CN114716995A - Authigenic acid and preparation method and application thereof - Google Patents
Authigenic acid and preparation method and application thereof Download PDFInfo
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- CN114716995A CN114716995A CN202110006737.4A CN202110006737A CN114716995A CN 114716995 A CN114716995 A CN 114716995A CN 202110006737 A CN202110006737 A CN 202110006737A CN 114716995 A CN114716995 A CN 114716995A
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- 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 self-generated acid and a preparation method thereof, and application in the field of production increase of deep layer/extra deep layer oil gas reservoir transformation, wherein the preparation raw materials comprise: the self-generated acid precursor, the resistance reducing agent, the regulator, the catalyst, the dispersant, the cleanup additive and the water. The authigenic acid provided by the invention is used for high-temperature deep layer/extra-deep layer oil gas reservoir transformation, so that full-fracture non-uniform etching can be realized, and deep penetration acid fracturing can be realized.
Description
Technical Field
The invention relates to the field of deep layer/extra-deep layer oil and gas reservoir transformation yield increase, and particularly relates to a self-generated acid and a preparation method and application thereof.
Background
Deep/ultra-deep carbonate rock is the key field of domestic exploration and development at present, and over 70 percent of wells need acid fracturing/acidification for construction. The temperature of an extra-deep reservoir is high, the acid rock reaction speed is high, the penetration distance of a conventional acid liquid is less than 120m, a remote reservoir is difficult to communicate, and the problem that the acid liquid seriously corrodes a construction manifold exists. The temperature resistance can be improved to a certain degree by increasing the using amount of the acid additive, but the construction friction resistance is increased and the cost is increased. The field gelled acid and cross-linked acid system can only meet the acid fracturing modification of a reservoir below 180 ℃, and the temperature resistance and the retarding performance of the cross-linked gelled acid are difficult to improve by a high-molecular synthesis technology and a cross-linking technology, so that the research and development of a low-friction, high-retarding and deep-penetrating acid system are urgently needed to meet the requirements of a deep-penetrating acid fracturing process of an ultrahigh-temperature reservoir.
The autogenous acid, also called latent acid, is a fluid or solid injected into the formation, and is the highest potential high temperature retarded acid system, which generates acid deep in the formation by using pyrohydrolysis or ion exchange. The most common self-generated acid system is a paraformaldehyde and ammonium chloride system, and has the problems of poor temperature resistance, toxic substance content, complex site construction and the like. The CN109880610B patent discloses a self-generated acid for oil and gas field acidification and fracturing and a preparation method thereof, which has the beneficial effect of effectively compensating the acid generation capacity of a paraformaldehyde-ammonium chloride system. CN111171803A discloses a crosslinking authigenic acid for reducing the reaction rate of acid rock, which has the advantages of high viscosity, strong temperature resistance (160 ℃), good shear resistance and the like. However, the self-acid-generating system cannot meet the ultra-high temperature acid fracturing and has the problem of high friction resistance.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a self-generated acid, a preparation method thereof, and a method for using the self-generated acid in high temperature (160-220 ℃) and deep/extra-deep oil and gas reservoir transformation. The authigenic acid provided by the invention is used for high-temperature deep layer/extra-deep layer oil and gas reservoir transformation, so that the non-uniform etching of a full crack can be realized, and the deep penetration acid fracturing can be realized.
The invention provides a self-generated acid, which is prepared from the following raw materials: the self-generated acid precursor, the resistance-reducing agent, the regulator, the catalyst, the dispersant, the cleanup additive and water.
According to some preferred embodiments of the authigenic acid of the present invention, the raw materials are prepared as follows in parts by weight:
according to some preferred embodiments of the authigenic acid of the present invention, the authigenic acid parent material is selected from at least one of chlorine-containing resins; preferably at least one of polyvinyl chloride and chlorinated propylene.
According to some preferred embodiments of the authigenic acid of the invention, the authigenic acid precursor material has a particle size of 20 to 300 mesh.
According to some preferred embodiments of the autogenous acid of the present invention, the friction reducer is selected from at least one of acrylamide friction reducers; preferably, the resistance reducing agent is an acid-resistant resistance reducing agent.
