CN111117590A - Crosslinked emulsified acid, preparation method and application - Google Patents
Crosslinked emulsified acid, preparation method and application Download PDFInfo
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- CN111117590A CN111117590A CN201811292119.5A CN201811292119A CN111117590A CN 111117590 A CN111117590 A CN 111117590A CN 201811292119 A CN201811292119 A CN 201811292119A CN 111117590 A CN111117590 A CN 111117590A
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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
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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
- C09K8/725—Compositions containing polymers
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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
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
Abstract
The invention discloses a cross-linked emulsified acid, a preparation method and application thereof. The crosslinked emulsified acid comprises: a crosslinking acid base solution, an oil phase 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 oil phase as 100 parts; the oil phase is one or a combination of diesel oil, kerosene, white oil and light crude oil; the cross-linking agent is an organic zirconium cross-linking agent, an organic aluminum cross-linking agent or an organic titanium cross-linking agent. The preparation method comprises the following steps: and slowly adding the oil phase into the crosslinking acid base solution according to the dosage, continuously stirring to uniformly mix the oil phase and the crosslinking acid base solution to form a uniform emulsion, and then adding a crosslinking agent to prepare the crosslinking emulsified acid. Compared with the conventional ground crosslinked acid system, the crosslinked emulsified 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.
Description
Technical Field
The invention relates to the field of acid fracturing production increase of carbonate reservoirs, in particular to a cross-linked emulsified acid, a preparation method and application.
Background
The ground crosslinked acid is the most common retarding acid system for low-permeability, fracture-cavity and fracture carbonate reservoirs and acid fracturing reconstruction. 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. In recent years, the technology of ground crosslinked acid is continuously improved,
chinese patent CN104194767A discloses a high-temperature emulsified acid liquid, the oil phase and acid phase of the emulsified acid liquid are 100 parts by weight, and the emulsified acid liquid comprises: oil phase: 30-50 parts of acid phase: 50-70 parts of a solvent; the oil phase comprises the following components in parts by mass based on 100 parts by mass: emulsifier: 8-21 parts of corrosion inhibitor: 2-8 parts of diesel oil and the balance of diesel oil; the acid phase comprises the following components in parts by mass based on 100 parts by mass: iron ion stabilizer: 2-4 parts of concentrated hydrochloric acid and the balance. But a temperature resistance of 120 ℃. It is difficult to meet the needs of high temperature reservoirs.
At present, a ground crosslinking acid system applied on site can resist the temperature of 160 ℃ at most, although the application of high-temperature reservoir acid fracturing modification can be met, the problems of short acid-etched fracture, limited reservoir communication range, poor acid fracturing modification effect and the like exist. With the continuous deepening of the exploration and development of the high-temperature carbonate reservoir, higher requirements are put forward on the performance of a high-temperature acid liquid system, so that the development of a novel acid liquid system with a good retarding effect at high temperature is urgently needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a cross-linked emulsified acid, a preparation method and application. The invention utilizes emulsification and crosslinking to wrap the oil phase in a network structure of crosslinking acid, thereby forming a novel acid liquid system with excellent oil-in-acid performance. The network structure formed by the cross-linked acid is utilized to wrap emulsified and dispersed oil drops, the oil drops are 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 oil drops, and meanwhile, the oil drops enhance the temperature resistance and the viscosity of a cross-linked acid system. Under the condition that the structure of the cross-linked emulsion is not damaged, oil drops are dispersed to slow down the diffusion coefficient of H + ions of the cross-linked acid, the contact area of the H + ions and rocks is reduced, and further the acid rock reaction is reduced. The cross-linked emulsified acid system reduces acid liquor filtration loss through film forming blocking effect, tackifying blocking effect, two-phase flow effect and Jamin effect, further effectively prolongs acid liquor etching distance, can form uneven etching effect and improves acid etching crack flow conductivity. Compared with the conventional ground crosslinked acid system, the crosslinked emulsified 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.
One of the objects of the present invention is to provide a crosslinked emulsified acid.
