CN114316935A - Micro-emulsified acid blockage removing system and preparation method thereof - Google Patents

Micro-emulsified acid blockage removing system and preparation method thereof Download PDF

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CN114316935A
CN114316935A CN202210026022.XA CN202210026022A CN114316935A CN 114316935 A CN114316935 A CN 114316935A CN 202210026022 A CN202210026022 A CN 202210026022A CN 114316935 A CN114316935 A CN 114316935A
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acid
micro
surfactant
feed liquid
emulsified
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CN114316935B (en
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李峰
崔忠余
徐爽
乔诗涵
项鹏心
徐冲
黄武鸣
李霖
燕宇鹏
张欣新
李军
何德文
李牧
蒋硕
王建伟
王俊良
郭子龙
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Petrochina Liaohe Oilfield Co Lengjia Oilfield Development Co
Panjin Hongding Oil And Gas Technology Service Co ltd
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Petrochina Liaohe Oilfield Co Lengjia Oilfield Development Co
Panjin Hongding Oil And Gas Technology Service Co ltd
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Abstract

The invention relates to the technical field of oil reservoir exploitation, and provides a micro-emulsified acid blockage removing system and a preparation method thereof. The raw materials for preparing the micro-emulsion acid blockage removing system comprise biodegradable surfactant, organic acid, surface assistant, cosolvent, plant-type organic solvent, ion regulator, surface regulator, complexing agent and water. The micro-emulsion acid blockage removing system provided by the invention has the characteristics of low reaction speed, strong corrosion capacity and friendly environment interface, has a good effect of removing inorganic matter blockage and organic matter blockage in the stratum, can also corrode part of mineral components in a reservoir, increases the pore volume and improves the permeability; and the micro-emulsion acid system has low surface tension, and can relieve water lock damage brought by external liquid to reservoirs and micropores. The main surfactant and the organic solvent used by the micro-emulsified acid blockage removing system provided by the invention are biodegradable and environment-friendly substances, have no pollution to the environment and have wide application prospects.

Description

Micro-emulsified acid blockage removing system and preparation method thereof
Technical Field
The invention relates to the technical field of oil reservoir exploitation, in particular to a micro-emulsified acid blockage removing system and a preparation method thereof.
Background
When low-permeability oil gas is hidden in the water injection development process, because the physical property of the stratum is poor, the clay of the reservoir is hydrated and expanded, dirt precipitation is generated by reinjection of sewage and dirt, and the like, the pore passages of the stratum are blocked, the permeability of the oil layer is reduced, the water injection pressure of a water injection well is increased, and the water injection quantity is reduced.
At present, measures such as acidification blockage removal and the like are generally adopted when the oil reservoir with blockage is subjected to pollution removal. The conventional acidification blockage removal method adopts a reagent mainly comprising inorganic acid, and the inorganic acid blockage removal method has the defects of small treatment radius, easy generation of secondary damage and the like, so that the acidification blockage removal effect is greatly influenced; in the process of reservoir transformation, a large amount of external liquid invades a reservoir, so that a water lock effect is easily caused, and severe damage is caused to a hypotonic or ultra-hypotonic reservoir, while the existing inorganic acid blockage removal can only realize blockage removal and cannot reduce the damage of the water lock to the reservoir. In addition, the existing method for removing the blockage by using the inorganic acid only has a good oil reservoir effect on inorganic blockage and does not have a blockage removing effect on oil-soluble organic blocking substances.
The microemulsion is a thermodynamically stable system composed of a surfactant, a cosurfactant, water, a hydrocarbon compound and the like, and at present, the microemulsion system is adopted as a cleanup additive to unblock a blocked oil reservoir in reports. However, the microemulsion system only has the effect of removing oil-soluble organic blocking substances, and has poor effect of removing oil deposits blocked by inorganic substances.
Disclosure of Invention
In view of the above, the invention provides a micro-emulsion acid blockage removing system and a preparation method thereof. The micro-emulsion acid blockage removing system provided by the invention can simultaneously remove inorganic substance blockage and organic substance blockage in the stratum, and has stronger water-lock removing capability.
In order to achieve the above object, the present invention provides the following technical solutions:
a micro-emulsified acid blockage removing system comprises the following preparation raw materials in parts by mass: 8-20% of biodegradable surfactant, 10-18% of organic acid, 4-15% of surface assistant agent, 4-15% of cosolvent, 9-20% of plant-type organic solvent, 0.2-2% of ion regulator, 0.05-2.5% of surface regulator, 0.3-1% of complexing agent and the balance of water; the biodegradable surfactant includes a nonionic surfactant and an anionic surfactant.
