid liquid gelatinizer, a preparation method and application thereof. The preparation method of the micro-nano spherical modified silica acid liquid gelatinizer comprises the following steps: making nano SiO 2 And silane coupling agent to obtain surface modified nano SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Surface modified nano SiO 2 And acrylic acid to obtain a macromolecular initiator; in the presence of an oxidant and a reducing agent, a macromolecular initiator is contacted and reacted with vinyl sulfonate, vinyl quaternary ammonium salt and N-vinyl pyrrolidone to obtain the micro-nano spherical modified silica acid liquid gelatinizer. The micro-nano spherical modified silica acid liquid gelatinizer is prepared by the method. The invention also provides application of the acid liquid gelling agent in acid fracturing. The acid liquid gelatinizing agent can reach 180 ℃ temperature resistance, and can support an oil-gas channel in a specific stratum, thereby improving recovery ratio.

Description

Micro-nano spherical modified silica acid liquid gelatinizer and preparation method and application thereof
Technical Field
The invention relates to the technical field of oil and gas field development, in particular to a micro-nano spherical modified silica acid liquid gelling agent and a preparation method and application thereof.
Background
The acid fracturing technology is the most dominant stimulation measure in oil and gas field stimulation technology. The method generally uses acid liquor to carry out corrosion or etching treatment on a target stratum so as to form an oil gas circulation channel and improve the yield increasing purpose. Studies have shown that the major contributors to acidizing and fracturing operations are the conductivity of the seam and the length of the eroded seam. Among them, how to reduce the corrosion rate of the acid solution is an important guarantee for ensuring the acidification operation. In field operation, the acid viscosity is generally increased to reduce the acidizing and fracturing operation, because the molecular chain grid structure can reduce the diffusion rate of hydrogen ions, thereby reducing the corrosion efficiency of the acid to the rock surface. Therefore, research on acid gelling agents has become one of the important subjects in the field of oil and gas field development.
In recent years, with the development difficulty of oil and gas wells gradually increasing, the number of deep wells and ultra-deep wells gradually increases, and the bottom hole temperature also increases. At high temperatures, polymer molecules are susceptible to thermal degradation, thermo-oxidative degradation, and the like, resulting in polymer molecule chain scission. Meanwhile, molecular thermal motion of hydrogen ions at high temperature can be aggravated, so that degradation of molecular chains is promoted, and the tackifying performance of drilling fluid is damaged. According to product investigation, most gelled acid developed by some companies faces the problems of poor acid resistance and weak temperature resistance; some retarding acids for high-temperature-resistant acid liquor developed by companies have excellent temperature resistance and acid resistance, but the price of the retarding acids is high, so that the production benefits of oilfield enterprises are affected.
At present, the improvement of the temperature resistance of polymer molecules mainly comprises the following modes: 1. introducing a macromolecular rigid side chain; 2. the rigidity of the main chain is improved; 3. introducing a monomer with a hydrolysis-resistant functional group; 4. introducing a hydrophobically associating monomer; 5. a rigid skeletal structure is introduced. Most researchers generally improve the temperature resistance of acid gelling agents by introducing macromolecular side chains or hydrolysis-resistant functional groups, mainly due to the clear polymerization mechanism and ease of synthesis.
CN113563505a discloses a heat-resistant acid-resistant salt-resistant acid liquid gelling agent and a preparation method thereof. The acid liquid gelatinizer is one kind of acid liquid gelatinizer synthesized with anionic monomer, cationic monomer, salt resisting monomer, heat resisting monomer, hydrophobic monomer, coupling agent and other treating agent. The acid liquid gelatinizer prepared by the invention has the characteristics of strong tackifying capability, small shearing influence, stable acid resistance, good temperature resistance, small secondary damage to stratum and the like. But the reaction steps are complicated, which is unfavorable for mass production.
CN113321764a discloses an acid liquid gelling agent, a preparation method and application thereof. The acid solution gelling agent is synthesized by acrylamide, functional monomers and methacryloxyethyl trimethyl ammonium chloride under the action of a chain control agent and an initiator, has high thickening performance and good temperature and shear resistance, and can better meet the high-temperature acidification requirements of the deep part of a stratum. But the reaction steps are complicated, which is unfavorable for mass production.
CN110982507a discloses an acid liquid gelling agent for acid fracturing, a preparation method and application thereof, which is synthesized by acrylamide, bio-based cationic monomer, temperature-resistant salt-resistant monomer and temperature-sensitive monomer. The acid liquid gelatinizer has excellent dissolubility and tackifying performance in acid liquid. But has poor temperature resistance and cannot be used in high-temperature wells with the temperature of more than 150 ℃.
CN108913119a discloses a gelatinizer for fracturing and a preparation method thereof, which is synthesized by monomers such as modified hydroxypropyl guar, acid liquid resistance-reducing agent, acid liquid corrosion inhibitor and the like. The gelatinizer has the advantages of high viscosity, low water insoluble matter, quick dissolution, and good fluidity, and can be used for preparing liquid rapidly. But has poor temperature resistance and cannot be used in high-temperature wells with the temperature of more than 150 ℃.