The crosslinked emulsified acid comprises:
a crosslinking acid base solution, an oil phase and a crosslinking agent;
based on 100 parts of the total volume of the crosslinking acid base solution and the oil phase,
0.6-1.5 parts of a crosslinking agent; preferably 0.8 to 1.2 parts.
The oil phase is one or a combination of diesel oil, kerosene, white oil and light crude oil;
the cross-linking agent is an organic zirconium cross-linking agent, an organic aluminum cross-linking agent or an organic titanium cross-linking agent.
The volume ratio of the cross-linking acid base liquid to the oil phase is (50-70): (50 to 30)
The crosslinking acid-based liquid is prepared from the following raw materials:
the concentration of the hydrochloric acid solution is 15-30 wt%; preferably 15% to 20% wt.
The acid thickening agent is selected from polyacrylamide acid thickening agents or guanidine gum natural polymers; the thickening agent for polyacrylamide acid is selected from at least one of cationic polyacrylamide or anionic acid-resistant polyacrylamide; the guanidine gum natural polymer is at least one of hydroxypropyl guanidine gum or carboxymethyl guanidine gum;
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; more preferably 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt, 2-methylquinoline benzyl quaternary ammonium salt or a combination thereof;
the iron ion stabilizer is organic acid; preferably one or a combination of citric acid, acetic acid, ethylene diamine tetraacetic acid and ascorbic acid.
The 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 crosslinking acid-based fluid is prepared by a method comprising the following steps:
and (3) adding the acid thickening agent, the iron ion stabilizer, the corrosion inhibitor and the emulsifier into the hydrochloric acid solution while stirring, fully and uniformly stirring, sealing and standing at room temperature to obtain the cross-linked acid base solution.
The second purpose of the invention is to provide a preparation method of the cross-linked emulsified acid.
The method comprises the following steps:
and slowly adding the oil phase into the crosslinking acid base solution according to the dosage, continuously stirring to uniformly mix the oil phase and the crosslinking acid base solution to form a uniform emulsion, and then adding a crosslinking agent to prepare the crosslinking emulsified acid.
The invention also aims to provide the application of the cross-linked emulsified acid in fracturing of carbonate reservoirs.
Preferably, the following technical scheme can be adopted in the invention:
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 corrosion inhibitor is a high-temperature corrosion inhibitor, and can be 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 can be at least one or a combination of organic acids such as citric acid, acetic acid, ethylene diamine tetraacetic acid, ascorbic acid and the like.
The emulsifier is one or a combination of more of cetyl trimethyl ammonium bromide, sorbitan fatty acid ester polyoxyethylene ether, polyoxyethylene monostearate, sodium dodecyl benzene sulfonate and polyoxyethylene octyl phenol ether-10.
The crosslinking agent may be selected from one of conventional surface crosslinking acids and crosslinking agents for subsurface crosslinking acids. Specifically, there may be mentioned, for example, an organic zirconium crosslinking agent, an organic aluminum crosslinking agent, an organic titanium crosslinking agent and the like.
A preparation method of a cross-linked emulsified acid comprises the following steps:
and slowly adding the oil phase into the cross-linked acid base solution according to the dosage, stirring during and after the addition of the oil phase so as to uniformly mix the oil phase and the cross-linked acid base solution to form uniform emulsion, and then adding a cross-linking agent into the emulsion to form cross-linked emulsified acid.
The preparation method of the crosslinking acid-based fluid can comprise the following steps:
preparing the hydrochloric acid solution, adding a thickening agent for acid, an iron ion stabilizer, a corrosion inhibitor and an emulsifier under full 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 liquid 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 preparation method of the cross-linked emulsified acid can comprise the following steps:
1) slowly adding the oil phase into the base solution of the cross-linking acid according to the dosage, stirring at 500-1000 r/min during and after the addition so as to uniformly mix the oil phase and the base solution, and stirring for 5-10 min to form a 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 acid system.
In order to further improve the acidification and acid fracturing effects, the invention provides a novel cross-linked emulsified acid used in the acidification, fracturing and reconstruction processes of carbonate reservoirs and a preparation method thereof. Compared with the conventional ground crosslinked acid system, the crosslinked emulsified acid obtained by the technical scheme of the invention has the characteristics of better retarding performance, stability, temperature resistance and the like, has good acid fracturing/acidizing effect after being injected into a stratum, and has wide popularization and application prospects.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 100 parts of hydrochloric acid solution (the concentration is 15% wt), slowly adding 0.6 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical petroleum engineering technical institute, SRAP-1) at the rotating speed of 500r/min, stirring for half an hour to form uniform solution, then adding 1.2 parts of iron ion stabilizer (ethylene diamine tetraacetic acid, Tianjin photoreplication 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;
2) 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 500r/min, wherein the volume ratio of the two phases is that of the crosslinking acid base liquid: the oil phase is 50:50, and stirring is continued for 5min after the dripping is finished;
4) 0.8 part 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 acid.
Example 2
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 100 parts of hydrochloric acid solution (the concentration is 20% wt), slowly adding 0.7 part of polyacrylamide thickening agent SRAP-1 (produced by China petrochemical petroleum engineering technical institute), stirring for half an hour 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 white oil into the prepared crosslinking acid base liquid under the condition that the stirring speed is 800r/min, wherein the volume ratio of the two phases is that of the crosslinking acid base liquid: the oil phase is 60:40, and the stirring is continued for 7min after the dripping is finished;
4) slowly adding 1.0 part of organic titanium crosslinking agent (produced by China petrochemical petroleum engineering technical research institute) into the emulsion, and slowly stirring for 3 minutes to obtain the crosslinked emulsified acid.
Example 3
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 100 parts of hydrochloric acid solution (the concentration is 25 percent by weight), slowly adding 0.8 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical petroleum engineering technical institute), stirring for half an hour to form a uniform solution, then adding 1.5 parts of iron ion stabilizer acetic acid (sold in the market), 3.5 parts of Mannich base 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;
2) 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;
4) 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 acid.
Example 4
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 100 parts of hydrochloric acid solution (the concentration is 15% by weight), slowly adding 0.8 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical petroleum engineering technical 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 markets), 3.5 parts of 2-methylquinoline benzyl quaternary ammonium salt corrosion inhibitor (sold in markets) and 3.0 parts of mixture (mass ratio is 1:1) (sold in markets) of sodium dodecyl benzene sulfonate and hexadecyl trimethyl ammonium bromide 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 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 55:45, and stirring is continued for 10min after the dripping is finished;
4) 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 acid.
Performance testing
(1) The viscosities of the crosslinked emulsified acids prepared in examples 1 to 4 at room temperature and 120 ℃ were measured and compared with the crosslinked acid, and the results are shown in table 1, where the apparent viscosities of the crosslinked emulsified acids prepared in examples 1 to 4 at room temperature and high temperature were greater than those of the crosslinked acid, and the crosslinked emulsified acids had good temperature stability and viscosities at both room temperature and high temperature.
Comparative example cross-linked acid manufactured by petrochemical petroleum engineering technology research institute,
the formula is as follows: 0.8 percent of thickening agent, 2 percent of corrosion inhibitor, 1 percent of iron ion stabilizer and 1 percent of demulsifier
TABLE 1 comparison of apparent viscosity of crosslinked emulsified acids
(2) The acid-rock reaction rate of the crosslinked emulsified acid prepared in the examples 1 to 4 at 120 ℃ is tested and compared with that of the crosslinked acid, and the results are shown in table 2, and the acid-rock reaction rate of the crosslinked emulsified acid system prepared in the examples 1 to 4 is lower than that of the crosslinked acid, which shows that the crosslinked emulsified 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 | Common emulsified acid |
| 1.10×10-5 | 1.08×10-5 | 1.11×10-5 | 1.101×0-5 | 2.47×10-5 |
As can be seen from the comparison of the four performances, the cross-linked emulsified acid has the advantages of high apparent viscosity, good temperature stability, good retarding effect and the like, and the preparation method is simple and is worthy of popularization and application.
