CN111117591B - Cross-linked emulsified self-generated acid and preparation method thereof - Google Patents
Cross-linked emulsified self-generated acid and preparation method thereof Download PDFInfo
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- CN111117591B CN111117591B CN201811292153.2A CN201811292153A CN111117591B CN 111117591 B CN111117591 B CN 111117591B CN 201811292153 A CN201811292153 A CN 201811292153A CN 111117591 B CN111117591 B CN 111117591B
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
Abstract
The invention discloses a cross-linking emulsified authigenic acid and a preparation method thereof. The crosslinked emulsified autogenous acid comprises: a crosslinking acid base solution, an emulsified self-generated acid and a crosslinking agent; 0.6-1.5 parts of a cross-linking agent by taking the total volume of the cross-linking acid base solution and the emulsified self-generated acid as 100 parts; wherein the volume ratio of the crosslinking acid base liquid to the emulsified self-generated acid is (50-80): (50-20). The invention integrates the crosslinking acid, the emulsifying acid and the self-generated acid, and forms a novel high-diversion deep-penetration retarding acid liquid system by utilizing the synergistic effect. Compared with the conventional ground crosslinked acid system, the system has the characteristics of better retarding performance, stability, temperature resistance and the like, and has good acid fracturing/acidizing effect after being injected into a stratum. Meanwhile, the acid liquid system is an acid liquid with cross-linked acid as an external phase and emulsified self-generated acid as an internal phase, and the problems of high friction resistance of the emulsified self-generated acid and difficulty in pumping in deep well acid fracturing construction are solved.
Description
Technical Field
The invention relates to the field of acid fracturing production increase of carbonate reservoirs, in particular to a cross-linked emulsified self-generated acid and a preparation method thereof.
Background
Ground crosslinked acid, emulsified acid and authigenic acid are the most commonly used retarding acid systems for low-permeability, fracture-cavity type and fracture-type carbonate reservoirs and acid fracturing modification. The ground crosslinked acid is prepared by adding thickener (or gelling agent) into acid (such as hydrochloric acid) to increase acid viscosity, adding crosslinking agent to form adjustable gel system, and further reducing H +The diffusion rate is transferred, the fluid filtration is reduced, the acid liquid action distance is prolonged, and the acid fracturing improvement effect is improved. The emulsified acid is oneThe oil-in-acid emulsion formed by mixing the oil phase and the acid phase has the advantages of good retarding performance, small filtration loss, low corrosion rate and the like. Autogenous acids, also known as latent acids, refer to acid precursors that form reactive acids in situ by chemical reaction under formation conditions, and different autogenous acid systems can produce HCl and HF or a mixture of both. In recent years, the ground crosslinked acid technology is continuously improved, the temperature resistance of the ground crosslinked acid system applied on site at present is up to 160 ℃, although the application of high-temperature reservoir acid fracturing modification can be met, the problems of short acid corrosion crack, limited communication reservoir range, poor acid fracturing modification effect and the like exist. According to the report of domestic special documents, the problems of poor temperature resistance, high friction resistance and the like exist in the current emulsified acid system, and the acid fracturing requirement of the high-temperature deep well cannot be met. The use of the self-acid-generating system in high-temperature stratum can not only avoid the problems of rapid inactivation of acid liquor at high temperature, shortening of effective length of acid corrosion cracks and the like, but also prevent corrosion of pipelines and equipment, but most of the self-acid-generating systems have the problems of poor temperature resistance, large filtration loss, poor flow conductivity and the like. With the continuous deepening of high temperature carbonate reservoir exploration and development, higher requirements are put forward on the retarding performance of a high temperature acid liquor system so as to achieve the purposes of deep penetration and high diversion, and therefore, the development of a novel acid liquor system with a good retarding effect at a high temperature is urgently needed.
Chinese patent CN104194767A discloses a high-temperature-resistant emulsified acid liquid, which adopts the technical scheme that a high-temperature emulsified acid system is formed by selecting a high-efficiency emulsifier, but the problems of poor temperature resistance, poor high-temperature retarding effect, high friction resistance and the like exist, so that a novel high-temperature retarding acid system is continuously developed.
Chinese patent CN107974246A discloses a high-temperature-resistant cross-linked acid system, a preparation method and application, the high-temperature-resistant cross-linked acid system for acid fracturing has viscosity of 50-70 mPa.s at 160 ℃, and is suitable for acid fracturing production increasing operation of carbonate reservoirs at 160 ℃. However, according to the use condition of the existing crosslinking acid system, the length and the flow conductivity of the acid-etched crack of the crosslinking acid at high temperature cannot meet the deep penetration requirement, so that a novel deep penetration acid system is urgently needed to be developed.