CN106047333a discloses a high temperature resistant acid liquid gelling agent and a preparation method thereof, wherein the acid liquid gelling agent is polymerized by three monomers, namely an acrylamide monomer, an acryloyloxyethyl trimethyl ammonium chloride monomer and a third monomer. The high-temperature resistant acid liquid gelling agent is simple and easy to synthesize, has the functions of high temperature resistance, salt resistance and retarding, and can be effectively applied to the acidification reconstruction construction of high-temperature carbonate rock. However, the gelling agent merely increases the molecular weight of the molecular chain, and does not increase the rigidity and heat resistance of the molecular chain structure.
CN104388075a discloses an acid liquor gelling agent suitable for high-temperature carbonate acidification and a preparation method thereof, wherein the acid liquor gelling agent is a cationic acid liquor gelling agent synthesized by initiating copolymerization of two monomers of methacryloxyethyl trimethyl ammonium chloride and acrylamide by an initiator, and the acid liquor gelling agent has the advantages of less consumption, simple preparation, low cost and stable performance, and meets the construction requirements of high-temperature carbonate acidification. However, the gelling agent merely increases the molecular weight of the molecular chain, and does not increase the rigidity and heat resistance of the molecular chain structure.
CN103923633a discloses a gelled acid solution suitable for acidification of high temperature carbonate rock, comprising the following components: 0.6-0.8% of acid liquid gelatinizer, 2-4% of corrosion inhibitor, 1-2% of cleanup additive, 1-2% of iron ion stabilizer and 15-22% of hydrochloric acid. The gelled acid liquid can be applied to high-temperature carbonate rock acidification construction, has the functions of high temperature resistance, salt resistance and retarding, and can be effectively applied to high-temperature carbonate rock acidification reconstruction construction. However, the invention only carries out simple compounding and does not carry out research and development of a molecular treating agent.
US20100028434A1 discloses a biopolymer liquid-water composition for production from gel systems and gels, the pH of the liquid composition being adjustable in the range 5.8 to 7.4 and forming a stable solid and homogeneous gel at 10 to 70 ℃. Wherein the water-soluble molecule is a monophosphate dibasic salt, a monosulfonate, a monosulfate, a monocarboxylate, etc. of the polyhydric alcohol. The composite gelling agent provided by the invention is not explored in the aspect of temperature resistance, and has a limited application range.
Therefore, how to prepare the acid gelling agent for high-temperature resistant acid is the current research key point and difficulty.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a micro-nano spherical modified silica acid liquid gelling agent, and a preparation method and application thereof. The invention provides micro-nano spherical modified SiO 2 The acid liquid gelatinizer can overcome the problem of degradation of the acid liquid gelatinizer at high temperature in the prior art, and has excellent acid resistance and temperature resistance.
In order to achieve the above object, the present invention provides a method for preparing a micro-nano spherical modified silica acid liquid gelling agent, which comprises the following steps:
(1) Making nano SiO 2 And silane coupling agent in a first solvent to perform a first contact reaction, and at least drying to obtain surface modified nano SiO 2 ；
(2) Nano SiO for modifying the surface 2 And acrylic acid in a second solvent for a second contact reaction, and at least drying to obtain a macromolecular initiator;
(3) And in the presence of an oxidant and a reducing agent, carrying out a third contact reaction on the macromolecular initiator, vinyl sulfonate, vinyl quaternary ammonium salt and N-vinyl pyrrolidone in a third solvent to obtain the micro-nano spherical modified silica acid liquid gelling agent.
In the above preparation method, preferably, in step (1), the nano SiO 2 The average particle diameter of (2) is 10-20 nm.
In the above preparation method, preferably, in the step (1), the silane coupling agent includes one or a combination of several of γ -aminopropyl triethoxysilane (KH 550), N- (β -aminoethyl) - γ -aminopropyl trimethoxysilane (KH 792), and N- (β -aminoethyl) - γ -aminopropyl methyldimethoxysilane (KH 602), etc.
In the above-mentioned production method, preferably, in the step (1), the amount of the silane coupling agent to be added is 8 to 12g (i.e., the amount of the silane coupling agent to be added is 80 to 120 g/L) with respect to 100mL of the first solvent.
In the above preparation method, preferably, in the step (1), the nano SiO is preferably used in an amount of 100mL of the first solvent 2 In an amount of 1 to 5g (i.e., the nano SiO 2 The amount of (C) added is 10-50 g/L), more preferably 1.5-3.5g.
In the above preparation method, preferably, in step (1), the first solvent may include water, for example, deionized water or distilled water, or the like.
In the above preparation method, preferably, in step (1), the conditions of the first contact reaction are: the reaction temperature is 25-40 ℃ and the reaction time is 5-8h. More preferably, the first contact reaction may be performed under stirring at a speed of 200 to 1200r/min. After the first contact reaction is completed, the reaction product may be subjected to conventional separation (e.g., filtration and/or centrifugation), washing, and the like. Drying to obtain the surface modified nano SiO 2 。
In the above preparation method, preferably, in step (1), the drying is freeze-drying under the following conditions: freezing for 8-12 min with liquid nitrogen, and freeze drying (vacuum drying) at-50deg.C and 9Pa for 24-48 h.