Preferably, the nonionic surfactant is alkylphenol ethoxylates; the anionic surfactant is one or more of fatty alcohol-polyoxyethylene ether sulfate, sulfonate and carboxylate.
Preferably, the surface conditioner is a fluorosurfactant.
Preferably, the fluorine-containing surfactant is one or more of 8-carbon perfluorocarbon surfactant, 10-carbon perfluorocarbon surfactant and 12-carbon perfluorocarbon surfactant.
Preferably, the organic acid is one or more of sulfamic acid, citric acid and oxalic acid.
Preferably, the complexing agent is one or more of citric acid, EDTA and ascorbic acid.
Preferably, the plant-type organic solvent comprises one or more of D-limonene oil, terpineol and castor oil;
the surface assistant agent is one or more of betaine zwitterionic surfactant and amine oxide surfactant;
the cosolvent is small molecular organic alcohol;
the ion regulator is a monovalent metal salt.
Preferably, the pH value of the micro-emulsified acid blockage removing system is 2-3.
The invention also provides a preparation method of the micro-emulsified acid blockage removing system in the scheme, which comprises the following steps:
(1) mixing an anionic surfactant, water and a cosolvent to obtain a first feed liquid;
(2) mixing the first feed liquid, organic acid, a nonionic surfactant and an ion regulator, and reacting at 70-75 ℃ for 2-4 h to obtain a second feed liquid;
(3) mixing the second feed liquid, the plant-type organic solvent, the surface assistant agent and the complexing agent, and reacting for 1-2 hours at the temperature of 60-75 ℃ to obtain a third feed liquid;
(4) and mixing the third feed liquid with a surface conditioning agent, and reacting for 1h at the temperature of 60-65 ℃ to obtain a micro-emulsion acid blockage removing system.
The invention provides a micro-emulsion acid blockage removing system which comprises the following preparation raw materials in parts by mass: 8-20% of cocoa biodegradable surfactant, 10-18% of organic acid, 4-15% of surface assistant agent, 4-15% of cosolvent, 9-20% of plant organic solvent, 0.2-2% of ion regulator, 0.05-2.5% of surface regulator, 0.3-1% of complexing agent and the balance of water; the biodegradable surfactant includes a nonionic surfactant and an anionic surfactant. The micro-emulsion acid unblocking system provided by the invention comprises organic acid and biodegradable surfactant, the organic acid and the biodegradable surfactant can perform nucleophilic addition reaction and oxidation reaction, and generate the zwitterionic polymer surfactant through intermolecular electron cloud rearrangement, and the polymer surfactant has strong water solubility, foaming capacity, salt resistance and temperature resistance, can make the micro-emulsion acid system more stable and has no pollution; and because the organic acid is added, the microemulsion acid system provided by the invention is acidic, has strong corrosion capacity, can remove inorganic substance blockage in the stratum, can partially corrode some mineral components in the reservoir, and has the functions of removing deposition, increasing porosity and improving permeability.
The micro-emulsion acid blockage removing system provided by the invention also comprises a complexing agent, so that the formed micro-emulsion acid system has a complexing function, and can mask dissolved metal ions in a complexing mode to eliminate secondary precipitation, so that the acidification blockage removing effect is greatly enhanced.
The micro-emulsified acid blockage removing system also comprises a plant-type organic solvent, wherein the plant-type organic solvent is a high-efficiency environment-friendly solvent and a nonpolar solvent, and can be combined with a surface polymerization agent through a non-chemical bond to finally form a micro-emulsified acid system with a water-soluble active molecular layer as an external phase and an organic solvent as an internal phase, so that the micro-emulsified acid system is more stable, the micro-emulsified acid system has the capacity of dissolving organic matters, organic matter blockage in pores can be removed in the blockage removing process, and the blockage removing and yield increasing effects on a shale oil-gas well are more effective.
In addition, the microemulsion acid system provided by the invention has a nano-scale particle size and can enter tiny pores and microcracks for action; compared with other acid solution blocking removers, the microemulsion acid system provided by the invention has lower surface tension and interfacial tension and also has a bidirectional wetting function, can penetrate deep into the deep part of a pore through the imbibition capacity in the blocking removal process, reduces or eliminates water lock by reducing the surface tension and changing the rock wettability, reduces the residual water saturation, increases the relative permeability of an oil phase, and achieves the effects of blocking removal and yield increase; more importantly, the micro-emulsified acid blockage removing system can be smoothly discharged back after the micro-emulsified acid blockage removing system is used, and secondary precipitation damage cannot be caused.