Chinese patent CN102899012A discloses a self-generated acid, a preparation method and application thereof, wherein the self-generated acid comprises paraformaldehyde, ammonium chloride and water, hydrochloric acid can be slowly generated by mixing the self-generated acid at room temperature, the acid is rapidly generated under the high-temperature heating condition, the problems of serious filtration loss, poor temperature resistance and poor etching form exist, the self-generated acid cannot be used in a high-temperature deep well, and the self-generated acid does not have double retarding effects. When the self-generated acid meets formation water, the acid liquor can be quickly diluted, and a good acidizing effect cannot be achieved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a crosslinking emulsifying authigenic acid and a preparation method thereof. The invention integrates the crosslinking acid, the emulsifying acid and the self-generated acid, and forms a novel high-diversion deep-penetration retarding acid liquid system by utilizing the synergistic effect. Compared with the conventional ground crosslinked acid system, the crosslinked emulsified self-generated acid has the characteristics of better retarding performance, stability, temperature resistance and the like, and has good acid fracturing/acidizing effect after being injected into a stratum. Meanwhile, the acid liquid system is an acid liquid with cross-linked acid as an external phase and emulsified self-generated acid as an internal phase, and the problems of high friction resistance of the emulsified self-generated acid and difficulty in pumping in deep well acid fracturing construction are solved.
One of the objects of the present invention is to provide a crosslinked emulsified authigenic acid.
The crosslinked emulsified autogenous acid comprises:
a crosslinking acid base solution, an emulsified self-generated acid and a crosslinking agent;
based on 100 parts of the total volume of the crosslinking acid base solution and the emulsified self-generated acid,
0.6-1.5 parts of cross-linking agent, preferably 0.8-1.2 parts;
wherein the volume ratio of the crosslinking acid base liquid to the emulsified self-generated acid is (50-80): (50-20); preferably (55-75): (45-25);
the crosslinking agent may be selected from one of conventional surface crosslinking acids and crosslinking agents for subsurface crosslinking acids. In the present invention, at least one selected from the group consisting of an organic zirconium crosslinking agent, an organic aluminum crosslinking agent and an organic titanium crosslinking agent is preferable.
The emulsified self-generated acid comprises an oil phase and a self-generated acid phase;
based on 100 parts of the total volume of the oil phase and the self-generated acid phase,
oil phase: 20-40 parts, preferably 25-35 parts;
self-acid generation phase: 80-60 parts, preferably 75-65 parts;
the oil phase contains 2.0 to 4.0 weight parts of oil-in-water emulsifier, preferably 2.5 to 3.5 weight parts, based on 100 weight parts of the total weight of the oil phase;
the oil-in-water emulsifier is one or a combination of dipolyhydroxystearate, sorbitan sesquioleate, sorbitan fatty acid ester, polyoxyethylene octyl phenol ether-10 and hexadecylamine;
the oil phase is one or a combination of diesel oil, kerosene, white oil and light crude oil;
the authigenic acid phase includes: chloroacetate, corrosion inhibitor, iron ion stabilizer and water;
the total weight of the self-generated acid phase is 100 parts by weight:
60-80 parts of chloroacetate, preferably 65-75 parts;
0.5-1.5 parts of iron ion stabilizer, preferably 0.8-1.2 parts;
0.5-1.5 parts of corrosion inhibitor and 0.8-1.2 parts of corrosion inhibitor;
the balance of water;
the corrosion inhibitor is selected from at least one of imidazoline corrosion inhibitors, quinoline quaternary ammonium salt corrosion inhibitors, ketone-aldehyde-amine condensate corrosion inhibitors and Mannich base corrosion inhibitors; specifically, the quaternary ammonium salt may be one or a combination of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt and 2-methylquinoline benzyl quaternary ammonium salt. The addition amount thereof can be adjusted by those skilled in the art according to the specific situation.
The iron ion stabilizer is at least one selected from citric acid, ethylenediamine tetraacetic acid, ascorbic acid and acetic acid.
Wherein the preparation steps of the lactic acid-producing phase are as follows:
adding chloroacetate, iron ion stabilizer and corrosion inhibitor into water in sequence, stirring uniformly, sealing, standing at room temperature for 1 hour, and obtaining the self-generated acid phase.
The preparation steps of the oil phase are as follows:
1) adding the high-efficiency emulsifier with the dosage into the oil phase, heating and stirring until the high-efficiency emulsifier is completely dissolved;
2) the oil mixture was cooled to room temperature for use.