In the preparation of the inventionIn the step (1) of the method, the silane coupling agent adopted by the invention can be prepared in nano SiO 2 Surface reaction to prepare the modified nano SiO with contact sites on the surface 2 And (3) microspheres.
In the above-mentioned production method, preferably, in the step (2), the acrylic acid is added in an amount of 0.05 to 0.5mol (i.e., the acrylic acid is added in an amount of 0.5 to 5 mol/L), more preferably 0.1 to 0.3mol, relative to 100mL of the second solvent.
In the above preparation method, preferably, in step (2), the surface-modified nano SiO is preferably used in an amount of 100mL of the second solvent 2 The amount of (C) added is 5-30g, more preferably 10-20g.
In the above-mentioned production method, preferably, in step (2), the second solvent may include water, for example, deionized water or distilled water, or the like.
In the above preparation method, preferably, in step (2), the conditions of the second contact reaction are: the reaction temperature is 25-40 ℃ and the reaction time is 5-8h. More preferably, the second contact reaction may be carried out with stirring at a speed of 600-1000r/min. After the second contact reaction is completed, the reaction product may be subjected to conventional separation (e.g., filtration and/or centrifugation), washing, and the like. And drying to obtain the macromolecular initiator.
In the above preparation method, preferably, in step (2), the drying is freeze-drying under the following conditions: freezing for 8-12 min with liquid nitrogen, and freeze drying (vacuum drying) at-50deg.C and 9Pa for 24-48 h.
In step (2) of the production method of the present invention, the surface-modified nano SiO 2 Can be used as a framework, the surface of the framework is provided with a reaction site with higher activity, and the surface of the framework can react with acrylic acid, so that the activity of the reaction site is increased, and the modified nano SiO is further improved 2 So that after subsequent addition reaction, the nano SiO can be modified 2 And polymer films are formed on the surfaces of the balls, so that the temperature resistance and acid resistance of the prepared acid liquid gelling agent are improved.
In the above-mentioned production method, preferably, in the step (3), the vinyl sulfonate (i.e., vinyl group-containing sulfonate) includes one or a combination of several of sodium 2-acrylamido-2-methylpropane sulfonate, sodium allylsulfonate, sodium styrenesulfonate, sodium vinylsulfonate, and the like.
In the above-mentioned production method, preferably, in the step (3), the vinyl quaternary ammonium salt comprises one or a combination of several of dimethyldiallylammonium chloride, methacryloxyethyl trimethylammonium chloride, trimethylvinylammonium bromide, 4-vinylbenzyltrimethylammonium chloride and the like.
In the above preparation method, preferably, in the step (3), the amount of the macroinitiator to be added is 10 to 20g (i.e., the amount of the macroinitiator to be added is 100 to 200 g/L) with respect to 100mL of the third solvent.
In the above-mentioned production method, preferably, in the step (3), the amount of the vinyl sulfonate to be added is 0.05 to 0.5mol (i.e., the amount of the vinyl sulfonate to be added is 0.5 to 5.0 mol/L), more preferably 0.1 to 0.3mol, with respect to 100mL of the third solvent.
In the above preparation method, preferably, in step (3), the molar ratio of the vinyl sulfonate, the vinyl quaternary ammonium salt, and the N-vinylpyrrolidone is 1: (1-3): (0.5-1.5), more preferably 1: (1.2-2.3): (0.7-1.3).
In the above production method, preferably, in step (3), the oxidizing agent comprises ammonium persulfate and/or potassium persulfate or the like.
In the above preparation method, preferably, in step (3), the reducing agent comprises sodium bisulphite.
In the above-mentioned production method, preferably, in the step (3), the amount of the oxidizing agent to be added is 0.001 to 0.005mol (i.e., the amount of the oxidizing agent to be added is 0.01 to 0.05 mol/L) with respect to 100mL of the third solvent.
In the above preparation method, preferably, in step (3), the molar ratio of the oxidizing agent to the reducing agent is 1: (0.5-1.5), more preferably 1: (0.8-1.3).
In the above preparation method, preferably, in step (3), the third solvent may include water, for example, deionized water or distilled water, etc.
In the above preparation method, preferably, in step (3), the conditions of the third contact reaction are: the reaction temperature is 65-80 ℃, the reaction time is 3-6h, and the third contact reaction is carried out under nitrogen atmosphere. More preferably, the third contact reaction may be performed under stirring at a speed of 600 to 800r/min. After the third contact reaction is completed, the reaction product may be subjected to conventional steps such as filtration and/or centrifugation, washing, and the like. And drying to obtain the micro-nano spherical modified silica acid liquid gelling agent.
In the above preparation method, preferably, in the step (3), the drying is vacuum drying, the drying temperature is 60 ℃, the drying time is 24 hours, and the vacuum degree is 9Pa.
In the present invention, the vinyl quaternary ammonium salt monomer, the vinyl sulfonate monomer and the N-vinyl pyrrolidone monomer are reacted after opening the double bond of c=c. The vinyl sulfonate monomer, the vinyl quaternary ammonium salt monomer and the N-vinyl pyrrolidone monomer can be subjected to polymerization reaction through atom transfer free radical in the presence of an oxidant and a reducing agent; the generated polymer can be combined with the nano SiO modified by the invention 2 The high-activity reaction sites on the surface react, and the steric hindrance effect provided by the macromolecular functional groups on the surface can effectively prevent the polymers from intertwining and adsorbing, so that the temperature resistance of the prepared acid liquid gelling agent is improved.
