CN116179179B - Multi-effect fracturing auxiliary agent and preparation method thereof - Google Patents
Multi-effect fracturing auxiliary agent and preparation method thereof Download PDFInfo
- Publication number
- CN116179179B CN116179179B CN202310162711.8A CN202310162711A CN116179179B CN 116179179 B CN116179179 B CN 116179179B CN 202310162711 A CN202310162711 A CN 202310162711A CN 116179179 B CN116179179 B CN 116179179B
- Authority
- CN
- China
- Prior art keywords
- parts
- stirring
- effect
- fracturing
- speed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
-
- 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
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
-
- 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
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
- C09K8/608—Polymer compositions
-
- 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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/26—Gel breakers other than bacteria or enzymes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Colloid Chemistry (AREA)
- Cosmetics (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a multi-effect fracturing auxiliary agent and a preparation method thereof, wherein the multi-effect fracturing auxiliary agent comprises the following raw materials: 10-15 parts of novel cross-linking agent, 5-10 parts of microcapsule gel breaker, 50-75 parts of water, 10-20 parts of clay swelling inhibitor, 8-10 parts of demulsifier and 0.5-1 part of pH regulator. The fracturing auxiliary agent introduces a novel cross-linking agent, has good cross-linking effect, and can cooperate with a gel breaker to play a role in rapid gel breaking. Meanwhile, the invention selects a plurality of functional fracturing auxiliary agents, and solves the problems that the compatibility among different functional auxiliary agents in the system is poor, the synergistic effect is not ideal, even antagonism is generated, and each single agent cannot exert the respective optimal effect.
Description
Technical Field
The invention relates to the field of petroleum fracturing fluids, in particular to a multi-effect fracturing auxiliary agent and a preparation method thereof.
Background
Fracturing reformation is a basic means of low permeability oil and gas field development, and the improvement of the performance of fracturing fluid serving as a medium for making a joint and carrying sand is always the subject of research. The fracturing fluid with excellent performance meets the following requirements: the viscosity is high, and the propping agent is convenient to carry; the friction is small, and the pressure can be effectively transmitted; the filtration loss is low, so that the formation pressure can rise quickly; less dissolved matters, low residue and easy reverse discharge, i.e. no emulsification, no precipitation and no blockage of stratum; the heat stability and the shearing property are good; easy to obtain, convenient to prepare, economical and reasonable; easy transportation, safe use, etc. In the performance of fracturing fluid, low fluid loss, low residue and rapid flowback are the basis of low damage of a reservoir.
Hydraulic fracturing is a main stimulation and injection measure of oil and gas reservoirs, and has been rapidly developed and widely used since fracturing is performed on a large scale.
Currently, there are a number of chemical additives used to improve the performance of water-based fracturing fluids, such as anti-swelling agents, drainage aids, blowing agent bactericides, demulsifiers, and the like. The addition of some bactericides to the fracturing fluid eliminates the degradation of the polymer surface in the reservoir and the proper bactericides stop the production of anaerobic bacteria in the formation. Many formations are where crude oil from the formation is sour due to hydrogen sulfide produced by sulfate reducing bacteria. In addition, due to the fact that the clay content of the sandstone oil and gas reservoir is high, water sensitivity is high, hydration expansion and dispersion migration can occur after the sandstone oil and gas reservoir meets water, the sandstone oil and gas reservoir is blocked, and the permeability of the sandstone oil and gas reservoir is reduced. Thus, the addition of clay stabilizers prevents the hydration swelling and dispersion migration of clay minerals in the hydrocarbon reservoir. When the oil well is subjected to water-based fracturing, the water-based fracturing fluid and the crude oil in the stratum can form an oil-water emulsion. The emulsion has higher stability because the natural emulsifying agent in the crude oil is adhered to the water drops to form a protective film. If emulsification occurs near the well bore, serious production blockage may occur, so that demulsifier needs to be added, the demulsifier can be strongly adsorbed on the oil/water interface to replace the original firm protective film, so that the strength of the interface film is greatly reduced, the protective effect is weakened, and the purpose of preventing emulsion breaking can be achieved. All well fluids can cause damage to the permeability of the reservoir, and the flowback of the fracturing fluid must be enhanced to achieve a good fracturing effect. The cleanup additive can improve the flowback rate of the fracturing fluid and reduce the damage of the fracturing fluid to the oilfield reservoir.
At present, most of the fracturing auxiliary agents are single-function type, workers are now matched according to geological conditions, the operation is troublesome, because products of various factories are different, compatibility among different products in a system is poor, a synergistic effect is not ideal, even antagonism can be generated, and each single agent cannot exert the respective optimal effect, so that the comprehensive performance of the whole fracturing fluid system is reduced, stratum is seriously injured, and meanwhile, the production cost of oil gas development is increased. The fracturing auxiliary agent with multiple functions and capable of being effectively applied to most geology is a new development idea, and defects caused by personal configuration are reduced. The defects are mainly concentrated on antagonism between the cross-linking agent and the gel breaker, and the cross-linking agent carries out cross-linking reaction with the thickener through chemical bonds or coordination bonds, so that each molecule of the thickener in the system is connected into a reticular body structure, and the thickener is further thickened to form typical viscoelastic gel; the gel breaker is a reagent capable of breaking gel and hydrating gel fracturing fluid, and can controllably degrade viscous fracturing fluid into thin fluid which can be easily returned from stratum within a specified time. How to balance the cross-linking agent and the gel breaker, and achieve the aim of keeping ideal high viscosity of the fracturing fluid in the sand carrying process, and immediately breaking gel and hydrating the pumped fluid is a great challenge.