The emulsified authigenic acid is prepared by a method comprising the following steps:
slowly adding the authigenic acid phase into the oil phase according to the dosage, and uniformly stirring and mixing at a high speed to prepare the emulsified authigenic acid; the stirring speed is 1000-3000 r/min, and the stirring time is 10-30 min;
the crosslinking acid base fluid comprises the following components in parts by weight:
based on 100 parts of the total weight of the crosslinking acid base solution,
90-96 parts of hydrochloric acid or hydrofluoric acid, preferably 90-94 parts;
1.5-3 parts of corrosion inhibitor, preferably 2.0-2.5 parts;
0.8-1.8 parts of iron ion stabilizer, preferably 1.0-1.5 parts;
2.0-4.0 parts of O/W efficient emulsifier, preferably 2.5-3.5 parts;
0.5-1.2 parts of thickening agent for acid, preferably 0.8-1.0 part;
The concentration of the hydrochloric acid or hydrofluoric acid is 15-30%, preferably 15-20% wt.
The corrosion inhibitor is selected from at least one of imidazoline corrosion inhibitors, quinoline quaternary ammonium salt corrosion inhibitors, ketone-aldehyde-amine condensate corrosion inhibitors and Mannich base corrosion inhibitors; specifically, the quaternary ammonium salt may be one or a combination of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt and 2-methylquinoline benzyl quaternary ammonium salt. The addition amount thereof can be adjusted by those skilled in the art according to the specific situation.
The iron ion stabilizer is at least one selected from citric acid, ethylenediamine tetraacetic acid, ascorbic acid and acetic acid;
the oil-in-water emulsifier is one or a combination of cetyl trimethyl ammonium bromide, sorbitan fatty acid ester polyoxyethylene ether, polyoxyethylene monostearate, sodium dodecyl benzene sulfonate and polyoxyethylene octyl phenol ether-10;
the acid thickener is at least one of a synthetic polymer and a natural polymer; the synthetic polymer can be selected from thickening agents for polyacrylamide acids, and the natural polymer can be selected from guanidine gum natural polymers. The thickening agent for polyacrylamide acid can be selected from at least one of cationic polyacrylamide or anionic acid-resistant polyacrylamide; the guanidine gum natural polymer can be at least one of hydroxypropyl guanidine gum or carboxymethyl guanidine gum.
The crosslinking acid-based fluid is prepared by a method comprising the following steps:
adding the acid thickening agent, the iron ion stabilizer, the corrosion inhibitor and the emulsifier into the hydrochloric acid or hydrofluoric acid solution while stirring, uniformly stirring, sealing and standing at room temperature to obtain the cross-linked acid base solution.
Specifically, the preparation method of the crosslinking acid-based fluid can comprise the following steps:
1) preparing the hydrochloric acid solution, measuring a certain volume, and putting the solution into a beaker;
2) stirring the hydrochloric acid solution by using a mechanical stirrer, wherein the stirring speed is based on the formation of a large vortex;
3) adding a thickening agent for acid under the stirring condition, and continuously stirring for 30-50 minutes;
4) and then sequentially adding the iron ion stabilizer, the corrosion inhibitor and the emulsifier, uniformly stirring, sealing, standing at room temperature for 4-6 hours, and obtaining the cross-linked acid base solution.
The second purpose of the invention is to provide a preparation method of the crosslinking emulsified self-generated acid.
The method comprises the following steps:
adding the emulsified authigenic acid into the crosslinking acid base liquid while stirring, uniformly mixing to form uniform emulsion, and adding the crosslinking agent with the dosage into the emulsion to obtain the crosslinking emulsified authigenic acid.
Wherein, the first and the second end of the pipe are connected with each other,
the stirring speed is 300-1500 r/min, preferably 500-1000 r/min;
The stirring time is 3-15 min, preferably 5-10 min.
The preparation method of the crosslinking emulsified authigenic acid specifically comprises the following steps:
1) slowly adding the emulsified autogenous acid into the base solution of the cross-linked acid according to the dosage, and stirring at 500-1000 r/min during and after the addition so as to uniformly mix the emulsified autogenous acid and the base solution, and stirring for 5-10 min to form uniform emulsion;
2) and (3) dropwise adding a cross-linking agent into the emulsion, stirring during and after the addition, and stirring for 3-5 minutes after the addition is finished to obtain a cross-linked emulsified self-generated acid system.