In addition, the main surfactant and the organic solvent used by the micro-emulsified acid blockage removing system provided by the invention are biodegradable and environment-friendly substances, so that the environment is not polluted, different strata and different use purposes can be met by compounding different types of reagents, and the micro-emulsified acid blockage removing system has wide application prospect.
In conclusion, the microemulsion acid-deblocking system provided by the invention has incomparable advantages in acid-deblocking and yield-increasing transformation of a low-permeability oil-gas reservoir.
The invention also provides a preparation method of the micro-emulsified acid unblocking system in the scheme, the preparation method provided by the invention is simple in step and easy to operate, and the obtained micro-emulsified acid unblocking system has nano-scale emulsion particles, is thermodynamically stable and has good temperature resistance.
The results of the examples show that the microemulsion acid-hydrolysis blocking system provided by the invention is a homogeneous emulsion, the diameter of emulsion particles is less than 50nm, the temperature resistance can reach more than 300 ℃, the microemulsion acid system is prepared into a 0.3% aqueous solution, the surface tension of the aqueous solution can reach 23-25 mN/m, and the interfacial tension is less than 2 mN/m; a micro-emulsion acid blockage removing system of 0.3 percent is added into the fluid of the injection well, and the permeability of 75 to 85 percent can be recovered in the sandstone stratum; the plugging agent has super-strong water-lock releasing capacity, larger plugging releasing radius, quicker flowback and the flowback rate of a hypotonic reservoir up to more than 80 percent.
Detailed Description
The invention provides a micro-emulsion acid blockage removing system which comprises the following preparation raw materials in parts by mass: 8-20% of cocoa biodegradable surfactant, 10-18% of organic acid, 4-15% of surface assistant agent, 4-15% of cosolvent, 9-20% of plant organic solvent, 0.2-2% of ion regulator, 0.05-2.5% of surface regulator, 0.3-1% of complexing agent and the balance of water.
Unless otherwise specified, the starting materials used in the present invention are commercially available.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise 8-20% by mass of biodegradable surfactant, and preferably 10-19%. In the present invention, the biodegradable surfactant is preferably a nonionic surfactant and an anionic surfactant; the mass ratio of the anionic surfactant to the nonionic surfactant is preferably 6-10: 23-25, and more preferably 6:25 or 10: 23; the nonionic surfactant is preferably alkylphenol polyoxyethylene, more preferably nonylphenol polyoxyethylene-9; the anionic surfactant is one or more of fatty alcohol sulfate, fatty alcohol sulfonate and fatty alcohol carboxylate, and is more preferably fatty alcohol polyoxyethylene ether carboxylate (AEC) and alpha-olefin sodium sulfonate (AOS) or fatty acid methyl ester sodium sulfonate (MES); in the embodiment of the present invention, it is preferable to use nonylphenol polyoxyethylene ether-9 in combination with sodium α -olefin sulfonate, or to use nonylphenol polyoxyethylene ether-9 in combination with fatty alcohol polyoxyethylene ether carboxylate.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise, by mass, 10-18% of organic acid, and preferably 12-17%. In the present invention, the organic acid is preferably one or more of sulfamic acid, citric acid and oxalic acid.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise 4-15% of surface assistant agent, preferably 6-14% by mass. In the invention, the surface assistant agent is preferably one or more of betaine zwitterionic surfactant, alkyl glycoside carboxylate and amine oxide surfactant; the betaine zwitterionic surfactant is preferably octadecyl hydroxyethyl sulfobetaine; the amine oxide-based surfactant is preferably an amine oxide. In the invention, the surface assistant agent can fully dissolve the organic phase and the water phase, so that the organic phase and the water phase are fully contacted to react, and the stability of a micro-emulsion acid system is facilitated.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise 4-15% of cosolvent by mass percent, and preferably 6-14% of cosolvent by mass percent. In the invention, the cosolvent is preferably a small-molecular organic alcohol, and the number of carbon atoms of the small-molecular organic alcohol is preferably 2-6; specifically, the small-molecular organic alcohol is preferably one or more of ethanol, isopropanol and ethylene glycol butyl ether. The invention takes micromolecule organic alcohol as a cosolvent, can promote the dispersion and dissolution of organic solvent, and improves the intersolubility.