FIG. 1 shows a micro-nano-scale spherical modified SiO according to the present invention 2 The preparation flow and molecular structure design diagram of the acid liquid gelatinizer. As shown in figure 1, the preparation method of the micro-nano spherical modified silica acid liquid gelatinizer provided by the invention comprises the following steps of firstly, using a silane coupling agent to prepare a nano SiO 2 The surface is added with active reaction sites, and then the active reaction sites react with acrylic acid, so that the activity of the reaction sites is increased, and the modified nano SiO is further improved 2 Is introduced by the reaction between the amine group and the carboxyl group in the vinyl quaternary ammonium salt monomer, the vinyl sulfonate monomer and the N-vinyl pyrrolidone monomerAnd C, the problem of low grafting rate of the monomer on the surface of the solid particles due to the steric hindrance effect caused by the existence of the solid particles can be effectively solved. Meanwhile, the vinyl quaternary ammonium salt monomer and the vinyl sulfonate monomer adopted by the invention can provide macromolecular side chains on one hand and improve the steric hindrance of the prepared polymer; on the other hand, the stability of the polymer molecular chain can be well maintained due to the anti-polyelectrolyte effect of anions and cations; the N-vinyl pyrrolidone monomer adopted by the invention further improves the branched chain rigidity of the prepared polymer molecular chain.
The second aspect of the invention provides a micro-nano spherical modified silica acid liquid gelling agent, which is prepared by the preparation method.
According to a specific embodiment of the present invention, preferably, the micro-nano-scale spherical modified silica acid gel agent has an average particle diameter of 500 to 2000nm, more preferably 500 to 900nm.
According to a specific embodiment of the present invention, preferably, the micro-nano-scale spherical modified silica acid solution gelling agent is prepared in a 20% HCl aqueous solution by mass fraction at 180 ℃ for 170s -1 Shearing for 1h under the condition, wherein the apparent viscosity is more than 45 mPa.s.
The third aspect of the invention provides an application of the micro-nano spherical modified silica acid liquid gelling agent in acidizing fracturing.
In the above application, the target reservoir temperature for the acid fracturing is preferably 150 ℃ or higher, more preferably 180 ℃ or higher.
The micro-nano spherical modified silica acid liquid gelatinizer is prepared from micro-nano spherical SiO 2 Is loaded on the micro-nano spherical SiO 2 The organic high molecular polymer. The invention adopts micro-nano spherical modified SiO 2 As an excellent template, a layer of polymer is wrapped on the surface, and a macromolecular side chain and a rigid main chain are introduced, so that the temperature resistance and acid resistance of the acid liquid gelling agent are improved. The gelled acid system formed by the acid liquid gelling agent can be applied to a high-temperature reservoir (180 ℃ or even more) and has apparent viscosityThe temperature is less affected by the high temperature, and the high apparent viscosity is still maintained under the condition of high shear rate, thereby further delaying H + The release speed is reduced, the acid rock reaction rate is reduced, the effective acting distance of acid liquor is increased, and the acidification modification effect of the high-temperature carbonate reservoir is improved. Therefore, the micro-nano spherical modified silica acid liquid gelatinizer has excellent temperature resistance and acid resistance, overcomes the problem of degradation of the acid liquid gelatinizer at high temperature in the prior art, and can support an oil gas channel in a specific stratum so as to improve the recovery ratio.
In conclusion, the micro-nano spherical modified SiO provided by the invention 2 The acid liquid gelling agent comprises the following excellent technical effects:
(1) Compared with the traditional acid liquid gelatinizer, the micro-nano spherical modified SiO of the invention 2 The acid liquid gelatinizer has rigid skeleton grains and can enter the pores of the target stratum to support the oil and gas channel;
(2) Compared with the traditional acid liquid gelatinizer, the micro-nano spherical modified SiO of the invention 2 The polymer molecular chain of the acid liquid gelatinizer has macromolecular side chains and functional groups, so that the temperature resistance of the acid liquid gelatinizer can be improved;
(3) Compared with the traditional acid liquid gelatinizer, the micro-nano spherical modified SiO of the invention 2 The reaction condition of the acid liquid gelling agent is easy to control, the reaction process is relatively stable, and industrialization is easy to realize.
Drawings
FIG. 1 shows a micro-nano-scale spherical modified SiO according to the present invention 2 The preparation flow and molecular structure design diagram of the acid liquid gelatinizer.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the nano-silica used was supplied by the gold technology limited of the island of the germany family.
The silane coupling agent, N-vinyl pyrrolidone, vinyl sulfonate and vinyl quaternary ammonium salt are all provided by Shanghai test group of China.
The potassium persulfate, ammonium persulfate, and sodium bisulfite used were all supplied by ala Ding Shiji limited.
The average particle size of the acid gellant was measured by a markov Zetasizer 3000 potential-particle size tester.