At present, the most advanced means is to seal and wrap the gel breaker by adopting a gel capsule wrapping technology, so that the gel breaker is prevented from playing a role too early, and after fracturing construction, stress is generated by closing cracks, so that the gel breaker permeates out for breaking. Its advantages are low breaking speed, high dosage and high cost.
CN 108641700B discloses a multi-effect fracturing auxiliary agent, which consists of clay stabilizer, amine oxide type amphoteric surfactant, synergist, wrapping agent and water. The adopted synergist is a block polyether demulsifier and a biquaternary ammonium salt bactericide mixture. The multi-effect fracturing auxiliary agent prepared by the method is subjected to primary optimization on different functional products under the condition that the antagonism is not generated by compounding. The invention only saves the batching time of workers, and does not have synergy so as to achieve the aim of saving the cost.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a multi-effect fracturing auxiliary agent and a preparation method thereof, wherein a novel cross-linking agent is introduced into the fracturing auxiliary agent, so that the multi-effect fracturing auxiliary agent has a good cross-linking effect, can cooperate with a gel breaker, and plays a role in rapid gel breaking.
A method for preparing a novel cross-linking agent, comprising the following steps:
s1, mixing 8-12 parts of ligand and 85-100 parts of water according to parts by weight, and stirring for 5-10min at a rotating speed of 80-120r/min to obtain a ligand aqueous solution;
s2, mixing 2-5 parts of an ion source and 1-2 parts of a 20-30wt% sodium hydroxide aqueous solution according to parts by mass, and stirring for 3-5min at a rotating speed of 80-120r/min to obtain a mixed ion solution;
and S3, heating the ligand aqueous solution prepared in the step S1 to 70-85 ℃ at a speed of 1-10 ℃/min, dropwise adding the mixed ion solution into the ligand aqueous solution at a speed of 2-5mL/min, regulating the pH value to 7.0 by using a 20-30wt% hydrochloric acid aqueous solution after the dropwise adding is finished, reacting at a constant temperature for 1-3h, cooling to room temperature, filtering, washing and drying at room temperature to obtain the novel cross-linking agent.
Preferably, the ligand is one of triethanolamine, glycerol and citric acid; further preferably, the ligand is triethanolamine.
Preferably, the ion source is formed by mixing one or two of molybdenum trioxide and borax; further preferably, the ion source is prepared from molybdenum trioxide and borax according to the mass ratio of (1-2): (1-2) and mixing.
The invention selects molybdenum trioxide and borax as ion sources, uses sodium hydroxide aqueous solution to dissolve to obtain molybdate and borate, uses triethanolamine as ligand, and synthesizes the novel cross-linking agent by amino chelating molybdate and hydroxyl chelating borate. The formed novel cross-linking agent has two ion centers of boron and molybdenum, can cross-link more thickening agents containing hydroxyl, amino and other active groups, has stronger cross-linking capability than the cross-linking agent with a single ion center, has more compact chelating molecular groups, and improves the concentration of fracturing fluid. The novel crosslinking agent can realize good crosslinking in colloid containing hydroxyl or amino. In addition, under the high temperature condition of 80 ℃ and above, molybdenum trioxide is formed by dehydration of molybdic acid radicals, the crosslinking effect is lost, and the effect of reducing the viscosity of the pyrolysis liquid is achieved. The damage research of the fracturing fluid carried out abroad on the diversion capacity of the propping fracture is considered that the fracturing fluid can be concentrated by 5-7 times due to fluid loss during pumping and closing, so that the propping fracture is greatly damaged; the concentration of the lysate greatly improves the viscosity, which causes great trouble to the flowback of the later-stage lysate. And molybdenum trioxide is formed by dehydration along with the penetration of the pyrolysis liquid, so that the crosslinking capability is gradually lost, the viscosity of the pyrolysis liquid is favorably inhibited from rising, the damage to supporting cracks is reduced, and the time for breaking gel is shortened. Meanwhile, molybdenum trioxide formed by dehydration of molybdic acid radical also has excellent thermocatalytic performance, and the semiconductor material can transfer electrons from valence band to conduction band under thermal excitation to generate hot electrons and holes, further generate superoxide radicals, destroy gel structure and play a role of gel breaker.
Due to the limitation of the material, the molybdenum trioxide has insufficient thermal catalytic gel breaking capacity, so that the traditional gel breaker needs to be supplemented. The traditional gel breakers include three types, namely an oxidant breaker, an enzyme breaker and a capsule breaker. The oxidant breaker is preferably selected because the common potassium persulfate, ammonium persulfate and hydrogen peroxide are peroxides, oxygen can be generated at the same time of oxidation, and the oxygen is a carrier of electrons and holes generated by thermal catalysis of molybdenum trioxide, so that the higher the oxygen content is, the more superoxide radicals and hydrogen peroxide generated by thermal catalysis of the molybdenum trioxide are, and the higher the gel structure is damaged.
However, if the oxidizing agent and the crosslinking agent are directly mixed, molybdenum trioxide is directly dehydrated to form by the oxidizing agent, and thus the crosslinking effect is lost, which is to be avoided in the present invention. Therefore, the microcapsule gel breaker is further selected, the peroxide is wrapped by the capsule wall, so that the peroxide is prevented from contacting with the molybdate, the peroxide is released at high temperature and high pressure after the microcapsule gel breaker penetrates into a stratum, and the microcapsule gel breaker cooperates with molybdenum trioxide formed by dehydrating the molybdate, so that quick gel breaking and the return discharge of the pyrolysis liquid are realized.
