CN112646563B - Solid slow-release acid and preparation method thereof - Google Patents
Solid slow-release acid and preparation method thereof Download PDFInfo
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Abstract
The invention provides a solid slow-release acid and a preparation method thereof, wherein the slow-release acid is prepared by mixing raw materials of p-toluenesulfonic acid, hydroxy ethylidene diphosphonic acid, a cross-linking conditioner, a temperature stabilizer and a dehydrating agent and performing polycondensation reaction under the action of a catalyst; wherein the weight portion of the p-toluenesulfonic acid is 14-20 portions; 5-15 parts of hydroxyethylidene diphosphonic acid; the weight portion of the crosslinking conditioning agent is 55-65 portions; the weight portion of the temperature stabilizer is 5-10 portions. The solid slow-release acid provided by the invention has a melting point of 90-150 ℃, is high-temperature resistant, has a viscosity of less than or equal to 30mPa & s, is used for acid rock fracturing, has a slow-release time of 3-7 days, requires 5-8 days for complete dissolution in water at 25 ℃, has good dispersibility, has an application temperature of 80-150 ℃, has a hydrogen ion concentration of 2-15/mg/L, and is strong in acidity; and the environment-friendly odor-free environment-friendly paint is environment-friendly and more safe and friendly to operators.
Description
Technical Field
The invention belongs to the technical field of oilfield production increase transformation, and particularly relates to a solid slow-release acid and a preparation method thereof.
Background
The slow release acid is an acid which can be used for acidizing modification in oil field reservoir development. At present, reservoir lithology of oil fields in China is generally fine sand, medium sandstone, coarse sandstone, gravelly sandstone and glutenite, and the physical properties of the reservoir lithology gradually deteriorate along with the increase of the burial depth. The mineral components of the rock are quartz and feldspar cuttings mixed, the argillaceous or carbonate is cemented, the rock is compact and hard, the geological conditions are complex, and the yield is low. Therefore, acidizing modifications are needed to build, increase and stabilize production.
Patent No. CN201910897693.1 provides a retarded acid system, which comprises alkyl trimethyl ammonium chloride and water soluble calcium salt; the alkyl is a long-chain alkyl containing 8-22 carbon atoms. The component also comprises 1 percent of corrosion inhibitor Mannich base and iron ion stabilizer. In practical application, the dosage mass percentage of the alkyl trimethyl ammonium chloride is 0.12-0.95%, and the dosage concentration of the calcium salt is 10-100 mmol/L. The alkyl trimethyl ammonium chloride is coated on the rock surface through physical adsorption, and is subjected to hydrophobic wetting modification to make hydrophilic H+The surface of the rock is not easy to contact, the reaction surface speed is controlled, the acid rock reaction time is prolonged, and the effect of retarding is achieved. However, the retarded acid has low temperature resistance and weak acidity. Patent No. CN201811451718.7 provides a graded retarded emulsion acid whose components comprise a cross-linking acid and an emulsion acid; the content of the crosslinking acid is 50-80 parts by volume, preferably 55-75 parts by volume; the emulsified acid is 20-50 parts, preferably 25-45 parts. The crosslinking acid comprises a crosslinking acid base fluid and a crosslinking agent; the content of the crosslinking acid base liquid in the crosslinking acid is 94.8-107 parts by weight, preferably 101.5-104.5 parts by weight; the content of the cross-linking agent is 0.6-1.5 parts, preferably 0.8-1.2 parts. The emulsified acid comprises an oil phase and an acid phase; the content of the oil phase is 20-40 parts by volume, preferably 25-35 parts by volume; the content of acid phase is 60-80 parts, preferably65-75 parts is selected, but the acid has low temperature resistance. Therefore, the slow-release acid disclosed in the above patent has problems of low temperature resistance and weak acidity.
Disclosure of Invention
The invention provides a solid slow-release acid and a preparation method thereof, which aim to solve the technical problems of low temperature resistance and weak acidity of the slow-release acid in the prior art.
On one hand, the invention provides a solid slow-release acid, which is prepared by mixing raw materials of p-toluenesulfonic acid, hydroxy ethylidene diphosphonic acid, a crosslinking conditioner, a temperature stabilizer and a dehydrating agent and performing polycondensation reaction under the action of a catalyst; wherein the weight portion of the p-toluenesulfonic acid is 14-20 portions; 5-15 parts of hydroxyethylidene diphosphonic acid; the weight portion of the crosslinking conditioning agent is 55-65 portions; the weight portion of the temperature stabilizer is 5-10 portions.