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise 9-20% by mass of plant-type organic solvent, and preferably 12-18%. In the present invention, the plant-type organic solvent preferably includes one or more of D-limonene oil, terpineol and castor oil; the invention adopts the plant type organic solvent, can realize the dissolution of organic matters in the stratum, and the used solvent is safe and environment-friendly and does not produce environmental pollution.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise 0.2-2% of ion regulator by mass fraction, and preferably 0.5-1.5%. In the present invention, the ion modifier is preferably a monovalent metal salt; the monovalent metal salt is preferably NaCl, KCl, NH4Cl and NaNO3One or more of the above; the invention improves the stability of the microemulsion acid system by adding the ion regulator to regulate the ion content in the microemulsion acid.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise 0.05-2.5% of surface conditioner by mass fraction, and preferably 0.06-2.0%. In the invention, the surface conditioning agent is preferably a fluorine-containing surfactant, and the fluorine-containing surfactant is preferably one or more of 8-carbon perfluorocarbon surfactant, 10-carbon perfluorocarbon surfactant and 12-carbon perfluorocarbon surfactant; the surface conditioning agent selected by the invention has the characteristics of stable performance, good compatibility, environmental protection and the like, and can be matched with a surfactant in a system to reduce the surface tension of a micro-emulsion acid system.
The raw materials for preparing the micro-emulsion acid blockage removing system comprise 0.3-1% of complexing agent, preferably 0.4-0.8% by mass. In the invention, the complexing agent is preferably one or more of citric acid, EDTA and ascorbic acid.
The invention also provides a preparation method of the micro-emulsified acid blockage removing system in the scheme, which comprises the following steps:
(1) mixing an anionic surfactant, water and a cosolvent to obtain a first feed liquid;
(2) mixing the first feed liquid, organic acid, a nonionic surfactant and an ion regulator, and reacting at 70-75 ℃ for 2-4 h to obtain a second feed liquid;
(3) mixing the second feed liquid, the plant-type organic solvent, the surface assistant agent and the complexing agent, and reacting for 1-2 hours at the temperature of 60-75 ℃ to obtain a third feed liquid;
(4) and mixing the third feed liquid with a surface conditioning agent, and reacting for 1h at the temperature of 60-65 ℃ to obtain a micro-emulsion acid blockage removing system.
The method mixes the anionic surfactant, water and cosolvent to obtain a first feed liquid. In the present invention, the mixing is carried out at room temperature; the invention has no special requirements on the specific mixing mode, and the raw materials can be uniformly mixed by adopting a mode known by the technical personnel in the field, such as stirring.
After the first feed liquid is obtained, the first feed liquid, the organic acid, the nonionic surfactant and the ion regulator are mixed and then react for 2-4 hours at the temperature of 70-75 ℃, preferably for 2.5-3.5 hours at the temperature of 72-73 ℃ to obtain a second feed liquid. According to the invention, the first material liquid is preferably heated to 60-65 ℃, then the ion regulator is added into the first material liquid and uniformly mixed, then the first material liquid is heated to 70-75 ℃, the organic acid and the nonionic surfactant are added, the mixture is stirred until the organic acid and the nonionic surfactant are dissolved and uniformly mixed, and then the heating temperature is maintained for reaction. In the reaction process, the organic acid and the surfactant undergo nucleophilic addition reaction and coupling reaction, and then the polyether surfactant is generated.
After the second feed liquid is obtained, the second feed liquid, the plant-type organic solvent, the surface assistant and the complexing agent are mixed and react for 1-2 hours at the temperature of 60-75 ℃, preferably for 1.3-1.5 hours at the temperature of 65-70 ℃ to obtain a third feed liquid. In the invention, preferably, the heating temperature of the second feed liquid is kept at 60-75 ℃, then the plant-type organic solvent, the surface assistant agent and the complexing agent are added, and the reaction is carried out under the stirring condition; in the present invention, the reactions occurring here are emulsification reactions and complexation reactions.
After the third feed liquid is obtained, the third feed liquid and the surface conditioning agent are mixed and react for 1 hour at the temperature of 60-65 ℃ to obtain the micro-emulsion acid blockage removing system. In the specific embodiment of the invention, the heating temperature of the third feed liquid is preferably kept at 60-65 ℃, and then a surface conditioning agent is added to react under the stirring condition; the reaction occurring here is an emulsion reaction; after the reaction is finished, a brown uniform liquid is obtained, namely the micro-emulsion acid system.