According to some preferred embodiments of the self-generated acid, the resistance reducing agent is obtained by adiabatic polymerization of an acrylamide monomer, a 2-acrylamide-2-methylpropanesulfonic acid monomer and a dimethylaminoethyl methacrylate monomer, the mass ratio of the monomers is preferably (35-45): 45-55): 5-15, and the molar ratio of the monomers is more preferably 40:50: 10. In the present invention, the adiabatic polymerization may be a polymerization method which is conventional in the art, and for example, ammonium persulfate and sodium bisulfite may be used as an initiator. In the adiabatic polymerization process, the mass ratio of the respective monomers of the present invention may be satisfied. Preferably, in the invention, the weight average molecular weight of the resistance reducing agent is 1000-2000 ten thousand.
According to some preferred embodiments of the autogenous acid of the present invention, the conditioning agent is selected from at least one of catalysts for the high-temperature hydrolysis of chlorine-containing resins.
According to some preferred embodiments of the autogenous acid of the present invention, the conditioning agent is selected from at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia, potassium hydroxide, and calcium oxide.
According to some preferred embodiments of the authigenic acid of the present invention, the catalyst is selected from organochlorine dechlorination catalysts, preferably at least one of nickel nitrate or platinum catalysts.
According to some preferred embodiments of the authigenic acid of the present invention, the catalyst is at least one of nickel nitrate, a Speier catalyst, and a kast catalyst.
According to some preferred embodiments of the authigenic acid of the present invention, the dispersant is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween 80, and tween 20.
According to some preferred embodiments of the self-generating acid of the present invention, the cleanup additive may be a mixture of an anionic surfactant and a fluorocarbon surfactant, and the anionic surfactant and the fluorocarbon surfactant have a wide selection range.
In the invention, the dosage of water has a wide selection range, and the purposes of dissolving various preparation raw materials and providing a reaction medium are achieved.
The second aspect of the present invention provides a method for producing the above-mentioned authigenic acid, comprising:
s1, mixing the resistance reducing agent with water to obtain resistance reducing agent water;
s2, mixing the resistance reducing agent water, a regulator and a catalyst to obtain a second solution;
s3, mixing the second solution, the dispersing agent and the cleanup additive to obtain a water reducing and blocking system;
s4, mixing the water-reducing water system with the authigenic acid mother body to obtain the authigenic acid.
According to some preferred embodiments of the preparation method of the present invention, the step S1 is performed by mixing under stirring at a speed of 600 to 1000 r/min.
According to some preferred embodiments of the preparation method of the present invention, the step S3 is performed by mixing under stirring at a speed of 300 to 600 r/min.
According to some preferred embodiments of the preparation method of the present invention, the step S4 is performed by mixing under stirring at a speed of 300 to 600 r/min.
The third aspect of the present invention provides the self-generated acid obtained by the above production method.
A fourth aspect of the invention provides the use of an authigenic acid as described above or a method of making an authigenic acid as described above in reservoir modification.
According to some preferred embodiments of the application of the present invention, the reservoir conditions of the hydrocarbon reservoir comprise: the depth is 6000 m-10000 m, and the temperature is 180-240 ℃.
According to some preferred embodiments of the use of the invention, the step of applying the authigenic acid in situ comprises:
1) adding the resistance reducing agent into high-speed stirred clear water to form resistance reducing agent water with certain viscosity;
2) adding a regulator and a catalyst into the resistance reducing agent water under the stirring condition to obtain a second solution;
3) adding a dispersing agent and a discharge aiding agent into the second solution, and stirring at a low speed to form a water reducing and blocking system;
4) during acid fracturing construction, adding a self-generated acid parent body to form high-temperature self-generated acid;
5) conveying the authigenic acid to a target position, closing the well and carrying out a closed reaction for 5 hours.
According to some preferred embodiments of the application according to the invention, in step 1), the friction reducer is delivered using a jet pump or a device equivalent in principle.
According to some preferred embodiments of the application of the present invention, in the step 1), the mixing is performed under stirring conditions, and the stirring speed is 600 to 1000 r/min.