Further, the dehydrating agent is at least one of: carbon tetrachloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and phosphorus pentoxide.
Further, the weight of the dehydrating agent is 1.5-3.5% of the weight of the crosslinking conditioning agent.
Further, the temperature stabilizer is at least one of: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid.
Further, the crosslinking conditioning agent is at least one of: glycolic acid, lactic acid, alpha-glycolic acid, gluconic acid, glycolic acid.
Further, the catalyst is at least one of: tin oxide, halide, organic acid salt, antimony oxide, zinc oxide, and aluminum oxide.
Further, the weight of the catalyst is 0.001-0.005% of the weight of the p-toluenesulfonic acid.
In another aspect, the present invention provides a method for preparing the solid sustained-release acid, the method comprising,
mixing the raw materials to obtain a first mixture; the raw materials comprise the following components in parts by weight: crosslinking conditioning agent: 55-65 parts; p-toluenesulfonic acid: 14-20 parts; hydroxyethylidene diphosphonic acid: 5-15 parts; temperature stabilizer: 5-10 parts;
and carrying out polycondensation reaction on the first mixture under the action of a catalyst to prepare the solid slow-release acid.
Further, the polycondensation reaction comprises normal pressure polycondensation reaction and reduced pressure polycondensation reaction, wherein the temperature of the normal pressure polycondensation reaction is 100-.
Further, the degree of vacuum of the reduced-pressure polycondensation reaction was 100-10000 Pa.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a solid slow-release acid and a preparation method thereof, wherein p-toluenesulfonic acid and hydroxy ethylidene diphosphonic acid are used as raw materials for providing hydrogen ions, a cross-linking conditioner, a temperature stabilizer and a dehydrating agent are added, and a polycondensation reaction is carried out under the action of a catalyst, so that a single chain is changed into a double-chain solid slow-release acid, the solid slow-release acid is more stable than the single chain at high temperature and is broken at a higher temperature, and the high-temperature resistance of the solid slow-release acid is improved, so that the solid slow-release acid can be applied to acid rock reaction at the high temperature of 90-150 ℃; meanwhile, the solid slow-release acid with the double-chain structure also enables the solid acid to have good dispersibility in hot water; the environment is protected, no peculiar smell is generated, and the method is safe and friendly to operators; and hydrogen ions can be released step by step, so that the catalyst has strong acidity; the solid slow-release acid provided by the invention has the melting point of 90-150 ℃, is high-temperature resistant, has the viscosity of less than or equal to 30mPa & s, is used for acid rock fracturing, has the slow-release time of 3-7 days, needs 5-8 days for completely dissolving in water at the temperature of 25 ℃, has good dispersibility, has the applicable temperature of 80-150 ℃, has the hydrogen ion concentration of 2-15/mg/L, and has strong acidity.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a process diagram of a preparation method of a solid sustained-release acid provided by an embodiment of the invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are illustrative of the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
on one hand, the embodiment of the invention provides a solid slow-release acid, which is prepared by mixing raw materials of p-toluenesulfonic acid, hydroxyethylidene diphosphonic acid, a crosslinking conditioner, a temperature stabilizer and a dehydrating agent and performing polycondensation reaction under the action of a catalyst; wherein the weight portion of the p-toluenesulfonic acid is 14-20 portions; 5-15 parts of hydroxyethylidene diphosphonic acid; the weight portion of the crosslinking conditioning agent is 55-65 portions; the weight portion of the temperature stabilizer is 5-10 portions.
The p-toluenesulfonic acid is a white needle-like or powdery crystal, is easily soluble in water, alcohol and ether, is very easy to deliquesce, is easy to dehydrate and carbonize carbohydrates such as cotton fabrics, wood, paper and the like, and is insoluble in benzene solvents such as benzene, toluene, xylene and the like. P-cresol is generated during alkali fusion, is an organic strong acid without oxidability, can be widely used for synthesizing medicines, pesticides, stabilizers of polymerization reactions and catalysts for organic synthesis (esters and the like), is used as an intermediate of medicines and coatings, is used as a resin curing agent and is also used as an electroplating intermediate. In the invention, the p-toluenesulfonic acid is a hydrogen ion source in the solid acid, and the p-toluenesulfonic acid and the hydroxyethylidene diphosphonic acid are subjected to polycondensation reaction to form the double-chain solid slow-release acid, and the double-chain solid slow-release acid can release hydrogen ions step by step, so that the high temperature resistance of the p-toluenesulfonic acid is improved, and the p-toluenesulfonic acid has good dispersibility.