According to the invention, the self-generated acid is wrapped in a network structure of the cross-linked emulsified self-generated acid by utilizing emulsification and cross-linking, so that a novel acid liquid system with excellent performance and formed by wrapping the emulsified self-generated acid with the cross-linked acid is formed. The network structure formed by the cross-linked acid is utilized to wrap the emulsified authigenic acid oil drops, the emulsified authigenic acid is filled in gaps of a network formed by the thickening agent for the acid and the cross-linking agent, the network structure has a stabilizing effect on the dispersed emulsified authigenic acid, and meanwhile the emulsified authigenic acid enhances the temperature resistance and the viscosity of a cross-linked acid system. The novel acid system can realize graded control and release of H + ions, and realize deep acidification and high diversion acid fracturing. Under the condition that the structure of the cross-linked emulsion is not damaged, the authigenic acid in the emulsified authigenic acid oil drops is heated and slowly hydrolyzed to generate H + ions, and the H + ions cannot contact with rocks due to the wrapping effect of the emulsion, so that the effect of reducing acid rock reaction is achieved; emulsified self-generated acid emulsion reduces the diffusion coefficient of H + ions of the cross-linked acid, reduces the contact area of the H + ions and the rock, and reduces the reaction of the cross-linked acid and the rock; under the conditions of high-temperature shearing and the reaction of the crosslinking acid and the rock, the structure of the crosslinking emulsion is gradually destroyed, H + ions wrapped in the emulsified self-generated acid and the self-generated acid are released, the H + ions contact the rock to react, and the self-generated acid is gradually hydrolyzed to generate H + ions which further react with the rock. The crosslinking emulsified self-acid-generating system reduces acid liquor filtration loss and reaction rate of crosslinking acid and rock through film forming blocking effect, tackifying blocking effect, two-phase flow effect and Jamin effect, and effectively prolongs acid liquor etching distance through acid liquor graded release, forms uneven etching effect and improves acid etching crack flow conductivity. Compared with the conventional ground crosslinked acid system, the crosslinked emulsified self-generated acid obtained by the technical scheme of the invention has the characteristics of better retarding performance, stability, temperature resistance and the like, and has good acid fracturing/acidizing effect after being injected into a stratum. Meanwhile, the acid liquid system is an acid liquid with cross-linked acid as an external phase and emulsified self-generated acid as an internal phase, and the problems of high friction resistance of the emulsified self-generated acid and difficulty in pumping in deep well acid fracturing construction are solved.
Compared with the conventional ground crosslinked acid system, the crosslinked emulsified self-generated acid obtained by the technical scheme of the invention has the characteristics of better retarding performance, stability, temperature resistance and the like, and has good acid fracturing/acidizing effect after being injected into a stratum. Meanwhile, the acid liquid system is an acid liquid with a cross-linked acid as an external phase and an emulsified self-generated acid as an internal phase, overcomes the problems of high friction resistance of the emulsified self-generated acid and difficulty in pumping in deep well acid fracturing construction, and has wide popularization and application prospects.
Drawings
FIG. 1 is a schematic diagram of a cross-linked emulsified self-produced acid preparation process;
preparing emulsified authigenic acid, dispersing the emulsified authigenic acid into a cross-linked acid base solution, and finally adding a cross-linking agent to form an emulsified cross-linked acid system.
Detailed Description
The present invention is further illustrated by the following examples.
Preparation of acid thickener: weighing a certain amount of distilled water, adding AM and AMPS according to a molar ratio of 3:1, adjusting pH to about 7.0 with sodium hydroxide, cooling to room temperature (25 ℃), introducing nitrogen for 30min, adding a certain amount of ammonium persulfate and sodium bisulfite to initiate polymerization, and sealing at room temperature for 12 h. And granulating the reacted rubber block, drying at 60 ℃, and crushing to obtain a polymer powder sample.
Other raw materials are all commercially available.
Example 1
1) Preparing an emulsified self-generated acid internal phase according to the following components in parts by weight: weighing 65.0 parts of sodium chloroacetate, adding into 33.4 parts of water at the rotating speed of 500r/min, sequentially adding 0.8 part of iron ion stabilizer ethylene diamine tetraacetic acid (commercially available) and 0.8 part of imidazoline corrosion inhibitor, uniformly stirring, and standing for 1h for later use;
2) preparing an oil external phase according to the following components in parts by weight: heating and dissolving 1.5 parts of dipolyhydroxystearate and 0.5 part of hexadecylamine in 98 parts of diesel oil, uniformly stirring, and cooling to room temperature;
3) the emulsified authigenic acid is prepared from the following components in parts by volume: slowly dripping the prepared authigenic internal acid phase into the oil external phase at the stirring speed of 1500r/min, wherein the volume ratio of the authigenic acid phase to the oil phase is 70:30, and continuously stirring for 20min after dripping to obtain the emulsified authigenic acid system.
4) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 93.5 parts of hydrochloric acid solution (the concentration is 15 percent by weight), slowly adding 0.8 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical petroleum engineering technical research institute), stirring for half an hour at the rotating speed of 500r/min to form uniform solution, then adding 1.2 parts of iron ion stabilizer (ethylene diamine tetraacetic acid, Tianjin optical complex chemical reagent factory), 2.0 parts of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt (sold in the market) and 2.5 parts of sorbitan fatty acid ester polyoxyethylene ether (sold in the market) emulsifier, stirring uniformly, sealing, standing at room temperature for 4 hours;
5) Preparing an emulsion according to the following components in parts by volume: slowly dripping the emulsified self-generated acid into the prepared cross-linked acid base liquid under the condition that the stirring speed is 500r/min, wherein the volume ratio of the two phases is the cross-linked acid base liquid: the oil phase is 50:50, and stirring is continued for 5min after the dripping is finished;
6) to the above emulsion, 0.8 part of an organic zirconium crosslinking agent (commercially available) was slowly added, and slowly stirred for 3 minutes to obtain a crosslinked emulsified nascent acid.
Example 2
1) Preparing an emulsified self-generated acid internal phase according to the following components in parts by weight: weighing 70.0 parts of sodium chloroacetate, adding into 28.0 parts of water at the rotating speed of 500r/min, sequentially adding 1.0 part of iron ion stabilizer (ethylene diamine tetraacetic acid (commercially available)) and 1.0 part of imidazoline corrosion inhibitor, uniformly stirring, and standing for 1h for later use;
2) preparing an oil external phase according to the following components in parts by weight: heating and dissolving 2.0 parts of sorbitan sesquioleate and 0.5 part of polyoxyethylene octyl phenol ether-10 in 97.5 parts of diesel oil, stirring uniformly, and cooling to room temperature;
3) the emulsified authigenic acid is prepared from the following components in parts by volume: slowly dripping the prepared internal acid phase into the oil external phase at the stirring speed of 2000r/min, wherein the volume ratio of the acid phase to the oil phase is 65:35, and continuously stirring for 15min after dripping to obtain the emulsified self-generating acid self-generating system.
4) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 91.4 parts of hydrochloric acid solution (the concentration is 20 percent by weight), slowly adding 0.9 part of polyacrylamide thickening agent SRAP-1 (produced by China petrochemical petroleum engineering research institute), stirring for half an hour at the rotating speed of 500r/min to form a uniform solution, then adding 1.5 parts of iron ion stabilizer citric acid (sold in the market), 3.0 parts of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt (sold in the market) and 3.0 parts of polyoxyethylene octylphenol ether-10 (sold in the market) emulsifier, stirring uniformly, sealing, standing at room temperature for 5 hours;
2) preparing an emulsion according to the following components in parts by volume: slowly dripping the emulsified self-generated acid into the prepared cross-linked acid base liquid under the condition that the stirring speed is 800r/min, wherein the volume ratio of the two phases is the cross-linked acid base liquid: the oil phase is 60:40, and the stirring is continued for 7min after the dripping is finished;
4) to the above emulsion, 1.0 part of an organic titanium crosslinking agent (commercially available) was slowly added, and the mixture was slowly stirred for 3 minutes to obtain a crosslinked emulsified authigenic acid.
Example 3
1) Preparing an emulsified self-generated acid internal phase according to the following components in parts by weight: weighing 65.0 parts of sodium chloroacetate, adding the sodium chloroacetate into 33.4 parts of water at the rotating speed of 500r/min, sequentially adding 0.8 part of a 1:1 mixture (sold in the market) of iron ion stabilizer acetic acid and citric acid and 0.8 part of paraformaldehyde/cyclohexane/acetophenone corrosion inhibitor (sold in the market), uniformly stirring, and standing for 1 hour for later use;
2) Preparing an oil external phase according to the following components in parts by weight: heating and dissolving 2.0 parts of sorbitan fatty acid ester and 2.0 parts of polyoxyethylene octyl phenol ether-10 in 96 parts of diesel oil, stirring uniformly, and cooling to room temperature;
3) the emulsified authigenic acid is prepared from the following components in parts by volume: slowly dripping the prepared internal acid phase into the oil external phase at the stirring speed of 2500r/min, wherein the volume ratio of the acid phase to the oil phase is 60:40, and continuously stirring for 10min after dripping to obtain the emulsified self-generated acid system.
4) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 90.8 parts of hydrochloric acid solution (the concentration is 25 percent by weight), slowly adding 1.0 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical petroleum engineering technical research institute), stirring for half an hour at the rotating speed of 500r/min to form a uniform solution, then adding 1.5 parts of iron ion stabilizer acetic acid (sold in the market), 3.5 parts of paraformaldehyde/cyclohexane/acetophenone corrosion inhibitor (sold in the market) and 3.0 parts of polyoxyethylene octylphenol ether-10 and hexadecyl trimethyl ammonium bromide mixture (the mass ratio is 1:1) (sold in the market) emulsifier, stirring uniformly, sealing, standing at room temperature for 5 hours;
5) preparing an emulsion according to the following components in parts by volume: slowly dripping white oil into the prepared crosslinking acid base liquid under the condition that the stirring speed is 1000r/min, wherein the volume ratio of the two phases is that of the crosslinking acid base liquid: the oil phase is 70:30, and stirring is continued for 8min after the dripping is finished;
6) 1.2 parts of organic aluminum cross-linking agent (produced by China petrochemical petroleum engineering technical research institute) is slowly added into the emulsion, and the emulsion is slowly stirred for 3 minutes to obtain the cross-linked emulsified authigenic acid.
Example 4
1) Preparing an emulsified self-generated acid internal phase according to the following components in parts by weight: weighing 70.0 parts of sodium chloroacetate, adding into 28.0 parts of water at the rotating speed of 500r/min, sequentially adding 1.0 part of iron ion stabilizer ethylene diamine tetraacetic acid (commercially available) and 1.0 part of imidazoline corrosion inhibitor, uniformly stirring, and standing for 1h for later use;
2) preparing an oil external phase according to the following components in parts by weight: heating and dissolving 2.5 parts of sorbitan fatty acid ester and 0.5 part of tetradecylamine in 97 parts of diesel oil, uniformly stirring, and cooling to room temperature;
3) the emulsified authigenic acid is prepared from the following components in parts by volume: slowly dripping the prepared internal acid phase into the oil external phase at the stirring speed of 2500r/min, wherein the volume ratio of the acid phase to the oil phase is 80:20, and continuously stirring for 15min after dripping to obtain the emulsified self-generated acid system.
4) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 90.8 parts of hydrochloric acid solution (the concentration is 20 percent by weight), slowly adding 1.0 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical petroleum engineering technical research institute), stirring for half an hour at the rotating speed of 500r/min to form a uniform solution, then adding 1.5 parts of iron ion stabilizer acetic acid (sold in the market), 3.5 parts of 2-methylquinoline benzyl quaternary ammonium salt corrosion inhibitor (sold in the market) and 3.0 parts of a mixture (the mass ratio is 1:1) (sold in the market) of sodium dodecyl benzene sulfonate and hexadecyl trimethyl ammonium bromide, stirring uniformly, sealing, standing at room temperature for 5 hours;
5) The emulsion is prepared from the following components in parts by volume: slowly dripping the emulsified self-generated acid into the prepared cross-linked acid base liquid under the condition that the stirring speed is 1000r/min, wherein the volume ratio of the two phases is the cross-linked acid base liquid: the oil phase is 55:45, and the stirring is continued for 10min after the dripping is finished;
6) 1.2 parts of organic zirconium cross-linking agent (produced by China petrochemical petroleum engineering technical research institute) is slowly added into the emulsion, and the emulsion is slowly stirred for 3 minutes to obtain the cross-linked emulsified authigenic acid.
Example 5
1) Preparing an emulsified self-generated acid internal phase according to the following components in parts by weight: weighing 75.0 parts of sodium chloroacetate, adding the sodium chloroacetate into 22.6 parts of water at the rotating speed of 500r/min, sequentially adding 1.2 parts of a 1:1 mixture (sold in the market) of iron ion stabilizer acetic acid and citric acid and 1.2 parts of paraformaldehyde/cyclohexane/acetophenone corrosion inhibitor (sold in the market), uniformly stirring, and standing for 1 hour for later use;
2) preparing an oil external phase according to the following components in parts by weight: heating and dissolving 2.0 parts of dipolyhydroxystearate and 0.5 part of hexadecylamine in 97.5 parts of diesel oil, uniformly stirring, and cooling to room temperature;
3) the emulsified authigenic acid is prepared from the following components in parts by volume: slowly dripping the prepared authigenic internal acid phase into the oil external phase at the stirring speed of 1500r/min, wherein the volume ratio of the authigenic acid phase to the oil phase is 70:30, and continuously stirring for 20min after dripping to obtain the emulsified authigenic acid system.
4) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 93.5 parts of hydrochloric acid solution (the concentration is 15 percent by weight), slowly adding 0.8 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical petroleum engineering technical research institute), stirring for half an hour at the rotating speed of 500r/min to form uniform solution, then adding 1.2 parts of iron ion stabilizer (ethylene diamine tetraacetic acid, Tianjin optical complex chemical reagent factory), 2.0 parts of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt (sold in the market) and 2.5 parts of sorbitan fatty acid ester polyoxyethylene ether (sold in the market) emulsifier, stirring uniformly, sealing, standing at room temperature for 4 hours;
5) the emulsion is prepared from the following components in parts by volume: slowly dripping the emulsified self-generated acid into the prepared cross-linked acid base liquid under the condition that the stirring speed is 500r/min, wherein the volume ratio of the two phases is the cross-linked acid base liquid: the oil phase is 50:50, and stirring is continued for 5min after the dripping is finished;
6) to the above emulsion, 0.8 part of an organic zirconium crosslinking agent (commercially available) was slowly added, and slowly stirred for 3 minutes to obtain a crosslinked emulsified nascent acid.
Performance testing
(1) The viscosities of the crosslinked emulsified authigenic acids prepared in examples 1 to 5 at room temperature and 160 ℃ were measured and compared with a crosslinked acid (a product of a petrochemical petroleum engineering research institute, a high-temperature clean low-corrosion crosslinked acid), and the results are shown in table 1, where the apparent viscosities of the crosslinked emulsified authigenic acids prepared in examples 1 to 4 at room temperature and high temperature are greater than those of the crosslinked acid, and the crosslinked emulsified authigenic acids have good temperature resistance, stability and viscosity at both room temperature and high temperature.
TABLE 1 comparison of apparent viscosity of crosslinked emulsified nascent acids
(2) The acid rock reaction rate of the cross-linked emulsified self-generated acid prepared in the examples 1 to 5 at 140 ℃ is tested and compared with that of the cross-linked acid, and the results are shown in table 2, and the acid rock reaction rate of the cross-linked emulsified self-generated acid system prepared in the examples 1 to 4 is lower than that of the cross-linked acid, which indicates that the cross-linked emulsified self-generated acid system of the invention has good high-temperature retarding performance.
TABLE 2 comparison of reaction rates
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Cross-linking acid |
| 1.11×10-5 | 1.10×10-5 | 1.16×10-5 | 1.12×0-5 | 1.02×0-5 | 2.67×10-5 |
The comparison of the two performances shows that the crosslinking emulsifying self-generating acid system has the advantages of high apparent viscosity, good temperature stability, good retarding effect and the like, meets the application of high-temperature reservoir acid fracturing, has a simple preparation method, and is worthy of popularization and application.
Claims (10)
1. A cross-linked emulsified authigenic acid, characterized in that it comprises:
a crosslinking acid base solution, an emulsified self-generated acid and a crosslinking agent;
based on 100 parts of the total volume of the crosslinking acid base solution and the emulsified self-generated acid,
0.6-1.5 parts of a crosslinking agent;
wherein the volume ratio of the crosslinking acid base liquid to the emulsified self-generated acid is (50-80): (50-20);
the cross-linking agent is selected from at least one of an organic zirconium cross-linking agent, an organic aluminum cross-linking agent and an organic titanium cross-linking agent;
The emulsified self-generated acid comprises an oil phase and a self-generated acid phase;
based on 100 parts of the total volume of the oil phase and the self-generated acid phase,
oil phase: 20-40 parts of a solvent;
self-acid generation phase: 80-60 parts of a solvent;
the total weight of the oil phase is 100 parts by weight, and the oil phase contains 2.0-4.0 parts by weight of water-in-oil emulsifier;
the water-in-oil emulsifier is one or a combination of dipolyhydroxystearate, sorbitan sesquioleate, sorbitan fatty acid ester, polyoxyethylene octyl phenol ether-10 and hexadecylamine;
the oil phase is one or a combination of diesel oil, kerosene, white oil and light crude oil;
the authigenic acid phase includes: chloroacetate, corrosion inhibitor, iron ion stabilizer and water;
based on the total weight of the self-generated acid phase as 100 parts:
60-80 parts of chloroacetate;
0.5-1.5 parts of iron ion stabilizer;
0.5-1.5 parts of corrosion inhibitor;
the balance of water;
the crosslinking acid base fluid comprises the following components in parts by weight:
based on 100 parts of the total weight of the crosslinking acid base solution,
90-96 parts of hydrochloric acid or hydrofluoric acid;
1.5-3 parts of a corrosion inhibitor;
0.8-1.8 parts of an iron ion stabilizer;
2.0-4.0 parts of an oil-in-water emulsifier;
0.5-1.2 parts of thickening agent for acid;
the concentration of the hydrochloric acid or hydrofluoric acid is 15% -30%.