The microemulsion acid system obtained by the method is uniform and transparent brown liquid, does not delaminate after being placed for a long time, and the particle size of emulsion liquid drops is less than 50 nm.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Adding 80mL of water into a beaker, putting the beaker into a water bath, adding the biodegradable surfactant and the cosolvent into a container, and uniformly stirring to obtain a first feed liquid. Wherein the added biodegradable surfactant is AOS (alpha-olefin sodium sulfonate), and the addition amount is 6 g; the cosolvent is 9.6g of isopropyl alcohol and ethylene glycol butyl ether, and the mass ratio of the isopropyl alcohol to the ethylene glycol butyl ether is 1: 1;
heating the first feed liquid to 65 ℃, adding an ion regulator, and stirring to dissolve the first feed liquid into uniform liquid. Wherein the ion regulator is sodium chloride, and the addition amount is 0.4 g;
heating the obtained liquid to 75 ℃, and adding 25g of nonionic surfactant and 25g of organic acid; the nonionic surfactant is nonylphenol polyoxyethylene ether-9; the added organic acid is citric acid and sulfamic acid, wherein the mass ratio of the sulfamic acid to the citric acid is 1: 1.5. and reacting the liquid at 75 ℃ for 2h to obtain a second feed liquid.
Adjusting the temperature of the second feed liquid to 65 ℃, and adding a plant type organic solvent, a surface assistant agent and a complexing agent, wherein the plant type organic solvent is terpineol, and the adding amount is 17 g; the surface assistant agent is alkyl polyglycoside carboxylate, the adding amount is 7g, the complexing agent is EDTA, the adding amount is 0.9g, and the mixture is stirred for 1 hour to obtain third feed liquid.
And continuously heating the obtained third feed liquid to maintain the temperature at 65 ℃, adding a surface regulator, wherein the surface regulator is a 10-carbon perfluorocarbon surfactant, the adding amount is 4g, stirring for 1h to obtain brown uniform liquid, namely a micro-emulsion acid blockage removing system, the pH value of the system is 3, and the diameter of emulsion particles is less than 50 nm.
The obtained micro-emulsified acid blockage removing system is prepared into 0.3 wt% of aqueous solution, the surface tension of the aqueous solution is 24.54mN/m, the interfacial tension is 0.85mN/m, and the wetting angle is 28.4 degrees. The obtained microemulsion acid system is placed at 300 ℃ for 4h, and the particle size, the surface tension, the interfacial tension and the wetting angle of the system are not obviously changed. And the water-lock releasing capacity is strong, the flowback rate can reach more than 80%, and the recovery value of the permeability is more than 2.
The microemulsion acid plugging removal system prepared in the example 1 is used in a low permeability reservoir water injection well, wherein inorganic plugging and organic plugging exist in the low permeability reservoir water injection well at the same time, 0.3% of microemulsion acid plugging removal system is added into fluid of an injection well, the water injection pressure is reduced to 12MPa.s from 14MPa.s, and the plugging removal effect is obvious.
Example 2
Adding 75mL of water into a beaker, putting the beaker into a water bath, adding the biodegradable surfactant and the cosolvent into the beaker, and uniformly stirring to obtain a first feed liquid. Wherein, the added biodegradable surfactant is AEC (fatty alcohol polyoxyethylene ether carboxylate), and the addition amount is 10 g; the cosolvent is isopropanol and ethylene glycol monobutyl ether, the adding amount is 8g, and the mass ratio of the isopropanol to the ethylene glycol monobutyl ether is 1: 1;
heating the first material liquid to 60-65 ℃, adding an ion regulator, and stirring and dissolving to obtain uniform liquid. Wherein the ion regulator is sodium chloride, and the addition amount is 2 g;
the liquid obtained above was heated to 70 ℃ and 23g of nonionic surfactant and 18g of organic acid were added. The added nonionic surfactant is nonylphenol polyoxyethylene ether-10; the organic acid added is citric acid. And reacting the liquid at 70 ℃ for 3h to obtain a second feed liquid.