Hydroxyethylidene diphosphonic acid (HEDP) is an organic phosphoric acid scale and corrosion inhibitor, can form a stable complex with iron, copper, zinc and other metal ions, and can dissolve oxides on the metal surface. HEDP still can play good inhibition and scale inhibition effects at 250 ℃, is stable under high pH value, is not easy to hydrolyze, and is not easy to decompose under common photo-thermal conditions. The acid and alkali resistance and the chlorine and oxidation resistance are better than those of other organic phosphates. HEDP can form a six-ring chelate with metal ions in water, especially calcium ions, so HEDP has a good scale inhibition effect and an obvious solubility limit effect, and shows an ideal synergistic effect when being used in combination with other water treatment agents. In the invention, the hydroxyethylidene diphosphonic acid is a hydrogen ion source in the solid acid, and the hydroxyethylidene diphosphonic acid and the p-toluenesulfonic acid generate polycondensation reaction to form double-chain solid slow-release acid, and the double-chain solid slow-release acid can release hydrogen ions step by step, thereby improving the high temperature resistance of the solid slow-release acid and having good dispersibility.
Crosslinking conditioning agent: the crosslinking conditioning agent can cause the p-toluenesulfonic acid and the hydroxyethylidene diphosphonic acid to carry out polycondensation reaction, and the crosslinking conditioning agent is too little to form double-chain solid slow-release acid, so that the high temperature resistance and the dispersibility are reduced; too much crosslinking conditioning agent and poor economy.
Temperature stabilizer: the temperature stabilizer can stabilize the reaction temperature of the solid acid, so that the fluctuation of the reaction temperature is small, the temperature stabilizer is too small, the reaction activity of the p-toluenesulfonic acid and the hydroxyethylidene diphosphonic acid is removed, the polycondensation reaction is difficult to occur, and the yield of the solid acid is low. Too much temperature stabilizer, poor economy.
The dehydrating agent can remove water in the hydroxyethylidene diphosphonic acid, thereby avoiding generating liquid components in the solid acid, and if the solid acid contains the liquid components, the solid slow-release acid can gradually release hydrogen ions to weaken the acidity.
Catalyst: the catalyst can reduce the reaction potential energy and promote the polycondensation reaction of the reactants under the conditions of lower temperature and pressure.
As an embodiment of the present invention, the dehydrating agent is at least one of: carbon tetrachloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and phosphorus pentoxide.
As an embodiment of the present invention, the weight of the dehydrating agent is 1.5 to 3.5% of the weight of the cross-linking conditioner.
Too much dehydrating agent in parts by weight, poor economy, too little dehydrating agent in parts by weight, and unobvious dehydrating effect.
As an implementation of the embodiment of the present invention, the temperature stabilizer is at least one of the following: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid.
As an embodiment of the embodiments of the present invention, the crosslinking conditioning agent is at least one of: glycolic acid, lactic acid, alpha-glycolic acid, gluconic acid, glycolic acid.
As an implementation of the embodiment of the present invention, the catalyst is at least one of the following: tin oxide, halide, organic acid salt, antimony oxide, zinc oxide, and aluminum oxide.
In one embodiment of the inventive process, the weight of the catalyst is 0.001 to 0.005% of the weight of the p-toluenesulfonic acid. The catalyst has too large weight part, poor economy, too small weight part and unobvious effect.
In another aspect, an embodiment of the present invention further provides a method for preparing a solid sustained-release acid, which, with reference to fig. 1, includes,
s1, mixing the raw materials to obtain a first mixture; the raw materials comprise the following components in parts by weight: crosslinking conditioning agent: 55-65 parts; p-toluenesulfonic acid: 14-20 parts; hydroxyethylidene diphosphonic acid: 5-15 parts; temperature stabilizer: 5-10 parts;
s2, carrying out polycondensation reaction on the first mixture under the action of a catalyst to obtain the solid slow-release acid.
As an implementation manner of the embodiment of the invention, the polycondensation reaction includes an atmospheric pressure polycondensation reaction and a reduced pressure polycondensation reaction, the temperature of the atmospheric pressure polycondensation reaction is 100-230 ℃, and the temperature of the reduced pressure polycondensation reaction is 160-240 ℃.