Further, the invention provides a preparation method of the microcapsule gel breaker, which comprises the following steps: mixing 70-75 parts of chloroform, 10-14 parts of liquid paraffin and 0.1-1 part of polyvinylpyrrolidone, adding 6-8 parts of ammonium persulfate, 0.1-1 part of absolute ethyl alcohol, 0.1-0.5 part of n-amyl alcohol, 0.01-0.2 part of polyethylene glycol 4000, 4-6 parts of ethylenediamine tetraacetic acid and 0.1-1 part of ethyl methacrylate, stirring for 20-40min, and filtering, washing and airing to obtain the microcapsule gel breaker.
The microcapsule gel breaker selected by the invention can be slowly degraded along with the change of temperature and pressure, and the capsule core material is intensively released after the capsule coating material is slowly degraded, so that the concentrated release of ammonium persulfate of the capsule core can be ensured, the rapid reaction with molybdate is realized, and the synergistic gel breaking is realized. Furthermore, the surface property of the capsule wall is regulated and controlled by a plurality of alcohols, so that the microcapsule gel breaker with the particle size below 5 mu m is obtained. The extremely small particle size is beneficial to the dispersion in fracturing fluid, and when the fracturing fluid breaks, the breaker ammonium persulfate and colloid in the fracturing fluid are in full contact and react rapidly.
Still further, the invention provides a preparation method of the multi-effect fracturing auxiliary agent, which comprises the following steps: and mixing the novel cross-linking agent and the microcapsule gel breaker prepared by the method to obtain the multi-effect fracturing auxiliary agent.
Furthermore, the invention provides a preparation method of the multi-effect fracturing auxiliary agent, which comprises the following steps:
heating 50-75 parts of water to 40-50 ℃ according to parts by mass, stirring at a rotating speed of 80-120r/min, adding 10-20 parts of clay swelling inhibitor into the water, and reacting for 0.5-1h; then adding 8-10 parts of demulsifier and continuously stirring for 0.5-1h; adding 0.5-1 part of pH regulator, and stirring for 20-30min; finally, heating to 50-60 ℃ at a speed of 1-10 ℃/min, adding 10-15 parts of novel cross-linking agent and 5-10 parts of microcapsule gel breaker, and stirring for 0.5-1h at a speed of 80-120r/min to obtain the multi-effect fracturing auxiliary agent.
Preferably, the demulsifier is one of an AP-type demulsifier, an AR-type demulsifier and an AE-type demulsifier; further preferably, the demulsifier is an AP-type demulsifier. The AP-type demulsifier is more suitable for liquid with higher water content, and can achieve the effect of rapid demulsification under the low-temperature condition. The SP-type demulsifier has a plurality of chain lengths and branched chains, and has higher hydrophilic capacity than that of a SP-type demulsifier with a single molecular structure. The characteristics of the multiple branched chains determine that the AP-type demulsifier has higher wettability and permeability, and molecules of the AP-type demulsifier can rapidly permeate into an oil-water interface film when a crude oil emulsion is demulsified.
Preferably, the pH regulator is one of citric acid, carbonic acid and acetic acid; further preferably, the pH adjuster is citric acid. Molybdenum trioxide is generated because molybdate ions are not easy to dehydrate under alkaline conditions; the molybdate is easy to be directly dehydrated in the presence of hydrochloric acid and nitric acid to generate molybdenum trioxide; in the presence of sulfuric acid, molybdic acid radicals are easy to react with sulfuric acid to generate molybdenum sulfate, so that a proper pH environment is provided, and the multi-effect fracturing auxiliary agent prepared by the method is necessary. Therefore, three weak acids are preferred in the invention, wherein, citric acid is more suitable for regulating the pH of the multi-effect fracturing auxiliary agent prepared by the invention because of high volatilization point and stronger acidity.
Preferably, the clay swelling preventing agent is one of cetyl trimethyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride and polymethyl acryloyloxyethyl trimethyl ammonium chloride; further preferably, the clay swelling inhibitor is tetradecyldimethylbenzyl ammonium chloride. When clay contacts with water, the surface of the flaky structure is negatively charged, and the clay is separated under the action of electrostatic repulsive force, so that expansion is generated. Clay expansion occurs in the water injection stratum, so that the water injection speed is reduced; the oil production stratum undergoes earth boring expansion, and the oil well yield is reduced. The invention prefers tetradecyldimethylbenzyl ammonium chloride, and because of the existence of benzyl, the benzene ring has a large pi bond influence, the capacity of containing electrons is stronger, and the capacity of resolving the negative charge on the clay surface is stronger.
The invention has the beneficial effects that:
1. the invention selects molybdenum trioxide and borax as ion sources, uses sodium hydroxide aqueous solution to dissolve to obtain molybdate and borate, uses triethanolamine as ligand, and synthesizes a novel cross-linking agent through amino chelating molybdate and hydroxyl chelating borate, wherein the novel cross-linking agent can realize good cross-linking effect in colloid containing hydroxyl or amino.
2. The microcapsule gel breaker is further selected, the peroxide is wrapped by the capsule wall, so that the peroxide is prevented from contacting with molybdic acid root, and the peroxide is released at high temperature and high pressure after the microcapsule gel breaker penetrates into a stratum; and the property of molybdenum trioxide formed by high-temperature dehydration of molybdate is utilized, so that the molybdenum trioxide and an oxidant cooperate, oxygen is generated by the oxidant while oxidizing, the oxygen is a carrier of electrons and holes generated by thermal catalysis of the molybdenum trioxide, the higher the oxygen content is, the more superoxide radicals and hydrogen peroxide generated by thermal catalysis of the molybdenum trioxide are, the higher the speed of destroying a gel structure is, and therefore, the rapid gel breaking and the reverse drainage of a pyrolysis liquid are realized.