Example 1
The embodiment provides a micro-nano spherical modified silica acid liquid gelling agent, which is prepared by the following method:
(1) 68g of nano SiO was added to 2000mL of deionized water 2 (20 nm), stirring magnetically for 20min to disperse in deionized water to obtain nanometer SiO 2 A suspension; at the nano SiO 2 Slowly dripping 200g of silane coupling agent KH550 into the suspension, and stirring under the condition of 1200r/min to dissolve the silane coupling agent KH 550; then continuously stirring and reacting for 8 hours at 40 ℃, filtering, freezing for 10 minutes by liquid nitrogen, and vacuum drying for 24 hours at-50 ℃ and 9Pa to obtain the surface modified nano SiO 2 ；
(2) Adding 0.6mol of Acrylic Acid (AA) into 200mL of deionized water to obtain an AA solution; 39.2g of the surface-modified nano SiO obtained in the step (1) was reacted with 2 Adding to the AA solution; reacting for 8 hours at 40 ℃ and 1000r/min stirring speed, filtering, freezing for 10 minutes by liquid nitrogen, and vacuum drying for 24 hours at-50 ℃ and 9Pa to obtain a macromolecular initiator;
(3) In a 500mL three-necked round bottom flask equipped with a thermometer, a stirring rod and a nitrogen guide tube, 38.6g of the macroinitiator obtained in the step (2), 137.54g (0.6 mol) of 2-acrylamide-2-methylpropanesulfonic acid sodium salt, 213.41g (1.32 mol) of dimethyldiallylammonium chloride, 86.58g (0.78 mol) of N-vinylpyrrolidone were dispersed into 200mL deionized water, the temperature was raised to 80 ℃, 2.7g (0.01 mol) of potassium persulfate and 1.35g (0.013 mol) of sodium hydrogensulfite were sequentially added, and the reaction was carried out at a stirring speed of 800r/min for 6 hours; after the reaction is finished, filtering, washing and drying (the drying is vacuum drying, the drying temperature is 60 ℃, the drying time is 24 hours, and the vacuum degree is 9 Pa) to obtain the micro-nano spherical modified silica acid liquid gelling agent which is named NSGA-1 (Nano Spheres of Gelling Agent-1).
The average particle size of NSGA-1 was 532.95nm.
Example 2
The embodiment provides a micro-nano spherical modified silica acid liquid gelling agent, which is prepared by the following method:
(1) 32g of nano SiO was added to 2000mL of deionized water 2 Magnetic stirring for 20min to uniformly disperse the nano SiO in deionized water 2 A suspension; at the nano SiO 2 160g of silane coupling agent KH792 is slowly added dropwise into the suspension, and 200r/min is stirred to dissolve the silane coupling agent KH 792; then continuously stirring and reacting for 8 hours at 40 ℃, filtering, freezing for 8 minutes by liquid nitrogen, and vacuum drying for 48 hours at-50 ℃ and 9Pa to obtain the surface modified nano SiO 2 ；
(2) Adding 0.2mol of Acrylic Acid (AA) into 200mL of deionized water to obtain an AA solution; 39.2g of the surface-modified nano SiO obtained in the step (1) was reacted with 2 Adding to the AA solution; reacting for 8 hours at 40 ℃ and 1000r/min stirring speed, filtering, freezing for 10 minutes by liquid nitrogen, and vacuum drying for 24 hours at-50 ℃ and 9Pa to obtain a macromolecular initiator;
(3) 29.48g of the macroinitiator obtained in the step (2), 57.64g (0.4 mol) of sodium allylsulfonate, 191.08g (0.92 mol) of methacryloyloxyethyl trimethyl ammonium chloride and 44.4g (0.4 mol) of N-vinylpyrrolidone are dispersed into 200mL of deionized water in a 500mL three-necked round bottom flask equipped with a thermometer, a stirring rod and a nitrogen guide tube, the temperature is raised to 80 ℃, 2.7g (0.01 mol) of potassium persulfate and 1.35g (0.013 mol) of sodium hydrogensulfite are sequentially added, and the reaction is carried out for 6 hours at a stirring speed of 800 r/min; after the reaction is finished, filtering, washing and drying are carried out to obtain the micro-nano spherical modified silica acid liquid gelling agent which is named NSGA-2 (Nano Spheres of Gelling Agent-2).
The average particle size of NSGA-2 was 732.95nm.