Adjusting the temperature of the second feed liquid to 60 ℃, and adding a plant-type organic solvent, a surface assistant agent and a complexing agent, wherein the plant-type organic solvent is D-limonene oil, and the adding amount is 17 g; the surfactant is 21g of octadecyl hydroxyethyl sulfobetaine and amine oxide, and the proportion of the octadecyl hydroxyethyl sulfobetaine to the amine oxide is 2: 1, the complexing agent is citric acid, and the addition amount is 0.8 g. Stirring for 1h to obtain a third feed liquid.
Continuously heating the third feed liquid, keeping the temperature at 60 ℃, adding a surface regulator, wherein the surface regulator is 8-carbon perfluorocarbon surfactant and 10-carbon perfluorocarbon surfactant, and the ratio of the two is 1: 3, stirring for 1h to obtain brown uniform liquid, namely a micro-emulsion acid blockage removal system, wherein the pH value of the system is 3, and the diameter of emulsion particles is less than 9-14 nm.
The obtained micro-emulsion acid is prepared into 0.3 weight percent aqueous solution, the surface tension of the aqueous solution is 23.24mN/m, the interfacial tension is 0.34mN/m, and the wetting angle is 19.3 degrees. The obtained microemulsion acid system is placed at 300 ℃ for 4h, and the particle size, the surface tension, the interfacial tension and the wetting angle of the system are not obviously changed. And the water-lock releasing capacity is strong, the flowback rate can reach more than 78%, and the recovery value of the permeability is more than 2.
The microemulsion acid plugging removal system prepared in the embodiment 2 is used in a low-permeability reservoir water injection well, wherein inorganic plugging and organic plugging exist in the low-permeability reservoir water injection well at the same time, 0.3% of microemulsion acid plugging removal system is added into fluid of an injection well, the water injection pressure is reduced to 11.9MPa.s from 14MPa.s, and the plugging removal effect is obvious.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A micro-emulsion acid blockage removing system is characterized by comprising the following preparation raw materials in parts by mass: 8-20% of biodegradable surfactant, 10-18% of organic acid, 4-15% of surface assistant agent, 4-15% of cosolvent, 9-20% of plant-type organic solvent, 0.2-2% of ion regulator, 0.05-2.5% of surface regulator, 0.3-1% of complexing agent and the balance of water; the biodegradable surfactant includes a nonionic surfactant and an anionic surfactant.
2. A microemulsion acid unblocking system according to claim 1, wherein the non-ionic surfactant is alkylphenol ethoxylate; the anionic surfactant is one or more of fatty alcohol sulfate, fatty alcohol sulfonate and fatty alcohol carboxylate.
3. A micro-emulsified acid blockage removing system according to claim 1, wherein the surface conditioner is a fluorine-containing surfactant.
4. A micro-emulsified acid blockage removal system according to claim 3, wherein the fluorine-containing surfactant is one or more of 8-carbon perfluorocarbon surfactant, 10-carbon perfluorocarbon surfactant and 12-carbon perfluorocarbon surfactant.
5. A micro-emulsified acid unblocking system according to claim 1, wherein the organic acid is one or more of sulfamic acid, citric acid and oxalic acid.
6. A micro-emulsified acid unblocking system according to claim 1, wherein the complexing agent is one or more of citric acid, EDTA and ascorbic acid.
7. A micro-emulsified acid unblocking system according to claim 1, wherein the plant-type organic solvent includes one or more of D-limonene oil, terpineol and castor oil.
8. A micro-emulsified acid unblocking system according to claim 1, wherein the co-surfactant is one or more of betaine zwitterionic surfactant and amine oxide surfactant;
the cosolvent is small molecular organic alcohol;
the ion regulator is a monovalent metal salt.
9. The micro-emulsified acid unblocking system according to claim 1, wherein the pH value of the micro-emulsified acid unblocking system is 2-3.
10. The preparation method of the micro-emulsified acid blockage removing system as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps:
(1) mixing an anionic surfactant, water and a cosolvent to obtain a first feed liquid;
(2) mixing the first feed liquid, organic acid, a nonionic surfactant and an ion regulator, and reacting at 70-75 ℃ for 2-4 h to obtain a second feed liquid;
(3) mixing the second feed liquid, the plant-type organic solvent, the surface assistant agent and the complexing agent, and reacting for 1-2 hours at the temperature of 60-75 ℃ to obtain a third feed liquid;
(4) and mixing the third feed liquid with a surface conditioning agent, and reacting for 1h at the temperature of 60-65 ℃ to obtain a micro-emulsion acid blockage removing system.
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