The yield is influenced by overhigh temperature of the normal-pressure polycondensation reaction, and meanwhile, the potential safety hazard is caused by overhigh temperature and pressure of a reaction system; the yield is affected by the over-low temperature of the normal pressure polycondensation reaction, which is not favorable for the polycondensation reaction. The yield is influenced by the overhigh temperature of the reduced pressure polycondensation reaction, and meanwhile, the overhigh temperature of a reaction system can cause potential safety hazard; the yield is affected by the temperature of the reduced pressure polycondensation, which is too low, and the polycondensation is not facilitated to occur.
As an embodiment of the present invention, the vacuum degree of the reduced pressure polycondensation reaction is 100-10000 Pa.
Hereinafter, a solid sustained-release acid and a method for preparing the same according to the present invention will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
Embodiment 1 provides a solid slow-release acid and a preparation method thereof, which are applied to a 1XX well in a Yanjiachuan operation area of a second oil production plant in a Changqing oilfield, wherein the reservoir temperature is 80 ℃, 200t of fracturing fluid is required, and 20t of environment-friendly solid slow-release acid is added.
Preparing environment-friendly solid slow-release acid: 55 parts of glycolic acid, 15 parts of p-toluenesulfonic acid, 5 parts of hydroxyethylidene diphosphonic acid and 5 parts of ethylene diamine tetraacetic acid are fully stirred and dissolved, 0.825 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is added, after full stirring and dissolution, 0.00015 parts of tin oxide is added as a catalyst to carry out normal pressure polycondensation reaction at the normal pressure of 100 ℃, after full stirring and dissolution, reduced pressure polycondensation reaction is carried out at the pressure of 0.01MPa and the temperature of 160 ℃, and after full stirring and dissolution, the environment-friendly solid slow-release acid is obtained. During construction, the environment-friendly solid slow-release acid is continuously added along with a stirring pool in the sand mixing truck. The yield of the 1XX well before acid fracturing is 0.62t/d, the yield of the 1XX well after acid fracturing is 2.52t/d, the daily oil increase of a single well is 1.9t/d, and the measure effect is obvious.
Example 2
Embodiment 2 provides a solid slow-release acid and a preparation method thereof, which are applied to a 658-XX well in a second oil production plant in a Hongkong oilfield, wherein the reservoir temperature is 100 ℃, and clear water is adopted to prepare acid liquid for construction. 200t of fracturing fluid, 40t of environment-friendly solid slow-release acid and 160t of clear water are needed.
Preparing environment-friendly solid slow-release acid: 60 parts of lactic acid, 17 parts of p-toluenesulfonic acid, 10 parts of hydroxy ethylidene diphosphonic acid and 10 parts of diethylenetriamine pentaacetic acid are fully stirred and dissolved, 2.1 parts of carbon tetrachloride dehydrating agent by weight is added, after full stirring and dissolution, 0.00085 part of tin oxide catalyst is added to carry out normal pressure polycondensation reaction at the normal pressure of 150 ℃, after full stirring and dissolution, reduced pressure polycondensation reaction is carried out under the conditions that the pressure is 0.01MPa and the temperature is 200 ℃, and after full stirring and dissolution, the environment-friendly solid slow-release acid is obtained. The yield of the harbor 658-XX well before acid fracturing is 0.27t/d, the yield of the well after construction is 1.89t/d, the daily oil increment of a single well is 1.62t/d, and the measure effect is obvious.
Example 3
Embodiment 3 provides a solid slow-release acid and a preparation method thereof, which are applied to NP1-X wells in a Jidong oil Nanbao operation area, wherein the reservoir temperature is 130 ℃, and acid liquor prepared by clear water is adopted for construction. 200t of fracturing fluid, 60t of environment-friendly solid slow-release acid and 140t of clear water are needed.