Example 3
The embodiment provides a micro-nano spherical modified silica acid liquid gelling agent, which is prepared by the following method:
(1) 50g of nano SiO was added to 2000mL of deionized water 2 Magnetic stirring for 20min to uniformly disperse the nano SiO in deionized water 2 A suspension; at the nano SiO 2 Slowly dripping 240g of silane coupling agent KH602 into the suspension, and stirring at 1000r/min to dissolve the silane coupling agent KH 602; then continuously stirring and reacting for 8 hours at 40 ℃, filtering, freezing for 12 minutes by liquid nitrogen, and vacuum drying for 24 hours at-50 ℃ and 9Pa to obtain the surface modified nano SiO 2 ；
(2) 0.4mol of Acrylic Acid (AA) is added into 200mL of deionized water to obtain an AA solution; 39.2g of the surface-modified nano SiO obtained in the step (1) was reacted with 2 Adding to the AA solution; reacting for 8h at 40 ℃ at a stirring speed of 1000r/min, filtering, freezing with liquid nitrogen for 12min, and vacuum drying for 36h at-50 ℃ under 9Pa to obtain a macromolecular initiator;
(3) In a 500mL three-necked round bottom flask equipped with a thermometer, a stirring rod and a nitrogen guide tube, 22.4g of the macroinitiator obtained in the step (2), 41.23g (0.2 mol) of sodium styrene sulfonate, 41.52g (0.25 mol) of trimethyl vinyl ammonium bromide and 15.54g (0.14 mol) of N-vinyl pyrrolidone are dispersed into 200mL deionized water, the temperature is raised to 80 ℃, 2.7g (0.01 mol) of potassium persulfate and 1.35g (0.013 mol) of sodium bisulfate are sequentially added to react for 6 hours at a stirring speed of 800 r/min; after the reaction is finished, filtering, washing and drying are carried out to obtain the micro-nano spherical modified silica acid liquid gelling agent which is named NSGA-3 (Nano Spheres of Gelling Agent-3).
The average particle size of NSGA-3 was 892.43nm.
Example 4
The embodiment provides a micro-nano spherical modified silica acid liquid gelling agent, which is prepared by the following method:
(1) 96g of nano SiO was added to 2000mL of deionized water 2 Magnetic stirring for 20min to uniformly disperse the nano SiO in deionized water 2 A suspension; at the nano SiO 2 190g of the silane coupling agent KH550 are slowly added dropwise to the suspension and 800r +.Stirring for dissolving; then continuously stirring and reacting for 8 hours at 40 ℃, filtering, freezing for 12 minutes by liquid nitrogen, and vacuum drying for 30 hours at-50 ℃ and 9Pa to obtain the surface modified nano SiO 2 ；
(2) 1.0mol of Acrylic Acid (AA) is added into 200mL of deionized water to obtain an AA solution; 39.2g of the surface-modified nano SiO obtained in the step (1) was reacted with 2 Adding to the AA solution; reacting for 8h at 40 ℃ at a stirring speed of 1000r/min, filtering, freezing with liquid nitrogen for 12min, and vacuum drying for 30h at-50 ℃ under 9Pa to obtain a macromolecular initiator;
(3) In a 500mL three-necked round bottom flask equipped with a thermometer, a stirring rod and a nitrogen guide tube, 37.2g of the macroinitiator obtained in the step (2), 110.58g (0.85 mol) of sodium vinylsulfonate, 451.98g (2.13 mol) of 4-vinylbenzyl trimethyl ammonium chloride and 133.2g (1.2 mol) of N-vinylpyrrolidone were dispersed into 200mL deionized water, the temperature was raised to 80 ℃, 2.7g (0.01 mol) of potassium persulfate and 1.35g (0.013 mol) of sodium hydrogensulfite were sequentially added and reacted for 6 hours at a stirring speed of 800 r/min; after the reaction is finished, filtering, washing and drying are carried out to obtain the micro-nano spherical modified silica acid liquid gelling agent which is named NSGA-4 (Nano Spheres of Gelling Agent-4).
The average particle size of NSGA-4 was 1035.28nm.
Example 5
The embodiment provides a micro-nano spherical modified silica acid liquid gelling agent, which is prepared by the following method:
(1) 24g of nano SiO was added to 2000mL of deionized water 2 Magnetic stirring for 20min to uniformly disperse the nano SiO in deionized water 2 A suspension; at the nano SiO 2 Slowly dripping 210g of silane coupling agent KH792 into the suspension, and stirring at 400r/min to dissolve the silane coupling agent KH 792; then continuously stirring and reacting for 8 hours at 40 ℃, filtering, freezing for 11 minutes by liquid nitrogen, and vacuum drying for 33 hours at-50 ℃ and 9Pa to obtain the surface modified nano SiO 2 ；
(2) Adding 0.12mol of Acrylic Acid (AA) into 200mL of deionized water to obtain an AA solution; 39.2g of the surface-modified nano SiO obtained in the step (1) was reacted with 2 Adding the saidAA in solution; reacting for 8h at 40 ℃ at a stirring speed of 1000r/min, filtering, freezing for 11min by liquid nitrogen, and vacuum drying for 33h at-50 ℃ under the condition of 9Pa to obtain a macromolecular initiator;
(3) 31.64g of the macroinitiator obtained in the step (2), 160.46g (0.7 mol) of sodium 2-acrylamido-2-methylpropanesulfonate, 124.49g (0.77 mol) of dimethyl diallyl ammonium chloride, 38.85g (0.35 mol) of N-vinylpyrrolidone are dispersed in 200mL of deionized water in a 500mL three-necked round bottom flask equipped with a thermometer, a stirring rod and a nitrogen guide tube, the temperature is raised to 80 ℃, 2.7g (0.01 mol) of potassium persulfate and 1.35g (0.013 mol) of sodium bisulphite are sequentially added, and the reaction is carried out for 6 hours at a stirring speed of 800 r/min; after the reaction is finished, filtering, washing and drying are carried out to obtain the micro-nano spherical modified silica acid liquid gelling agent which is named NSGA-5 (Nano Spheres of Gelling Agent-5).
The average particle size of NSGA-5 was 1486.38nm.