3. The invention further provides a multi-effect fracturing auxiliary agent, the novel cross-linking agent and the microcapsule gel breaker are adopted, and the prepared multi-effect fracturing auxiliary agent can be matched with various thickening agents for use, and has excellent performance under the high-temperature environment of 70-280 ℃.
Detailed Description
Liquid paraffin, CAS number: 32384-98-8, cat No.: KL816415, shanghai kang biosciences limited.
Polyvinylpyrrolidone, cat No.: s30268 Shanghai Source leaf Biotechnology Co., ltd.
AP demulsifier, cat No.: f-6, nantong Runfeng petrochemical Co., ltd.
Polyethylene glycol 4000, cat: 180-9187-4298 pharmaceutical excipients, inc. of Jinxiang, west An.
Example 1
A preparation method of a multi-effect fracturing auxiliary comprises the following steps:
heating 60 parts of water to 45 ℃ according to parts by mass, stirring at a rotating speed of 100r/min, adding 15 parts of clay swelling preventing agent into the water, and reacting for 1h; then adding 9 parts of demulsifier and continuing stirring for 0.5h; adding 0.7 part of pH regulator, and continuously stirring for 25min; and finally, heating to 55 ℃ at a speed of 5 ℃/min, adding 15 parts of novel cross-linking agent, and stirring for 0.5h at a rotating speed of 100r/min to obtain the multi-effect fracturing auxiliary agent.
The demulsifier is an AP-type demulsifier.
The pH regulator is citric acid.
The clay swelling preventing agent is tetradecyl dimethyl benzyl ammonium chloride.
The preparation method of the novel cross-linking agent comprises the following steps:
s1, mixing 10 parts of ligand and 90 parts of water according to parts by mass, and stirring for 8 minutes at a rotating speed of 100r/min to obtain a ligand aqueous solution;
s2, mixing 3 parts of an ion source and 1.5 parts of 24wt% sodium hydroxide aqueous solution according to parts by mass, and stirring for 4min at a rotating speed of 100r/min to obtain a mixed ion solution;
and S3, heating the ligand aqueous solution prepared in the step S1 to 80 ℃ at a speed of 5 ℃/min, dripping the mixed ion solution into the ligand aqueous solution at a speed of 3mL/min, regulating the pH value to 7.0 by using 24wt% hydrochloric acid aqueous solution after the dripping is finished, reacting at constant temperature for 2 hours, cooling to room temperature, filtering, washing and drying at room temperature to obtain the novel cross-linking agent.
The ligand is triethanolamine.
The ion source is prepared from molybdenum trioxide and borax according to the mass ratio of 1:2, mixing.
Example 2
A preparation method of a multi-effect fracturing auxiliary comprises the following steps:
heating 60 parts of water to 45 ℃ according to parts by mass, stirring at a rotating speed of 100r/min, adding 15 parts of clay swelling preventing agent into the water, and reacting for 1h; then adding 9 parts of demulsifier and continuing stirring for 0.5h; adding 0.7 part of pH regulator, and continuously stirring for 25min; and finally, heating to 55 ℃ at a speed of 5 ℃/min, adding 15 parts of novel cross-linking agent and 8 parts of oxidant gel breaker, and stirring for 0.5h at a speed of 100r/min to obtain the multi-effect fracturing auxiliary agent.
The oxidant breaker is ammonium persulfate.
The demulsifier is an AP-type demulsifier.
The pH regulator is citric acid.
The clay swelling preventing agent is tetradecyl dimethyl benzyl ammonium chloride.
The preparation method of the novel cross-linking agent comprises the following steps:
s1, mixing 10 parts of ligand and 90 parts of water according to parts by mass, and stirring for 8 minutes at a rotating speed of 100r/min to obtain a ligand aqueous solution;
s2, mixing 3 parts of an ion source and 1.5 parts of 24wt% sodium hydroxide aqueous solution according to parts by mass, and stirring for 4min at a rotating speed of 100r/min to obtain a mixed ion solution;
and S3, heating the ligand aqueous solution prepared in the step S1 to 80 ℃ at a speed of 5 ℃/min, dripping the mixed ion solution into the ligand aqueous solution at a speed of 3mL/min, regulating the pH value to 7.0 by using 24wt% hydrochloric acid aqueous solution after the dripping is finished, reacting at constant temperature for 2 hours, cooling to room temperature, filtering, washing and drying at room temperature to obtain the novel cross-linking agent.
The ligand is triethanolamine.
The ion source is prepared from molybdenum trioxide and borax according to the mass ratio of 1:2, mixing.
Example 3
A preparation method of a multi-effect fracturing auxiliary comprises the following steps:
heating 60 parts of water to 45 ℃ in parts by mass, stirring at a rotating speed of 100r/min, adding 15 parts of clay swelling preventing agent into the mixture, and reacting for 1h; then adding 9 parts of demulsifier and continuing stirring for 0.5h; adding 0.7 part of pH regulator, and continuously stirring for 25min; and finally, heating to 55 ℃ at a speed of 5 ℃/min, adding 15 parts of novel cross-linking agent and 8 parts of microcapsule gel breaker, and stirring for 0.5h at a speed of 100r/min to obtain the multi-effect fracturing auxiliary agent.