2. The crosslinked emulsified autogenous acid of claim 1 wherein:
based on 100 parts of the total volume of the crosslinking acid base solution and the emulsified self-generated acid,
0.8-1.2 parts of a crosslinking agent;
wherein the volume ratio of the crosslinking acid base liquid to the emulsified self-generated acid is (55-75): (45-25).
3. The crosslinked emulsified autogenous acid of claim 1 wherein:
the emulsified self-generated acid comprises an oil phase and a self-generated acid phase;
based on 100 parts of the total volume of the oil phase and the self-generated acid phase,
oil phase: 25-35 parts;
75-65 parts of a self-generated acid phase;
the total weight of the oil phase is 100 parts by weight, and the oil phase contains 2.5-3.5 parts by weight of water-in-oil emulsifier.
4. The crosslinked emulsified autogenous acid of claim 1 wherein:
the total weight of the self-generated acid phase is 100 parts by weight:
65-75 parts of chloroacetate;
0.8-1.2 parts of iron ion stabilizer;
0.8-1.2 parts of corrosion inhibitor;
the balance of water.
5. The crosslinked emulsified autogenous acid of claim 1 wherein:
based on 100 parts of the total weight of the crosslinking acid base solution,
the concentration of the hydrochloric acid or hydrofluoric acid is 15-20 wt%.
6. The crosslinked emulsified autogenous acid of claim 1 wherein:
the corrosion inhibitor is selected from at least one of imidazoline corrosion inhibitors, quinoline quaternary ammonium salt corrosion inhibitors, ketone-aldehyde-amine condensate corrosion inhibitors and Mannich base corrosion inhibitors;
The iron ion stabilizer is at least one selected from citric acid, ethylenediamine tetraacetic acid, ascorbic acid and acetic acid;
the oil-in-water emulsifier is one or a combination of cetyl trimethyl ammonium bromide, sorbitan fatty acid ester polyoxyethylene ether, polyoxyethylene monostearate, sodium dodecyl benzene sulfonate and polyoxyethylene octyl phenol ether-10;
the acid thickener is at least one of polyacrylamide acid thickeners, guanidine gum or carboxymethyl guanidine gum natural polymers.
7. The crosslinked emulsified autogenous acid of claim 1 wherein:
the emulsified authigenic acid is prepared by a method comprising the following steps:
slowly adding the authigenic acid phase into the oil phase according to the dosage, and uniformly stirring and mixing at a high speed to prepare the emulsified authigenic acid; the stirring speed is 1000-3000 r/min, and the stirring time is 10-30 min;
the crosslinking acid-based fluid is prepared by a method comprising the following steps:
adding the acid thickening agent, the iron ion stabilizer, the corrosion inhibitor and the emulsifier into the hydrochloric acid or hydrofluoric acid solution while stirring, uniformly stirring, sealing and standing at room temperature to obtain the cross-linked acid base solution.
8. A process for the preparation of a cross-linked emulsified acid according to any one of claims 1 to 7, which comprises:
Adding the emulsified authigenic acid into the crosslinking acid base liquid while stirring, uniformly mixing to form uniform emulsion, and adding the crosslinking agent with the dosage into the emulsion to obtain the crosslinking emulsified authigenic acid.
9. The method of preparing a cross-linked emulsified authigenic acid as claimed in claim 8, wherein:
the stirring speed is 300-1500 r/min; the stirring time is 3-15 min.
10. The method of preparing a cross-linked emulsified authigenic acid as claimed in claim 9, wherein:
the stirring speed is 500-1000 r/min;
the stirring time is 5-10 min.
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| CN107699222A (en) * | 2017-11-02 | 2018-02-16 | 中国石油化工股份有限公司 | A kind of high temperature resistant crosslinking acid solution and preparation method thereof |
| CN108285784A (en) * | 2017-01-09 | 2018-07-17 | 中国石油化工股份有限公司 | A kind of gelling emulsified acid and preparation method thereof |
| CN108384529A (en) * | 2018-05-08 | 2018-08-10 | 中联煤层气有限责任公司 | A kind of water-in-oil emulsion fluid, preparation method and oil exploitation method |
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| CN108285784A (en) * | 2017-01-09 | 2018-07-17 | 中国石油化工股份有限公司 | A kind of gelling emulsified acid and preparation method thereof |
| CN107699222A (en) * | 2017-11-02 | 2018-02-16 | 中国石油化工股份有限公司 | A kind of high temperature resistant crosslinking acid solution and preparation method thereof |
| CN108384529A (en) * | 2018-05-08 | 2018-08-10 | 中联煤层气有限责任公司 | A kind of water-in-oil emulsion fluid, preparation method and oil exploitation method |
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