Example 6
The embodiment provides a micro-nano spherical modified silica acid liquid gelling agent, which is prepared by the following method:
(1) 60g of nano SiO was added to 2000mL of deionized water 2 Magnetic stirring for 20min to uniformly disperse the nano SiO in deionized water 2 A suspension; at the nano SiO 2 220g of silane coupling agent KH602 is slowly added dropwise into the suspension, and the suspension is stirred for 300r/min to be dissolved; then continuously stirring and reacting for 8 hours at 40 ℃, filtering, freezing for 10 minutes by liquid nitrogen, and vacuum drying for 44 hours at-50 ℃ and 9Pa to obtain the surface modified nano SiO 2 ；
(2) 0.5mol of Acrylic Acid (AA) is added into 200mL of deionized water to obtain AA solution; 39.2g of the surface-modified nano SiO obtained in the step (1) was reacted with 2 Adding to the AA solution; reacting at 40deg.C and 1000r/min stirring speed for 8 hr, filtering, freezing with liquid nitrogen for 10min, and vacuum drying at-50deg.C and 9Pa for 44 hr to obtain macromolecular initiator;
(3) In a 500mL three-necked round bottom flask equipped with a thermometer, a stirring rod and a nitrogen guide tube, 20.5g of the macroinitiator obtained in the step (2), 20.17g (0.14 mol) of sodium allylsulfonate, 78.93g (0.38 mol) of methacryloyloxyethyl trimethyl ammonium chloride, 9.32g (0.084 mol) of N-vinylpyrrolidone were dispersed into 200mL deionized water, the temperature was raised to 80 ℃, 2.7g (0.01 mol) of potassium persulfate and 1.35g (0.013 mol) of sodium hydrogensulfite were sequentially added, and the mixture was reacted for 6 hours at a stirring speed of 800 r/min; after the reaction is finished, filtering, washing and drying are carried out to obtain the micro-nano spherical modified silica acid liquid gelling agent which is named NSGA-6 (Nano Spheres of Gelling Agent-6).
The average particle size of NSGA-6 was 1967.47nm.
Comparative example 1
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (1), the silane coupling agent KH550 was not added, and other raw materials and amounts and preparation procedures were the same as those of example 1, to obtain an acid gelling agent D1, whose average particle diameter was measured to be 3.28 μm.
Comparative example 2
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (2), acrylic Acid (AA) was not added, and other raw materials and amounts and preparation procedures were the same as in example 1, to obtain an acid gelling agent D2, whose average particle diameter was measured to be 15.28 μm.
Comparative example 3
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (3), the addition amount of sodium 2-acrylamido-2-methylpropanesulfonate was changed to 0.48g, and the other raw materials and the amounts and preparation process were the same as in example 1, to obtain an acid gelling agent D3, the average particle diameter of which was measured to be 1.52. Mu.m.
Comparative example 4
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (3), the amount of N-vinylpyrrolidone added was changed to 1.16g, and the other raw materials and amounts and preparation process were the same as in example 1, to obtain an acid gelling agent D4, the average particle diameter of which was measured to be 1.24. Mu.m.
Comparative example 5
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (3), dimethyl diallyl ammonium chloride was not added, and other raw materials and amounts and preparation procedures were the same as in example 1, to obtain an acid gelling agent D5 having an average particle diameter of 1.12 μm.
Comparative example 6
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (3), dimethyl diallyl ammonium chloride was replaced with 1.32mol of acrylamide, and other raw materials and amounts and preparation procedures were the same as in example 1, to obtain an acid gelling agent D6, the average particle diameter of which was measured to be 0.98 μm.
Comparative example 7
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (3), N-vinylpyrrolidone was replaced with styrene by 0.78mol, and the other raw materials and amounts and preparation process were the same as in example 1, to obtain an acid gelling agent D7, the average particle diameter of which was measured to be 2.26. Mu.m.
Comparative example 8
This comparative example provides an acid gelling agent which was prepared substantially in accordance with the method of example 1, except that in step (3), sodium 2-acrylamido-2-methylpropanesulfonate was replaced with 0.6mol of styrene, and the other raw materials and amounts and preparation process were the same as in example 1, to obtain an acid gelling agent D8, the average particle diameter of which was measured to be 2.46 μm.
Test case
The acid gelling agents provided in examples 1 to 6 and comparative examples 1 to 8 were tested for apparent viscosity at room temperature at 180℃with a mass fraction of 20% aqueous HCl, and the results are shown in Table 1.
TABLE 1 Performance parameters of different types of acid gellants
Wherein, the normal temperature is 25 ℃.
As apparent from Table 1, the micro-nano spherical modified silica acid liquid gelling agent prepared by the embodiment of the invention has the following characteristics that the temperature is 180 ℃ and the time is 170 seconds -1 Shearing for 1h under the condition, the apparent viscosity is more than 45 mPa.s, so that the modified polypropylene has excellent temperature resistance and acid resistance.