The demulsifier is an AP-type demulsifier.
The pH regulator is citric acid.
The clay swelling preventing agent is tetradecyl dimethyl benzyl ammonium chloride.
The preparation method of the microcapsule gel breaker comprises the following steps: according to the mass parts, 73.09 parts of chloroform, 11.73 parts of liquid paraffin and 0.59 part of polyvinylpyrrolidone are mixed, then 7.73 parts of ammonium persulfate, 0.59 part of absolute ethyl alcohol, 0.2 part of n-amyl alcohol, 0.1 part of polyethylene glycol 4000, 5.28 parts of ethylenediamine tetraacetic acid and 0.59 part of ethyl methacrylate are added for mixing, stirring is carried out for 30 minutes, and the microcapsule gel breaker is obtained after filtering, washing and airing.
The preparation method of the novel cross-linking agent comprises the following steps:
s1, mixing 10 parts of ligand and 90 parts of water according to parts by mass, and stirring for 8 minutes at a rotating speed of 100r/min to obtain a ligand aqueous solution;
s2, mixing 3 parts of an ion source and 1.5 parts of 24wt% sodium hydroxide aqueous solution according to parts by mass, and stirring for 4min at a rotating speed of 100r/min to obtain a mixed ion solution;
and S3, heating the ligand aqueous solution prepared in the step S1 to 80 ℃ at a speed of 5 ℃/min, dripping the mixed ion solution into the ligand aqueous solution at a speed of 3mL/min, regulating the pH value to 7.0 by using 24wt% hydrochloric acid aqueous solution after the dripping is finished, reacting at constant temperature for 2 hours, cooling to room temperature, filtering, washing and drying at room temperature to obtain the novel cross-linking agent.
The ligand is triethanolamine.
The ion source is prepared from molybdenum trioxide and borax according to the mass ratio of 1:2, mixing.
Example 4
A preparation method of a multi-effect fracturing auxiliary comprises the following steps:
heating 60 parts of water to 45 ℃ in parts by mass, stirring at a rotating speed of 100r/min, adding 15 parts of clay swelling preventing agent into the mixture, and reacting for 1h; then adding 9 parts of demulsifier and continuing stirring for 0.5h; adding 0.7 part of pH regulator, and continuously stirring for 25min; and finally, heating to 55 ℃ at a speed of 5 ℃/min, adding 15 parts of novel cross-linking agent and 8 parts of microcapsule gel breaker, and stirring for 0.5h at a speed of 100r/min to obtain the multi-effect fracturing auxiliary agent.
The demulsifier is an AP-type demulsifier.
The pH regulator is citric acid.
The clay swelling preventing agent is tetradecyl dimethyl benzyl ammonium chloride.
The preparation method of the microcapsule gel breaker comprises the following steps: according to the parts by mass, 73.09 parts of chloroform, 11.73 parts of liquid paraffin and 0.59 part of polyvinylpyrrolidone are mixed, then 7.73 parts of ammonium persulfate, 0.59 part of absolute ethyl alcohol, 0.2 part of n-amyl alcohol, 0.1 part of polyethylene glycol 4000, 5.28 parts of ethylenediamine tetraacetic acid and 0.59 part of ethyl methacrylate are added for mixing, and the microcapsule gel breaker is obtained after stirring, washing and airing.
The preparation method of the novel cross-linking agent comprises the following steps:
s1, mixing 10 parts of ligand and 90 parts of water according to parts by mass, and stirring for 8 minutes at a rotating speed of 100r/min to obtain a ligand aqueous solution;
s2, mixing 3 parts of an ion source and 1.5 parts of 24wt% sodium hydroxide aqueous solution according to parts by mass, and stirring for 4min at a rotating speed of 100r/min to obtain a mixed ion solution;
and S3, heating the ligand aqueous solution prepared in the step S1 to 80 ℃ at a speed of 5 ℃/min, dripping the mixed ion solution into the ligand aqueous solution at a speed of 3mL/min, regulating the pH value to 7.0 by using 24wt% hydrochloric acid aqueous solution after the dripping is finished, reacting at constant temperature for 2 hours, cooling to room temperature, filtering, washing and drying at room temperature to obtain the novel cross-linking agent.
The ligand is triethanolamine.
The ion source is borax.
Example 5
A preparation method of a multi-effect fracturing auxiliary comprises the following steps:
heating 60 parts of water to 45 ℃ in parts by mass, stirring at a rotating speed of 100r/min, adding 15 parts of clay swelling preventing agent into the mixture, and reacting for 1h; then adding 9 parts of demulsifier and continuing stirring for 0.5h; adding 0.7 part of pH regulator, and continuously stirring for 25min; and finally, heating to 55 ℃ at a speed of 5 ℃/min, adding 15 parts of novel cross-linking agent and 8 parts of microcapsule gel breaker, and stirring for 0.5h at a speed of 100r/min to obtain the multi-effect fracturing auxiliary agent.
The demulsifier is an AP-type demulsifier.
The pH regulator is citric acid.
The clay swelling preventing agent is tetradecyl dimethyl benzyl ammonium chloride.
The preparation method of the microcapsule gel breaker comprises the following steps: according to the parts by mass, 73.09 parts of chloroform, 11.73 parts of liquid paraffin and 0.59 part of polyvinylpyrrolidone are mixed, then 7.73 parts of ammonium persulfate, 0.59 part of absolute ethyl alcohol, 0.2 part of n-amyl alcohol, 0.1 part of polyethylene glycol 4000, 5.28 parts of ethylenediamine tetraacetic acid and 0.59 part of ethyl methacrylate are added for mixing, and the microcapsule gel breaker is obtained after stirring, washing and airing.