According to some preferred embodiments of the application of the present invention, in the step 3), the mixing is performed under stirring conditions, and the stirring speed is 300 to 600 r/min.
According to some preferred embodiments of the use according to the invention, the autogenous acid precursor material is added in step 4) by means of a sand mixing truck.
According to some preferred embodiments of the use according to the invention, step 4) the authigenic acid is formed in a sand-mixing truck and a well casing.
According to some preferred embodiments of the application of the present invention, in the step 4), the mixing is performed under stirring conditions, and the stirring speed is 300 to 600 r/min.
The beneficial effects of the invention at least comprise:
the high-temperature authigenic acid obtained by the technical scheme of the invention has the characteristics of better retarding performance, temperature resistance, high flow conductivity and the like than the conventional authigenic acid, after being injected into a stratum, the authigenic acid is dechlorinated by high-temperature hydrothermal, the authigenic acid speed is slow below 180 ℃, the authigenic acid speed is increased above 180 ℃, the authigenic acid speed and concentration can be controlled by adjusting the using amounts of the regulator and the catalyst, and the authigenic acid is controlled; the adding proportion and the discharge capacity of the acid-generating material are adjusted, particularly in the preferable dosage range of each substance, the distribution of the acid-generating material in the cracks is controlled, the non-uniform etching can be realized, and a high flow guide channel is formed. The acid generating material has good temperature resistance, can enter the front end of a crack along with fracturing fluid, further realizes non-uniform etching of the whole crack, and realizes deep penetration acid fracturing.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.
In the following embodiments, the starting materials involved in the preparation include:
1) the resistance reducing agent is prepared by the following method: carrying out adiabatic polymerization on an acrylamide monomer, a 2-acrylamide-2-methylpropanesulfonic acid monomer and a dimethylaminoethyl methacrylate monomer according to the mass ratio of 40:50: 10. The conditions of the polymerization reaction include: polymerization temperature 20 ℃, polymerization pH 7, initiator 0.01 wt% ammonium persulfate and 0.02 wt% sodium bisulfite to give a friction reducer having a weight average molecular weight of 1200 ten thousand as determined by gel chromatography.
2) The cleanup additive was prepared according to example 1 of CN 108239532B.
3) Polyvinyl chloride (PVC) is purchased from Hahong science and technology Limited, industrial grade, and processed into 20-300 mesh particles.
4) Sodium hydroxide, ammonia water, sodium carbonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween 80 and nickel nitrate are all purchased from chemical reagents of national medicine group, ltd, and are analytically pure.
5) The cleanup additive is purchased from petroleum engineering research institute of China petrochemical group, Inc., at industrial level.
[ example 1 ]
S1, slowly adding the resistance reducing agent into the high-speed stirring tap water to obtain resistance reducing agent water with certain viscosity; wherein the stirring speed is 600 r/min;
s2, adding ammonia water and nickel nitrate into the resistance reducing agent water, and uniformly stirring to obtain a second solution;
s3, adding sodium dodecyl sulfate and a cleanup additive into the second solution, and stirring at a low speed to obtain a water-reducing and blocking system; wherein the stirring speed is 300 r/min;
s4, adding PVC with the particle size of 300 meshes into the water reducing and blocking system under mechanical stirring, and stirring to form uniform suspension liquid to form a high-temperature self-generated acid system.
In the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.05 wt% of resistance reducing agent, 1 wt% of ammonia water, 0.02 wt% of nickel nitrate, 0.2 wt% of sodium dodecyl sulfate, 0.05 wt% of cleanup additive, 20 wt% of PVC and the balance of water.
[ example 2 ]
Example 2 is essentially the same as preparation 1, except that:
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.1 wt% of resistance reducing agent, 2 wt% of ammonia water, 0.03 wt% of nickel nitrate, 0.3 wt% of sodium dodecyl sulfate, 0.1 wt% of cleanup additive, 30 wt% of PVC and the balance of water.
[ example 3 ]
Example 3 is essentially the same as preparation 1, except that:
in step S4, 200-mesh PVC is added;
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.2 wt% of resistance reducing agent, 3 wt% of sodium carbonate, 0.03 wt% of nickel nitrate, 0.3 wt% of sodium dodecyl benzene sulfonate, 0.1 wt% of cleanup additive, 30 wt% of PVC and the balance of water.
[ example 4 ]
Example 4 is essentially the same as preparation 1, except that:
in step S4, 100-mesh PVC is added;
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.3 wt% of resistance reducing agent, 4 wt% of ammonia water, 0.04 wt% of nickel nitrate, 0.4 wt% of sodium dodecyl sulfate, 0.15 wt% of cleanup additive, 40 wt% of PVC and the balance of water.
[ example 5 ]
Example 5 is essentially the same as preparation 1, except that:
in step S4, 50-mesh PVC is added;
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.4 wt% of resistance reducing agent, 5 wt% of sodium carbonate, 0.05 wt% of nickel nitrate, 0.6 wt% of sodium dodecyl sulfate, 0.15 wt% of cleanup additive, 50 wt% of PVC and the balance of water.
[ example 6 ]
Example 6 is essentially the same as preparation 1, except that:
in step S4, 50-mesh PVC is added;
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.5 wt% of resistance reducing agent, 3 wt% of sodium carbonate, 0.05 wt% of nickel nitrate, 0.5 wt% of sodium dodecyl sulfate, 0.2 wt% of cleanup additive, 60 wt% of PVC and the balance of water.
[ example 7 ]
Example 7 is essentially the same as preparation 1, except that:
in step S4, 200-mesh PVC is added;
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.6 wt% of resistance reducing agent, 5 wt% of sodium carbonate, 0.06 wt% of nickel nitrate, 0.8 wt% of sodium dodecyl sulfate, 0.15 wt% of cleanup additive, 50 wt% of PVC and the balance of water.
[ example 8 ]
Example 8 is essentially the same as preparation 1, except that:
in step S4, 200-mesh PVC is added;
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.4 wt% of resistance reducing agent, 3 wt% of sodium carbonate, 0.04 wt% of nickel nitrate, 0.5 wt% of sodium dodecyl sulfate, 0.1 wt% of cleanup additive, 50 wt% of PVC and the balance of water.
[ example 9 ]
Example 9 is essentially the same as preparation 1, except that:
in step S4, 200-mesh PVC is added;
in the finally formed high-temperature self-generating acid system, the contents of all substances are as follows: 0.4 wt% of resistance reducing agent, 2 wt% of sodium carbonate, 0.02 wt% of nickel nitrate, 0.5 wt% of sodium dodecyl benzene sulfonate, 0.1 wt% of cleanup additive, 50 wt% of PVC and the balance of water.
[ example 10 ]
Example 10 is essentially the same as preparation 1, except that:
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.02 wt% of resistance reducing agent, 0.3 wt% of sodium carbonate, 0.008 wt% of nickel nitrate, 0.1 wt% of sodium dodecyl sulfate, 0.01 wt% of cleanup additive, 10 wt% of PVC and the balance of water.
[ example 11 ]
Example 11 is essentially the same as preparation 1, except that:
in the finally formed high-temperature self-acid generation system, the contents of all the substances are as follows: 0.8 wt% of resistance reducing agent, 6 wt% of sodium carbonate, 0.08 wt% of nickel nitrate, 1 wt% of sodium dodecyl sulfate, 0.3 wt% of cleanup additive, 70 wt% of PVC and the balance of water.
However, under these conditions, the acid generation rate is too fast.
The acid generating systems of examples 1-11 were tested for acid generating performance.
1) And (3) testing the concentration of raw acid: heating the acid generating systems at 30 deg.C, 160 deg.C, 180 deg.C and 200 deg.C for 3h, standing, cooling to room temperature, filtering, and measuring chlorine content in liquid phase product by potentiometric titration to determine acid generating concentration.
2) Apparent viscosity test: the apparent viscosities of the different systems were measured at 100r/min at room temperature using a six-speed viscometer.
The acid formation concentrations and test results are shown in Table 1.
TABLE 1 acid Generation Capacity and System viscosity
As can be seen from Table 1, the respective acid generating systems can not hydrolyze acid at 30 ℃, which shows that the acid generating systems of the invention have good stability, are beneficial to the on-site storage of materials, and have no corrosion effect on liquid preparation equipment and pipelines in the construction process. The preferred practical working stability is 180 to 200 c, therefore, the acid forming concentration is preferably less than 5 wt% at less than 180 c, while above 180 c, the greater the acid forming concentration is preferred, but the acid forming rate is also considered comprehensively, and if too fast, is not conventionally desired in the art. As can be seen from table 1, the autogenous acid of the present invention can meet different acid fracturing process requirements.
The viscosity result of the system shows that the viscosity of the system is gradually increased along with the increase of the dosage of the acid resistance reducing agent, and different dosages of the resistance reducing agent can be selected according to the field requirements, so that the purposes of reducing the friction resistance and carrying the acid generating material are achieved.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the appended claims, and changes can be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An authigenic acid, which is prepared from the following raw materials: the self-generated acid precursor, the resistance reducing agent, the regulator, the catalyst, the dispersant, the cleanup additive and the water.
2. The authigenic acid of claim 1, comprising, in weight fractions, the following starting materials:
3. the authigenic acid of claim 1 or 2, wherein the authigenic acid precursor is selected from at least one of chlorine-containing resins; preferably at least one of polyvinyl chloride and chlorinated propylene; further preferably, the particle size of the particle of the authigenic acid parent substance is 20-300 meshes; and/or the presence of a gas in the gas,
the resistance reducing agent is selected from at least one of acrylamide resistance reducing agents; the monomer is preferably obtained by carrying out adiabatic polymerization on an acrylamide monomer, a 2-acrylamide-2-methylpropanesulfonic acid monomer and a dimethylaminoethyl methacrylate monomer, and more preferably, the mass ratio of the monomers is (35-45): (45-55): 5-15);
the regulator is selected from at least one of alkali substances for hydrolysis; preferably at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, potassium hydroxide and calcium oxide; and/or the presence of a gas in the gas,
the catalyst is selected from dechlorination catalysts, preferably at least one of nickel nitrate and platinum gold catalysts, more preferably at least one of nickel nitrate, Speier catalysts and Kaster catalysts; and/or the presence of a gas in the atmosphere,
the dispersant is at least one selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween 80 and tween 20.
4. A method of producing an authigenic acid, comprising:
s1, mixing the resistance reducing agent with water to obtain resistance reducing agent water;
s2, mixing the resistance reducing agent water with a regulator and a catalyst to obtain a second solution;
s3, mixing the second solution with a dispersant and a cleanup additive to obtain a water-reducing and blocking system;
s4, mixing the water-reducing water system with the authigenic acid mother body to obtain the authigenic acid.
5. The method according to claim 4, wherein the step S1 is carried out under stirring at a speed of 600-1000 r/min.
6. The method according to claim 4 or 5, wherein the step S3 is carried out under stirring at a speed of 300-600 r/min.
7. The method according to any one of claims 4 to 6, wherein the step S4 is carried out under stirring at a speed of 300 to 600 r/min.
8. An authigenic acid prepared according to the method of any one of claims 4-7.
9. Use of an authigenic acid as claimed in any one of claims 1 to 3 and 8 or a method of making an authigenic acid as claimed in any one of claims 4 to 7 in reservoir reconstruction.
10. The use of claim 9, wherein the reservoir reconstruction is a reconstruction in a hydrocarbon reservoir;
preferably, the reservoir conditions of the hydrocarbon reservoir include: the depth is 6000 m-10000 m, and the temperature is 180-240 ℃.
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2021
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| US4143045A (en) * | 1975-12-03 | 1979-03-06 | The Goodyear Tire & Rubber Company | Method of preparing dibenzothiazolyl disulfides |
| CN106634927A (en) * | 2016-12-15 | 2017-05-10 | 中国石油大学(华东) | Authigenic acid-induced tackifying conrol system with oil washing effect and preparation method |
| CN110358522A (en) * | 2018-03-26 | 2019-10-22 | 中国石油化工股份有限公司 | A kind of compound resistance reduction retarded acid for deep-well acid fracturing |
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