Claims (12)

1. The preparation method of the micro-nano spherical modified silica acid liquid gelatinizer comprises the following steps:
(1) Making nano SiO 2 And silane coupling agent in a first solvent to perform a first contact reaction, and at least drying to obtain surface modified nano SiO 2 ；
(2) Nano SiO for modifying the surface 2 And acrylic acid in a second solvent for a second contact reaction, and at least drying to obtain a macromolecular initiator;
(3) And in the presence of an oxidant and a reducing agent, carrying out a third contact reaction on the macromolecular initiator, vinyl sulfonate, vinyl quaternary ammonium salt and N-vinyl pyrrolidone in a third solvent to obtain the micro-nano spherical modified silica acid liquid gelling agent.
2. The preparation method according to claim 1, wherein, in step (1), the nano SiO 2 The average grain diameter of the polymer is 10-20 nm;
preferably, in the step (1), the silane coupling agent includes one or a combination of several of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl methyldimethoxysilane;
preferably, in the step (1), the silane coupling agent is added in an amount of 8 to 12g with respect to 100mL of the first solvent;
preferably, in step (1), the nano SiO is used in an amount of 100mL of the first solvent 2 The addition amount of (2) is 1-5g;
preferably, in step (1), the first solvent comprises water.
3. The production method according to claim 1, wherein in step (1), the conditions of the first contact reaction are: the reaction temperature is 25-40 ℃ and the reaction time is 5-8h; preferably, the first contact reaction is carried out under stirring, and the stirring speed is 200-1200 r/min;
preferably, in step (1), the drying is freeze-drying, and the conditions of the freeze-drying are: freezing for 8-12 min with liquid nitrogen, and freeze drying at-50 deg.c and 9Pa for 24-48 hr.
4. The production process according to claim 1, wherein, in the step (2), the acrylic acid is added in an amount of 0.05 to 0.5mol with respect to 100mL of the second solvent;
preferably, in step (2), the surface-modified nano-SiO is compared to 100mL of the second solvent 2 The addition amount of (2) is 5-30g;
preferably, in step (2), the second solvent comprises water.
5. The production method according to claim 1, wherein in the step (2), the conditions of the second contact reaction are: the reaction temperature is 25-40 ℃ and the reaction time is 5-8h; preferably, the second contact reaction is carried out under stirring at a speed of 600-1000r/min;
preferably, in step (2), the drying is freeze-drying, and the conditions of the freeze-drying are: freezing for 8-12 min with liquid nitrogen, and freeze drying at-50 deg.c and 9Pa for 24-48 hr.
6. The production method according to claim 1, wherein in the step (3), the vinyl sulfonate comprises one or a combination of several of sodium 2-acrylamido-2-methylpropanesulfonate, sodium allylsulfonate, sodium styrenesulfonate, and sodium vinylsulfonate.
7. The production method according to claim 1, wherein in the step (3), the vinyl quaternary ammonium salt comprises one or a combination of several of dimethyldiallylammonium chloride, methacryloxyethyltrimethylammonium chloride, trimethylvinylammonium bromide and 4-vinylbenzyltrimethylammonium chloride.
8. The production method according to any one of claims 1, 6 and 7, wherein, in the step (3), the macroinitiator is added in an amount of 10 to 20g with respect to 100mL of the third solvent;
preferably, in step (3), the vinyl sulfonate is added in an amount of 0.05 to 0.5mol with respect to 100mL of the third solvent;
preferably, in step (3), the molar ratio of the vinyl sulfonate, the vinyl quaternary ammonium salt, and the N-vinylpyrrolidone is 1: (1-3): (0.5-1.5), more preferably 1: (1.2-2.3): (0.7-1.3).
9. The production method according to claim 1, wherein in step (3), the oxidizing agent comprises ammonium persulfate and/or potassium persulfate;
preferably, in step (3), the reducing agent comprises sodium bisulphite;
preferably, in step (3), the oxidizing agent is added in an amount of 0.001 to 0.005mol with respect to 100mL of the third solvent;
preferably, in step (3), the molar ratio of the oxidizing agent to the reducing agent is 1: (0.5-1.5), more preferably 1: (0.8-1.3);
preferably, in step (3), the third solvent comprises water.
10. The production method according to claim 1, wherein in the step (3), the conditions of the third contact reaction are: the reaction temperature is 65-80 ℃, the reaction time is 3-6h, and the third contact reaction is carried out under nitrogen atmosphere; preferably, the third contact reaction is carried out under stirring at a speed of 600-800r/min.
11. A micro-nano-scale spherical modified silica acid liquid gelling agent prepared by the preparation method of any one of claims 1 to 10;
preferably, the average particle size of the micro-nano spherical modified silica acid liquid gelatinizer is 500-2000nm, more preferably 500-900nm;
preferably, the micro-nano spherical modified silica acid liquid gelatinizer is in an aqueous solution of HCl with the mass fraction of 20 percent, at 180 ℃ for 170s -1 Shearing for 1h under the condition, wherein the apparent viscosity is more than 45 mPa.s.
12. Use of the micro-nano-scale spherical modified silica acid gelling agent of claim 11 in acidizing fracturing;
preferably, the target reservoir temperature for the acid fracturing is 150 ℃ or higher, more preferably 180 ℃ or higher.
CN202210799342.9A 2022-07-08 2022-07-08 Micro-nano spherical modified silica acid liquid gelatinizer and preparation method and application thereof Pending CN117402299A (en)

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