The preparation method of the novel cross-linking agent comprises the following steps:
s1, mixing 10 parts of ligand and 90 parts of water according to parts by mass, and stirring for 8 minutes at a rotating speed of 100r/min to obtain a ligand aqueous solution;
s2, mixing 3 parts of an ion source and 1.5 parts of 24wt% sodium hydroxide aqueous solution according to parts by mass, and stirring for 4min at a rotating speed of 100r/min to obtain a mixed ion solution;
and S3, heating the ligand aqueous solution prepared in the step S1 to 80 ℃ at a speed of 5 ℃/min, dropwise adding the mixed ion solution into the ligand aqueous solution at a speed of 3mL/min, regulating the pH value to 7.0 by using 24wt% hydrochloric acid aqueous solution after the dropwise adding is finished, reacting at a constant temperature for 2 hours, filtering while the solution is hot to remove insoluble matters, treating the filtrate by using 95wt% ethanol aqueous solution, and crystallizing, filtering, washing and drying to obtain the novel cross-linking agent.
The ligand is triethanolamine.
The ion source is molybdenum trioxide.
Comparative example 1
A preparation method of a multi-effect fracturing auxiliary comprises the following steps:
heating 60 parts of water to 45 ℃ according to parts by mass, stirring at a rotating speed of 100r/min, adding 15 parts of clay swelling preventing agent into the water, and reacting for 1h; then adding 9 parts of demulsifier and continuing stirring for 0.5h; adding 0.7 part of pH regulator, and continuously stirring for 25min; and finally, heating to 55 ℃ at a speed of 5 ℃/min, adding 15 parts of cross-linking agent and 8 parts of oxidant gel breaker, and stirring for 0.5h at a speed of 100r/min to obtain the multi-effect fracturing auxiliary agent.
The demulsifier is an AP-type demulsifier.
The pH regulator is citric acid.
The clay swelling preventing agent is tetradecyl dimethyl benzyl ammonium chloride.
The cross-linking agent is borax.
The oxidant breaker is ammonium persulfate.
Test example 1
Apparent viscosity test
Apparent viscosity test is carried out by referring to a high-temperature high-pressure coaxial cylinder viscometer in SY/T5107-2016 water-based fracturing fluid evaluation method. After the fracturing fluid is prepared, adding the fracturing fluid into a viscosimeter to a height of 2cm immediately, pressurizing by taking nitrogen with a pressure of 3MPa as a system, and starting 100s after the pressurization is finished -1 After shearing and stabilizing the rotation speed for 40s, the viscosity of the fracturing fluid at 25 ℃ is recorded. The test results are shown in Table 1.
Viscosity calculation formula: μ=kγ (n-1)
μ is viscosity in millipascal seconds (mpa.s);
k is the consistency coefficient independent of the geometrical parameters of the instrument, in millipascal seconds to the power n (mpa.s n )；
Gamma is the shear rate in seconds to the negative power (s -1 )；
n is the flow behavior index.
The preparation method of the fracturing fluid for the test comprises the following steps: mixing 15 parts of polyvinyl alcohol (PVA), 14 parts of carboxymethyl hydroxypropyl guanidine gum and 1000 parts of deionized water, and stirring at a speed of 800r/min for 15min to obtain a base solution; the multi-effect fracturing auxiliary agent and the base fluid prepared in the example and the comparative example are mixed according to the mass ratio of 1.5:100, and stirring for 15min at a rotation speed of 600r/min to obtain the fracturing fluid for testing.
Table 1: apparent viscosity test results
| Apparent viscosity/mPa.s at 25 DEG C | |
| Example 1 | 562 |
| Example 2 | 482 |
| Example 3 | 564 |
| Example 4 | 546 |
| Example 5 | 536 |
| Comparative example 1 | 461 |
As can be seen from table 1, the apparent viscosity of example 3 is highest at 25 ℃, because triethanolamine is used as a ligand, the chelation mode is that amino chelated molybdate and hydroxyl chelated borate in triethanolamine, and triethanolamine links the molybdate and borate, so that a novel cross-linking agent is formed, which has two ion centers of boron and molybdenum, can cross-link more thickening agents containing hydroxyl, amino and other active groups, has stronger cross-linking capability than the cross-linking agent with a single ion center, and has tighter chelated molecular groups, thus leading to the increase of viscosity. Examples 4 and 5 show an apparent viscosity slightly lower than example 3, further demonstrating that triethanolamine is used to link the molybdate and borate, and the novel chelating agent formed has a greater crosslinking capacity. The viscosity of the fracturing fluid corresponding to the embodiment 2 is extremely low, because the ammonium persulfate gel breaker is directly added, and ammonium persulfate and molybdate react, so that molybdenum trioxide is formed by dehydration of molybdate, and meanwhile, the ammonium persulfate also damages the molecular chain structure of the thickener, and antagonizes with the crosslinking agent, so that the viscosity of the fracturing fluid is reduced.
Test example 2
Gel breaking Performance test
The breaking performance of the fracturing fluid for test is tested by referring to the 7.9 th test of SY/T5107-2016 water-based fracturing fluid evaluation method.