Claims (10)
1. A crosslinked emulsified acid characterized in that said crosslinked emulsified acid comprises:
a crosslinking acid base solution, an oil phase and a crosslinking agent;
based on 100 parts of the total volume of the crosslinking acid base solution and the oil phase,
0.6-1.5 parts of a crosslinking agent;
the oil phase is one or a combination of diesel oil, kerosene, white oil and light crude oil;
the cross-linking agent is an organic zirconium cross-linking agent, an organic aluminum cross-linking agent or an organic titanium cross-linking agent.
2. The crosslinked emulsified acid as set forth in claim 1, wherein:
based on 100 parts of the total volume of the crosslinking acid base solution and the oil phase,
0.8-1.2 parts of a crosslinking agent.
3. The crosslinked emulsified acid as set forth in claim 1, wherein:
the volume ratio of the cross-linking acid base liquid to the oil phase is (50-70): (50-30).
4. The crosslinked emulsified acid as set forth in claim 1, wherein:
the crosslinking acid-based liquid is prepared from the following raw materials:
the concentration of the hydrochloric acid solution is 15-30 wt%.
5. The crosslinked emulsified acid as set forth in claim 4, wherein:
the concentration of the hydrochloric acid solution is 15-20 wt%.
6. The crosslinked emulsified acid as set forth in claim 4, wherein:
the acid thickening agent is selected from polyacrylamide acid thickening agents or guanidine gum natural polymers;
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 organic acid;
the 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.
7. The crosslinked emulsified acid as set forth in claim 6, wherein:
the thickening agent for polyacrylamide acid is selected from at least one of cationic polyacrylamide or anionic acid-resistant polyacrylamide; the guanidine gum natural polymer is at least one of hydroxypropyl guanidine gum or carboxymethyl guanidine gum;
the corrosion inhibitor is one or a combination of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt and 2-methylquinoline benzyl quaternary ammonium salt;
the iron ion stabilizer is one or a combination of citric acid, acetic acid, ethylene diamine tetraacetic acid and ascorbic acid.
8. The crosslinked emulsified acid as set forth in claim 4, wherein:
the crosslinking acid-based fluid is prepared by a method comprising the following steps:
and (3) adding the acid thickening agent, the iron ion stabilizer, the corrosion inhibitor and the emulsifier into the hydrochloric acid solution while stirring, fully and uniformly stirring, sealing and standing at room temperature to obtain the cross-linked acid base solution.
9. A process for the preparation of a cross-linked emulsified acid as claimed in any one of claims 1 to 8, which comprises:
and slowly adding the oil phase into the crosslinking acid base solution according to the dosage, continuously stirring to uniformly mix the oil phase and the crosslinking acid base solution to form a uniform emulsion, and then adding a crosslinking agent to prepare the crosslinking emulsified acid.
10. Use of a cross-linked emulsified acid according to any one of claims 1 to 8 in fracturing a carbonate reservoir.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111234800A (en) * | 2018-11-29 | 2020-06-05 | 中国石油化工股份有限公司 | Emulsified crosslinked acid and preparation method thereof |
| CN112195020A (en) * | 2020-10-09 | 2021-01-08 | 西南石油大学 | Dynamic nano-gel system for improving oil field recovery ratio and water control method |
| CN113969775A (en) * | 2020-07-22 | 2022-01-25 | 中国石油化工股份有限公司 | Method for improving effective acid corrosion seam length of ultra-deep carbonate rock reservoir and application |
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| CN113969775A (en) * | 2020-07-22 | 2022-01-25 | 中国石油化工股份有限公司 | Method for improving effective acid corrosion seam length of ultra-deep carbonate rock reservoir and application |
| CN112195020A (en) * | 2020-10-09 | 2021-01-08 | 西南石油大学 | Dynamic nano-gel system for improving oil field recovery ratio and water control method |
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