Preparing environment-friendly solid slow-release acid: 65 parts of glycollic acid, 20 parts of p-toluenesulfonic acid, 15 parts of hydroxy ethylidene diphosphonic acid and 10 parts of diethylenetriamine pentaacetic acid are fully stirred and dissolved, 2.28 parts of phosphorus pentoxide are added and fully stirred and dissolved, 0.001 part of zinc oxide is added to carry out normal pressure polycondensation reaction under the normal pressure condition of 180 ℃, after fully stirred and dissolved, reduced pressure polycondensation reaction is carried out under the conditions that the pressure is 0.01MPa and the temperature is 240 ℃, and after fully stirred and dissolved, the environment-friendly solid slow-release acid is obtained. During construction, the environment-friendly solid slow-release acid is continuously added along with a stirring pool in the sand mixing truck. The pressure is stable in the NP1-X well construction process, the daily liquid production after pressing is improved by more than 2 times, and the measure effect is obvious.
Example 4
Example 4 provides a solid sustained-release acid and a preparation method thereof, wherein, taking example 1 as a reference, example 4 is different from example 1 in that the weight part of p-toluenesulfonic acid is 18 parts, the weight part of hydroxy ethylidene diphosphonic acid is 13 parts, gluconic acid is used for replacing glycolic acid, and aluminum oxide is used for replacing tin oxide.
Example 5
Example 5 provides a solid slow-release acid and a preparation method thereof, and takes example 1 as a reference, and the difference of example 5 from example 1 is that alpha-glycolic acid is used for replacing glycolic acid, and halide is used for replacing tin oxide.
Comparative example 1
Comparative example 1 provides a slow-release acid prepared by adding an oxide of aluminum to a starting material of polyacetic acid and citric acid, and performing polycondensation reaction. Wherein the weight parts of the raw materials are respectively as follows: 60 parts of polyacetic acid, 25 parts of citric acid and 10 parts of aluminum oxide. The slow-release acid is applied to a 1XX well in a second oil production factory of a Changqing oilfield in a Jiachuan operation area, and the reservoir temperature is 80 ℃.
Comparative example 2
Comparative example 2 provides a slow release acid, and with reference to example 1, comparative example 1 differs from example 1 in that 30 parts by weight of p-toluenesulfonic acid, 25 parts by weight of hydroxyethylidene diphosphonic acid, 80 parts by weight of hydroxyethyl acid, 20 parts by weight of ethylenediaminetetraacetic acid, and a suitable reservoir temperature of 140 ℃.
Comparative example 3
Comparative example 3 provides a slow release acid, which is prepared by taking example 1 as a reference, and the difference between the comparative example 3 and the example 1 is that the weight part of p-toluenesulfonic acid is 8 parts, the weight part of hydroxyethylidene diphosphonic acid is 2 parts, the weight part of hydroxyethyl acid is 30 parts, the weight part of ethylene diamine tetraacetic acid is 2 parts, and the applicable reservoir temperature is 130 ℃.
TABLE 1
As can be seen from Table 1, the solid slow-release acid provided in examples 1 to 5 has a melting point of 90 to 150 ℃, is resistant to high temperature, has a viscosity of not more than 30mPa · s, is used for acid rock fracturing, has a slow-release time of 3 to 7 days, requires 5 to 8 days to achieve complete dissolution in water at 25 ℃, has good dispersibility, is applicable at a temperature of 80 to 150 ℃, has a hydrogen ion concentration of 2 to 15/mg/L, and has strong acidity.
It should be noted that comparison of the solid sustained-release acid is meaningful under the same temperature condition (reservoir temperature), and comparison cannot be directly performed under different temperature conditions; thus, example 5 and comparative example 1 described above can be compared, example 4 and comparative example 2 can be compared, and example 3 and comparative example 3 can be compared.
Comparative example 1 provides a slow-release acid having a melting point of 150 c, a viscosity of 10mPa · s, lower than that of example 5, poor fluidity, and an extended acid rock fracturing time, a slow-release time for acid rock fracturing of 5 days, a time required for achieving complete dissolution in water at 25 c of 8 days, poor dispersibility than that of example 5, a working temperature of 150 c, a hydrogen ion concentration of 12/mg/L, and lower acidity than that of example 5.
The sustained-release acid provided in comparative example 2 has a melting point of 130 ℃, a viscosity of 15mPa · s, a sustained-release time of 5 hours, a dissolution time of 8 days, an applicable temperature of 140 ℃, and a hydrogen ion concentration of 8mg/L, and is less acidic than that of example 4.
The slow-release acid provided in comparative example 3 has a melting point of 110 ℃, a viscosity of 10 mPas, a slow-release time of 6h, a dissolution time of 9 days, an applicable temperature of 130 ℃, a hydrogen ion concentration of 5mg/L, and is less acidic than that of example 3.
The embodiment of the invention provides a solid slow-release acid and a preparation method thereof, the solid slow-release acid is a novel graded slow-release crosslinking emulsified acid, comprehensive properties such as acid liquid rheology, gel breaking, compatibility and the like are fully considered, and the solid slow-release acid has the advantages of high apparent viscosity, low filtration loss, good temperature stability, good slow-release effect and the like; delay the reaction speed of acid rock, enlarge the action range of acid etching and improve the yield-increasing effect of acid etching. The solid slow-release acid provided by the invention also has the following advantages:
(1) the highest temperature resistance can reach 150 ℃, the melting point is high, and the heat resistance is good;
(2) it has no caking in hot water and good dispersibility.
(3) The acid has strong acidity, 10% solid slow-release acid aqueous solution is dissolved for 24 hours at the temperature of 90 ℃, and the concentration of hydrogen ions is equivalent to 6% hydrochloric acid; dissolving 30% solid slow-release acid aqueous solution for 24h at 120 ℃, wherein the hydrogen ion concentration is equivalent to 12% hydrochloric acid; the amount of the fracturing process is small, and the economical efficiency is good;
(4) the dual-dosage form slow-release acid contains formaldehyde, compared with the dual-dosage form, the solid acid can ionize hydrogen ions step by step, and the dual-dosage form slow-release acid is environment-friendly, free of peculiar smell and safer and more friendly to operators.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (4)
1. The solid slow-release acid is characterized in that the slow-release acid is prepared by mixing raw materials of p-toluenesulfonic acid, hydroxy ethylidene diphosphonic acid, a crosslinking conditioner, a temperature stabilizer and a dehydrating agent and performing polycondensation reaction under the action of a catalyst; wherein the weight portion of the p-toluenesulfonic acid is 14-20 portions; 5-15 parts of hydroxyethylidene diphosphonic acid; the weight portion of the crosslinking conditioning agent is 55-65 portions; the weight portion of the temperature stabilizer is 5-10 portions;
the dehydrating agent is at least one of the following: carbon tetrachloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, phosphorus pentoxide;
the weight of the dehydrating agent is 1.5-3.5% of the weight of the crosslinking conditioning agent;
the temperature stabilizer is at least one of the following: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid;
the crosslinking conditioning agent is at least one of the following: glycolic acid, lactic acid, gluconic acid;
the catalyst is at least one of the following: tin oxide, halide, organic acid salt, antimony oxide, zinc oxide, aluminum oxide;
the weight of the catalyst is 0.001-0.005% of the weight of the p-toluenesulfonic acid.
2. The method of claim 1, wherein the method comprises,
mixing the raw materials to obtain a first mixture; the raw materials comprise the following components in parts by weight: crosslinking conditioning agent: 55-65 parts; p-toluenesulfonic acid: 14-20 parts; hydroxyethylidene diphosphonic acid: 5-15 parts; temperature stabilizer: 5-10 parts;
and carrying out polycondensation reaction on the first mixture under the action of a catalyst to prepare the solid slow-release acid.
3. The method as claimed in claim 2, wherein the polycondensation reaction comprises an atmospheric polycondensation reaction and a reduced-pressure polycondensation reaction, the temperature of the atmospheric polycondensation reaction is 100-230 ℃, and the temperature of the reduced-pressure polycondensation reaction is 160-240 ℃.
4. The method as claimed in claim 3, wherein the vacuum degree of the reduced pressure polycondensation reaction is 100-10000 Pa.
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| US20060054325A1 (en) * | 2004-09-15 | 2006-03-16 | Brown J E | Solid sandstone dissolver |
| WO2009016549A2 (en) * | 2007-07-27 | 2009-02-05 | Schlumberger Canada Limited | System, method and apparatus for acid fracturing with scale inhibitor protection |
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| CN108822827A (en) * | 2018-07-21 | 2018-11-16 | 东营市宝泽能源科技有限公司 | A kind of superhigh temperature cross-linked acid |
| CN110628410A (en) * | 2019-10-16 | 2019-12-31 | 北京弘毅恩泽能源技术有限公司 | High-temperature-resistant cross-linked acid system for acid fracturing and preparation method thereof |
| CN110643345A (en) * | 2019-10-16 | 2020-01-03 | 北京弘毅恩泽能源技术有限公司 | Adsorption slow-release acid system for acid fracturing and preparation method thereof |
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