The testing method comprises the following steps: the breaking speed and the complete breaking time are two important parameters of the breaking performance of the fracturing fluid. Placing the prepared fracturing fluid in a closed container, heating the fracturing fluid to 90 ℃ from 25 ℃ at a speed of 5 ℃/min, performing gel breaking experiments on the fracturing fluid at the temperature, and measuring the viscosity of supernatant. The viscosity of the supernatant can be measured by an NDJ28S type rotational viscometer, and the time required for the viscosity of the supernatant to reach 10 mPa.s can be measured, including the heating time at a rate of 5 ℃/min.
The preparation method of the fracturing fluid for the test comprises the following steps: mixing 15 parts of polyvinyl alcohol (PVA), 14 parts of carboxymethyl hydroxypropyl guanidine gum and 1000 parts of deionized water, and stirring at a speed of 800r/min for 15min to obtain a base solution; the multi-effect fracturing auxiliary agent and the base fluid prepared in the example and the comparative example are mixed according to the mass ratio of 1.5:100, and stirring for 15min at a rotation speed of 600r/min to obtain the fracturing fluid for testing.
Table 2: gel breaking Property
| Gel breaking time/min | |
| Example 1 | 60 |
| Example 2 | 15 |
| Example 3 | 18 |
| Example 4 | 80 |
| Example 5 | 25 |
| Comparative example 1 | 40 |
As can be seen from Table 2, the gel breaking time required in example 3 is shorter, 13min of the heating process at the rate of 5 ℃/min is removed, and after the temperature reaches 90 ℃, the viscosity of the gel solution is reduced to 10 mPa.s only for 5min, because at 85 ℃, the capsule shell of the microcapsule gel breaker begins to melt, ammonium persulfate is released, the triethanolamine-chelated molybdate ions are dehydrated under the action of the oxidant ammonium persulfate to generate molybdenum trioxide, the crosslinking effect of the triethanolamine-chelated molybdenum is reduced, further, as the temperature rises, the molybdenum trioxide is heated to excite to generate hot electrons and holes, and the molybdenum persulfate is synergistic with the ammonium persulfate, a large number of superoxide radicals can be further generated, and the gel structure is rapidly destroyed. Compared with example 3, the gel breaking time and the gel breaking performance shown in example 2 are shorter, but because the ammonium persulfate in example 2 is directly added, molybdenum trioxide is generated by premature reaction with molybdic acid radicals playing a role in crosslinking, the crosslinking capacity of the crosslinking agent is weakened, the viscosity of the fracturing fluid is reduced, meanwhile, the molybdenum trioxide and the ammonium persulfate cooperate, and the gel is broken prematurely, so that the viscosity of the initial fracturing fluid cannot meet the requirement of fracturing work, the performance of the fracturing work is not facilitated, and the fracturing fluid is not suitable for the fracturing work. Comparison of example 1 and example 3 shows that molybdenum trioxide is generated by virtue of thermal decomposition of molybdic acid radicals alone, and then the adhesive structure is destroyed by utilizing the thermal catalysis capability of the molybdenum trioxide, so that the adhesive breaking is performed too slowly. Firstly, molybdenum trioxide generated by thermal decomposition of molybdate is too slow, and the quantity of molybdenum trioxide generated in a short time is too small, so that quick gel breaking is not realized; secondly, the movement distance of hot electrons and holes generated by the thermal catalysis of the independent molybdenum trioxide is too short, and the catalytic degradation range is too small, so that the independent gel breaking speed is low. And ammonium persulfate can oxidize molybdate so as to quickly generate molybdenum trioxide, and meanwhile, oxygen molecules generated when the ammonium persulfate oxidizes and damages the viscose structure can become a transfer carrier of molybdenum trioxide hot electrons so as to generate superoxide radicals with longer service life, expand the catalytic degradation range of the superoxide radicals and realize quick gel breaking. As can be seen from the comparative examples, ammonium persulfate alone is also weak in breaking ability, which is determined by its own properties, and it is slow in breaking the viscose structure by oxidation and is also severely affected by concentration, temperature, etc. Therefore, the novel cross-linking agent synthesized by the invention and the microcapsule gel breaker containing ammonium persulfate cooperate to realize rapid gel breaking at a specific temperature, and the novel cross-linking agent can adapt to the fracturing work of a high-temperature oil layer and has excellent performance.
Claims (4)
1. The preparation method of the multi-effect fracturing auxiliary agent is characterized by comprising the following steps of:
heating 50-75 parts of water to 40-50 ℃ according to parts by mass, stirring at a rotating speed of 80-120r/min, adding 10-20 parts of clay swelling inhibitor into the water, and reacting for 0.5-1h; then adding 8-10 parts of AP-type demulsifier, and continuously stirring for 0.5-1h; adding 0.5-1 part of pH regulator, and stirring for 20-30min; finally, heating to 50-60 ℃ at a speed of 1-10 ℃/min, adding 10-15 parts of cross-linking agent and 5-10 parts of microcapsule gel breaker, and stirring for 0.5-1h at a speed of 80-120r/min to obtain the multi-effect fracturing auxiliary agent;
the preparation method of the cross-linking agent comprises the following steps:
s1, mixing 8-12 parts of ligand and 85-100 parts of water according to parts by weight, and stirring for 5-10min at a rotating speed of 80-120r/min to obtain a ligand aqueous solution;
s2, mixing 2-5 parts of an ion source and 1-2 parts of a 20-30wt% sodium hydroxide aqueous solution according to parts by mass, and stirring for 3-5min at a rotating speed of 80-120r/min to obtain a mixed ion solution;
s3, heating the ligand aqueous solution prepared in the step S1 to 70-85 ℃ at a speed of 1-10 ℃/min, dropwise adding a mixed ion solution into the ligand aqueous solution at a speed of 2-5mL/min, regulating the pH value to 7.0 by using a 20-30wt% hydrochloric acid aqueous solution after the dropwise adding is finished, reacting at a constant temperature for 1-3h, cooling to room temperature, filtering, washing and drying at room temperature to obtain the cross-linking agent;
the ion source is formed by mixing molybdenum trioxide and borax;
the ligand is triethanolamine;
the preparation method of the microcapsule gel breaker comprises the following steps: mixing 70-75 parts of chloroform, 10-14 parts of liquid paraffin and 0.1-1 part of polyvinylpyrrolidone, adding 6-8 parts of ammonium persulfate, 0.1-1 part of absolute ethyl alcohol, 0.1-0.5 part of n-amyl alcohol, 0.01-0.2 part of polyethylene glycol 4000, 4-6 parts of ethylenediamine tetraacetic acid and 0.1-1 part of ethyl methacrylate, stirring for 20-40min, and filtering, washing and airing to obtain the microcapsule gel breaker.
2. The method for preparing the multi-effect fracturing aid according to claim 1, wherein the pH regulator is one of citric acid, carbonic acid and acetic acid.
3. The method for preparing a multi-effect fracturing aid according to claim 1, wherein the clay swelling inhibitor is one of cetyl trimethyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride and polymethyl acryloyloxyethyl trimethyl ammonium chloride.
4. A multi-effect fracturing aid, characterized in that it is prepared by the preparation method of the multi-effect fracturing aid according to any one of claims 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310162711.8A CN116179179B (en) | 2023-02-24 | 2023-02-24 | Multi-effect fracturing auxiliary agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310162711.8A CN116179179B (en) | 2023-02-24 | 2023-02-24 | Multi-effect fracturing auxiliary agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116179179A CN116179179A (en) | 2023-05-30 |
| CN116179179B true CN116179179B (en) | 2023-08-25 |
Family
ID=86441992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310162711.8A Active CN116179179B (en) | 2023-02-24 | 2023-02-24 | Multi-effect fracturing auxiliary agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116179179B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236532A (en) * | 2017-06-19 | 2017-10-10 | 四川银宇化工科技有限公司 | A kind of New Clear Fracturing Fluid and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110105369A1 (en) * | 2009-10-30 | 2011-05-05 | Halliburton Energy Services, Inc. | Well treatment fluids containing a viscoelastic surfactant and a cross-linking agent comprising a water-soluble transition metal complex |
-
2023
- 2023-02-24 CN CN202310162711.8A patent/CN116179179B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236532A (en) * | 2017-06-19 | 2017-10-10 | 四川银宇化工科技有限公司 | A kind of New Clear Fracturing Fluid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 有机硼锆交联剂的制备与延缓交联效果;胡世平;李建平;韩俊华;张云玲;段辉彬;;油田化学(01);第37-39+62页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116179179A (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4215001A (en) | Methods of treating subterranean well formations | |
| US6209646B1 (en) | Controlling the release of chemical additives in well treating fluids | |
| CA1246850A (en) | Liquid fluid loss control additive for oil field cements | |
| US3058909A (en) | Method and composition for formation fracturing | |
| EA004093B1 (en) | Viscosity reduction of viscoelastic surfactant based fluids | |
| GB2416792A (en) | Well treatment fluid | |
| US20080103066A1 (en) | Use of mineral oils to reduce fluid loss for viscoelastic surfactant gelled fluids | |
| CN102634328A (en) | Carboxymethyl hydroxypropyl guanidine gum fracturing fluid | |
| AU2010338032B2 (en) | Delivering water-soluble polysaccharides for well treatments | |
| CN106753315A (en) | A kind of temperature control type becomes mucic acid and preparation method thereof | |
| CN116179179B (en) | Multi-effect fracturing auxiliary agent and preparation method thereof | |
| AU2015308696B2 (en) | Method and materials for hydraulic fracturing with delayed crosslinking of gelling agents | |
| CN104927005B (en) | A kind of alkaline-resisting profile control agent of pre-crosslinked gel volume expansion grain and preparation method thereof and purposes | |
| CN102643637A (en) | Clear fracturing fluid | |
| CN116355606B (en) | Fracturing auxiliary agent | |
| CN105778883A (en) | Full-suspension cleaning polymer fracturing fluid and preparation method thereof | |
| CN115404062A (en) | PH value and temperature dual-response supramolecular gel temporary plugging agent, preparation method and application thereof, and temporary plugging diversion fracturing method | |
| CN110408375B (en) | Low-temperature guar gum fracturing fluid | |
| CN115851251A (en) | Fracturing oil displacement agent and preparation method and application thereof | |
| CN115926771B (en) | Self-breaking modified soap kernel glue fracturing fluid and use method thereof | |
| CN115044357B (en) | Supermolecule-macromolecule double-network gel system and preparation method and application thereof | |
| EP3697864A1 (en) | Fracturing fluids comprising alkanolamine borates as crosslinkers for polysaccharides | |
| CN109503759A (en) | A kind of supermolecule fracturing fluid and preparation method thereof with self-healing properties | |
| CN110903817B (en) | Viscosity reducer for reducing viscosity of base liquid of vegetable gum temporary plugging rubber plug and preparation method thereof | |
| CN114806527B (en) | Ternary viscous micelle scale degradation agent of nonylphenol polyoxyethylene ether oxalic acid sodium salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |