CN112111264A - Guar gum graft copolymer nano composite gel fracturing fluid and preparation method thereof - Google Patents
Guar gum graft copolymer nano composite gel fracturing fluid and preparation method thereof Download PDFInfo
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Abstract
The invention provides guar gum graft copolymer nano composite gel fracturing fluid and a preparation method thereof, wherein the fracturing fluid comprises the following components in percentage by mass: guar gum graft copolymer thickener 0.4-1.2%, nanometer material 0.05-0.5%, cross-linking agent 0.2-1%, and water in balance. The invention takes guar gum or a diffraction product thereof and acrylamide monomers as raw materials to synthesize a guar gum graft copolymer, and then takes the guar gum graft copolymer as a thickening agent, and nano material dispersion liquid is added to prepare the nano composite gel fracturing fluid under the action of a cross-linking agent. According to the invention, the hydrophilic flexible polymer branched chain is introduced on the semi-rigid macromolecular chain of the guar gum, so that mutual entanglement and adsorption between the guar gum and the nano material are facilitated, the compatibility between the guar gum and the nano material can be greatly increased, the interaction between the nano material and a polymer matrix is further increased, and the nano composite gel fracturing fluid prepared by the nano composite gel fracturing fluid has better temperature resistance, shearing resistance, sand carrying property and filtration loss reduction property.
Description
Technical Field
The invention belongs to the technical field of oil and gas field development, and particularly relates to guar gum grafted copolymer nano composite gel fracturing fluid and a preparation method thereof.
Background
Hydraulic fracture reformation is an important stimulation tool for the development of low permeability reservoirs. The method is characterized in that a ground high-pressure pump set is used for injecting viscous liquid into a well, high pressure is generated at the low position of the well, when the pressure exceeds the ground stress near the wall of the well and the tensile strength of rock, a crack is generated in the stratum near the bottom of the well, sand-carrying liquid with propping agent is injected into the crack continuously, the crack extends forwards, and the propping agent is filled in the crack. After the pump is stopped, the high-viscosity liquid is gradually broken and discharged back to the ground, and the propping agent is left in the cracks, so that one or more supporting cracks which are long enough and have high flow conductivity are formed in the stratum, and the oil-gas flow can be favorably infiltrated into a shaft from the stratum. The fracturing fluid is a high-viscosity liquid used for making seams and carrying sand in hydraulic fracturing, is a key component of the hydraulic fracturing, and the performance of the fracturing fluid directly determines the quality of construction effect.
The most widely applied home and abroad is the water-based fracturing fluid system. The chemical additive components of the water-based fracturing fluid are many, and mainly comprise a thickening agent, a cross-linking agent and a gel breaker. The thickening agent has the functions of thickening, reducing filtration loss and reducing friction resistance, and is the core part of the fracturing fluid. The thickening agent can further form fracturing fluid gel under the action of the cross-linking agent so as to greatly improve the viscosity and stability of the fracturing fluid. Current water-based gel fracturing fluids typically employ guar or its derivatives (hydroxypropyl guar, carboxymethylhydroxypropyl guar) as viscosifying agents, crosslinked with various ions (B, Zr or Ti) to form viscoelastic gels. Guar gum is a natural high molecular polysaccharide extracted from endosperm of guar, the main chain of the molecule is formed by linking (1,4) -beta-D-mannose as a unit, the side chain is formed by single alpha-D-galactose and is connected with the main chain by a (1,6) bond, wherein, approximately every two mannose units are connected with a galactose side group. The guar gum has rich sources, low cost and good water solubility and thickening property, and the formed fracturing fluid jelly has the advantages of strong fracture forming capability, good sand carrying property, good filtration control property and the like. However, with the increasing demand for oil and gas energy in recent years, the exploitation of oil and gas fields is developed from shallow layers to deep layers, and high-temperature wells are increased day by day, so that higher requirements are provided for the temperature resistance of a fracturing fluid system. Under the condition of high temperature, the glycosidic bond on the guar gum macromolecular chain is easy to break, so that the molecular weight of the guar gum is reduced, the crosslinking system is decomposed, and the solution system loses viscosity, thereby losing the effects of suspension and carrying a propping agent. Therefore, modification of guar gum is needed.
The nano composite technology provides a new way for modifying the performance of the existing material. By uniformly dispersing nano-sized materials in a matrix material, a composite system containing nano-materials is formed. In the polymer nano composite system, the interaction of hydrogen bond, van der waals force, electrostatic force and the like is generated between a polymer chain and the high-activity surface of the nano phase, so that the rigidity, the size and the thermal stability of the nano phase and the characteristics of the polymer are combined on a nano scale, and the comprehensive performance of the polymer is improved.
The final properties of polymer nanocomposite systems are largely dependent on the uniformity of the dispersion of the nanomaterial in the polymer matrix and the interaction between the nanomaterial and the polymer matrix. Therefore, the key technology for preparing the high-performance nano composite fracturing fluid is to solve the problems in the two aspects. In the existing guar gum nano composite modification technology, most of the guar gum nano composite modification technologies are used for directly adding nano materials or modifying the surfaces of the nano materials to increase the interaction between guar gum molecular chains and the nano materials and improve the performance of the nano composite materials. However, guar gum is a semi-rigid macromolecule, and affinity, adsorption and entanglement effects between the guar gum and a nano material are limited to a certain extent, so that the method of only modifying the surface of the nano material to increase the interaction between the nano material and the guar gum is far insufficient, the obtained fracturing fluid is poor in temperature resistance, shear resistance, sand carrying performance and fluid loss reduction performance, and insufficient in viscoelasticity performance and stability, and the use of the fracturing fluid is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the guar grafted copolymer nano composite gel fracturing fluid and the preparation method thereof provided by the invention can be used for preparing the guar grafted copolymer nano composite gel fracturing fluid with more excellent performance, and effectively solve the problems of poor temperature resistance and shear resistance, insufficient viscoelasticity performance and stability and the like of the guar fracturing fluid in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the guar gum graft copolymer nano composite gel fracturing fluid comprises the following components in percentage by mass: guar gum graft copolymer thickener 0.4-1.2%, nanometer material 0.05-0.5%, cross-linking agent 0.2-1%, and water in balance.
Further, the guar gum graft copolymer thickening agent is synthesized by the following components in parts by weight: 2-10 parts of guar gum or guar gum derivative, 5-25 parts of acrylamide monomer, 0.1-2 parts of initiator and 800-1500 parts of water.
Further, the guar gum derivative is hydroxypropyl guar gum, carboxymethyl guar gum or carboxymethyl hydroxypropyl guar gum.
Further, the acrylamide monomer is acrylamide or a mixture of acrylamide and at least one of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
Further, when the acrylamide monomer is a mixture of acrylamide and acrylic acid, the acrylic acid accounts for 5-30% of the mixture by mole percent;
when the acrylamide monomer is a mixture of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid, the molar percentage of the 2-acrylamido-2-methylpropanesulfonic acid in the mixture is 10 to 60 percent;
when the acrylamide monomer is a mixture of acrylamide, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, the molar percentage of acrylic acid in the mixture is 5 to 30%, and the molar percentage of 2-acrylamido-2-methylpropanesulfonic acid in the mixture is 10 to 60%.
Further, the acrylamide monomer is acrylamide.
Further, the acrylamide monomer is a mixture of acrylamide and acrylic acid, and the acrylic acid accounts for 5-30% of the mixture in mole percentage.
Further, the acrylamide monomer is a mixture of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid, and the molar percentage of the 2-acrylamido-2-methylpropanesulfonic acid in the mixture is 10 to 60%.
Further, the acrylamide monomer is a mixture of acrylamide, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, wherein the acrylic acid accounts for 5-30% of the mixture in mol percent, and the 2-acrylamido-2-methylpropanesulfonic acid accounts for 10-60% of the mixture in mol percent.
Further, the initiator is cerium ammonium nitrate or potassium persulfate.
Further, the guar grafted copolymer thickening agent is synthesized by the following method:
(1) slowly adding guar gum or guar gum derivative powder under the water bath condition of 30-50 ℃ and 500-;
(2) dissolving acrylamide monomers in water, and adjusting the pH value to 7 +/-0.5 by using 20-30 wt% of sodium hydroxide solution to obtain a monomer solution;
(3) adding the monomer solution obtained in the step (2) into the guar gum water solution obtained in the step (1), stirring for 20-40min under the condition of 200-600r/min, introducing nitrogen to remove oxygen for 30-60min, then heating in a water bath to 30-65 ℃, adding an initiator, stirring and reacting for 12-24h under the condition of 200-600r/min under the protection of nitrogen, introducing oxygen, cooling to room temperature, precipitating with acetone, filtering, and finally drying in vacuum at 40-50 ℃ to constant weight to obtain a crude guar gum graft copolymer product;
(4) heating, refluxing and dissolving the crude product of the guar gum graft copolymer obtained in the step (3) by using a mixed solvent formed by mixing glacial acetic acid and formamide according to the volume ratio of 1:1, adding cooled reflux liquid into acetone until no precipitate is separated out, and then drying in vacuum at 40-50 ℃ to constant weight to obtain the thickening agent of the guar gum graft copolymer.
Further, the nano material is at least one of nano silicon dioxide, cellulose nano fiber and montmorillonite.
Further, the particle size of the nano silicon dioxide is 5-50 nm; the length of the cellulose nanofiber is 1-3um, and the diameter is 4-10 nm.
Further, the cellulose nanofiber is at least one of cellulose nanofiber with a surface which is not chemically modified, TEMPO system oxidized cellulose nanofiber, carboxymethylated modified cellulose nanofiber and anion modified cellulose nanofiber.
Further, the crosslinking agent is a boron crosslinking agent and/or a transition metal (Zr, Ti) crosslinking agent.
The preparation method of the guar gum graft copolymer nano composite gel fracturing fluid comprises the following steps:
(1) adding the nanometer material into water, and high-speed shearing and dispersing for 10-15min by using a homogenizer to obtain solution A;
(2) adding the guar gum graft copolymer thickening agent into water, stirring and dissolving completely to obtain solution B;
(3) and (3) stirring the solution A obtained in the step (1) and the solution B obtained in the step (2) for 1-2h under the condition of 1000r/min, then adding a cross-linking agent and uniformly stirring to obtain the guar gum graft copolymer nano composite gel fracturing fluid.
In summary, the invention has the following advantages:
1. the invention firstly grafts a polyacrylamide branched chain on a guar gum molecular chain to prepare the guar gum branched copolymer fracturing fluid thickening agent. On one hand, the new performance of the branch chain of the guar gum is endowed, and the inherent advantages of the guar gum are not completely destroyed, so that the advantages of the two on the performance are made up. On the other hand, the graft copolymer takes guar gum as a semi-rigid main chain and polyacrylamide as a flexible branch chain to form a rigid, flexible and bulky reticular macromolecule, so that the graft copolymer has more stable performance under high-temperature and high-shear environments.
2. The synthesized guar grafted copolymer densifier is easy to have the interaction of affinity, adsorption, entanglement and the like with the added nano material due to the flexible polyacrylamide branched chains and the large molecular space volume, so that the compatibility of semi-rigid guar molecular chains and the nano material can be greatly improved, and the interaction of hydrogen bonds, electrostatic force and the like between rich functional groups (amide groups, carboxyl groups or sulfonic groups) on the molecular chains and the surface of the nano material is further improved.
3. When the nano composite gel fracturing fluid is prepared, firstly, a homogenizer is adopted to shear and disperse the nano material at a high speed to prepare the dispersion liquid, so that the dispersion problem of the nano material can be effectively solved.
The invention considers the dispersion of the nanometer material and the interaction between the nanometer material and the polymer matrix, and can further improve the viscoelasticity and the stability of the formed nanometer composite gel fracturing fluid, so that the nanometer composite gel fracturing fluid has better temperature resistance, shearing resistance, sand carrying property and filtration loss reduction property.
Drawings
FIG. 1 is a NMR hydrogen spectrum of a guar grafted copolymer nanocomposite gel fracturing fluid obtained in example 1;
FIG. 2 is a NMR hydrogen spectrum of a guar grafted copolymer nanocomposite gel fracturing fluid obtained in example 2;
FIG. 3 shows the temperature and shear resistance test results of the guar grafted copolymer nanocomposite gel fracturing fluid obtained in example 1;
FIG. 4 shows the temperature and shear resistance test results of the guar grafted copolymer nanocomposite gel fracturing fluid obtained in example 2;
FIG. 5 is a comparison of the temperature and shear resistance test results for the fracturing fluids of example 2 and the comparative example.
Detailed Description
Example 1
The guar gum graft copolymer nano composite gel fracturing fluid comprises the following components in percentage by mass: 0.5% of guar gum graft copolymer thickening agent, 0.1% of nano silicon dioxide powder, 0.3% of borax and the balance of water.
The guar gum graft copolymer thickening agent is synthesized from the following components in parts by weight: 3 parts of guar gum powder, 8 parts of acrylamide, 0.8 part of ammonium ceric nitrate and 900 parts of water.
The guar grafted copolymer thickening agent is synthesized by the following method:
(1) slowly adding guar gum powder in water bath at 40 deg.C and 600r/min, stirring for 30min, and standing at 30 deg.C for 4 hr to obtain guar gum water solution;
(2) dissolving acrylamide in water, and adjusting the pH value to 7 +/-0.5 by using 25 wt% of sodium hydroxide solution to obtain a monomer solution;
(3) adding the monomer solution obtained in the step (2) into the guar gum aqueous solution obtained in the step (1), stirring for 30min under the condition of 300r/min, introducing nitrogen to remove oxygen for 60min, heating in a water bath to 45 ℃, adding ammonium ceric nitrate, stirring and reacting for 24h under the condition of 300r/min under the protection of nitrogen, introducing oxygen, cooling to room temperature, precipitating with acetone, filtering, and finally drying in vacuum at 45 ℃ to constant weight to obtain a guar gum graft copolymer crude product;
(4) and (3) heating, refluxing and dissolving the crude guar gum graft copolymer product obtained in the step (3) by using a mixed solvent formed by mixing glacial acetic acid and formamide according to the volume ratio of 1:1, adding cooled reflux liquid into acetone until no precipitate is separated out, and then drying in vacuum at 45 ℃ to constant weight to obtain the guar gum graft copolymer thickening agent.
The preparation method of the guar gum graft copolymer nano composite gel fracturing fluid comprises the following steps:
(1) adding the nano silicon dioxide powder into water, and shearing and dispersing for 15min at a high speed by using a homogenizer to obtain a solution A;
(2) adding the guar gum graft copolymer thickening agent into water, stirring and dissolving completely to obtain solution B;
(3) and (3) stirring the solution A obtained in the step (1) and the solution B obtained in the step (2) for 1h at the speed of 800r/min, then adding borax and uniformly stirring to obtain the guar gum graft copolymer nano composite gel fracturing fluid.
Example 2
The guar gum graft copolymer nano composite gel fracturing fluid comprises the following components in percentage by mass: 0.6% of guar gum graft copolymer thickening agent, 0.1% of cellulose nano-fiber, 0.8% of triethanolamine boron crosslinking agent and the balance of water.
The guar gum graft copolymer thickening agent is synthesized from the following components in parts by weight: 5 parts of guar gum powder, 7 parts of acrylamide, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1 part of ammonium ceric nitrate and 1200 parts of water.
The guar grafted copolymer thickening agent is synthesized by the following method:
(1) slowly adding guar gum powder in water bath at 40 deg.C and 800r/min, stirring for 60min, and standing at 30 deg.C for 4 hr to obtain guar gum water solution;
(2) dissolving acrylamide and 2-acrylamido-2-methylpropanesulfonic acid in water, and adjusting the pH value to 7 +/-0.5 by using 25 wt% of sodium hydroxide solution to obtain a monomer solution;
(3) adding the monomer solution obtained in the step (2) into the guar gum aqueous solution obtained in the step (1), stirring for 30min under the condition of 500r/min, introducing nitrogen to remove oxygen for 60min, heating in a water bath to 50 ℃, adding ammonium ceric nitrate, stirring and reacting for 12h under the condition of 500r/min under the protection of nitrogen, introducing oxygen, cooling to room temperature, precipitating with acetone, filtering, and finally drying in vacuum at 45 ℃ to constant weight to obtain a guar gum graft copolymer crude product;
(4) and (3) heating, refluxing and dissolving the crude guar gum graft copolymer product obtained in the step (3) by using a mixed solvent formed by mixing glacial acetic acid and formamide according to the volume ratio of 1:1, adding cooled reflux liquid into acetone until no precipitate is separated out, and then drying in vacuum at 45 ℃ to constant weight to obtain the guar gum graft copolymer thickening agent.
The preparation method of the guar gum graft copolymer nano composite gel fracturing fluid comprises the following steps:
(1) adding the cellulose nano-fiber hydrosol with the solid content of 1% and subjected to surface carboxymethylation into water, and performing high-speed shearing dispersion for 10min by using a homogenizer to obtain a solution A;
(2) adding the guar gum graft copolymer thickening agent into water, stirring and dissolving completely to obtain solution B;
(3) and (3) stirring the solution A obtained in the step (1) and the solution B obtained in the step (2) for 1 hour at the speed of 600r/min, then adding a triethanolamine boron crosslinking agent and uniformly stirring to obtain the guar gum graft copolymer nano composite gel fracturing fluid.
Example 3
The guar gum graft copolymer nano composite gel fracturing fluid comprises the following components in percentage by mass: 0.5 percent of guar gum graft copolymer thickening agent, 0.2 percent of sodium-based montmorillonite powder, 0.5 percent of zirconium lactate crosslinking agent and the balance of water.
The guar gum graft copolymer thickening agent is synthesized from the following components in parts by weight: 6 parts of hydroxypropyl guar gum powder, 9 parts of acrylamide, 1 part of acrylic acid, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 0.5 part of potassium persulfate and 1000 parts of water.
The guar grafted copolymer thickening agent is synthesized by the following method:
(1) slowly adding hydroxypropyl guar gum powder in water bath at 40 deg.C and 1000r/min, stirring for 60min, and standing at 30 deg.C for 4 hr to obtain guar gum water solution;
(2) dissolving acrylamide, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid in water, and adjusting the pH value to 7 +/-0.5 by using 25 wt% of sodium hydroxide solution to obtain a monomer solution;
(3) adding the monomer solution obtained in the step (2) into the guar gum aqueous solution obtained in the step (1), stirring for 30min under the condition of 600r/min, introducing nitrogen to remove oxygen for 60min, heating in a water bath to 55 ℃, adding potassium persulfate, stirring and reacting for 16h under the condition of 600r/min under the protection of nitrogen, introducing oxygen, cooling to room temperature, precipitating with acetone, filtering, and finally drying in vacuum at 45 ℃ to constant weight to obtain a guar gum graft copolymer crude product;
(4) and (3) heating, refluxing and dissolving the crude guar gum graft copolymer product obtained in the step (3) by using a mixed solvent formed by mixing glacial acetic acid and formamide according to the volume ratio of 1:1, adding cooled reflux liquid into acetone until no precipitate is separated out, and then drying in vacuum at 45 ℃ to constant weight to obtain the guar gum graft copolymer thickening agent.
The preparation method of the guar gum graft copolymer nano composite gel fracturing fluid comprises the following steps:
(1) adding sodium-based montmorillonite powder into water, and shearing and dispersing for 15min at high speed by using a homogenizer to obtain solution A;
(2) adding the guar gum graft copolymer thickening agent into water, stirring and dissolving completely to obtain solution B;
(3) and (3) stirring the solution A obtained in the step (1) and the solution B obtained in the step (2) for 1h at the speed of 1000r/min, adding a zirconium lactate cross-linking agent, and uniformly stirring to obtain the guar gum graft copolymer nano composite gel fracturing fluid.
Example 4
The guar gum graft copolymer nano composite gel fracturing fluid comprises the following components in percentage by mass: 0.6% of guar gum graft copolymer thickening agent, 0.2% of nano silicon dioxide, 0.3% of borax and the balance of water.
The guar gum graft copolymer thickening agent is synthesized from the following components in parts by weight: 5 parts of carboxymethyl hydroxypropyl guar gum powder, 6 parts of acrylamide, 2 parts of acrylic acid, 1 part of ammonium ceric nitrate and 1500 parts of water.
The guar grafted copolymer thickening agent is synthesized by the following method:
(1) slowly adding carboxymethyl hydroxypropyl guar gum powder in water bath at 40 deg.C and 800r/min, stirring for 30min, and standing at 30 deg.C for 4 hr to obtain guar gum water solution;
(2) dissolving acrylamide and acrylic acid in water, and adjusting the pH value to 7 +/-0.5 by using 25 wt% of sodium hydroxide solution to obtain a monomer solution;
(3) adding the monomer solution obtained in the step (2) into the guar gum aqueous solution obtained in the step (1), stirring for 30min under the condition of 500r/min, introducing nitrogen to remove oxygen for 60min, heating in a water bath to 50 ℃, adding ammonium ceric nitrate, stirring and reacting for 12h under the condition of 500r/min under the protection of nitrogen, introducing oxygen, cooling to room temperature, precipitating with acetone, filtering, and finally drying in vacuum at 45 ℃ to constant weight to obtain a guar gum graft copolymer crude product;
(4) and (3) heating, refluxing and dissolving the crude guar gum graft copolymer product obtained in the step (3) by using a mixed solvent formed by mixing glacial acetic acid and formamide according to the volume ratio of 1:1, adding cooled reflux liquid into acetone until no precipitate is separated out, and then drying in vacuum at 45 ℃ to constant weight to obtain the guar gum graft copolymer thickening agent.
The preparation method of the guar gum graft copolymer nano composite gel fracturing fluid comprises the following steps:
(1) adding the nano silicon dioxide powder into water, and shearing and dispersing for 15min at a high speed by using a homogenizer to obtain a solution A;
(2) adding the guar gum graft copolymer thickening agent into water, stirring and dissolving completely to obtain solution B;
(3) and (3) stirring the solution A obtained in the step (1) and the solution B obtained in the step (2) for 1h at the speed of 600r/min, then adding a borax cross-linking agent and uniformly stirring to obtain the guar gum graft copolymer nano composite gel fracturing fluid.
Comparative example
The guar gum nano composite gel fracturing fluid comprises the following components in percentage by mass: 0.6% of guar gum, 0.1% of cellulose nano-fiber, 0.8% of triethanolamine boron crosslinking agent and the balance of water. The preparation method comprises the following steps:
(1) adding the cellulose nano-fiber hydrosol with the solid content of 1% and subjected to surface carboxymethylation into water, and performing high-speed shearing dispersion for 10min by using a homogenizer to obtain a solution A;
(2) slowly adding guar gum powder in water bath at 40 deg.C and 800r/min, stirring for 60min, and standing at 30 deg.C for 4 hr to obtain solution B;
(3) and (3) stirring the solution A obtained in the step (1) and the solution B obtained in the step (2) for 1 hour at the speed of 600r/min, then adding a triethanolamine boron crosslinking agent and uniformly stirring to obtain the guar gum nano composite gel fracturing fluid.
Examples of the experiments
The NMR hydrogen spectra of the guar gum graft copolymer nanocomposite gel fracturing fluid obtained in the examples 1-2 are respectively shown in the figures 1-2; the Haake RS600 rheometer tested the temperature and shear resistance, and the results are shown in FIGS. 3-4.
As can be seen from FIGS. 3 to 4, the fracturing fluid system obtained in example 1 was maintained at 140 ℃ for 170 seconds-1The viscosity can be maintained above 50mPa & s after 120min of lower shearing; the fracturing fluid system obtained in example 2 was maintained at 160 ℃ for 170s-1The viscosity can be maintained above 100 mPa.s after 120min of shear, and the prepared guar grafted copolymer nano composite gel fracturing fluid shows good temperature resistance and shear resistance.
The temperature resistance and shear resistance of the guar gum graft copolymer nanocomposite gel fracturing fluid obtained in example 2 and the guar gum nanocomposite gel fracturing fluid obtained in the comparative example with the same concentration were measured, and the results are shown in fig. 5.
As can be seen from FIG. 5, the guar gum nano-composite gel fracturing fluid obtained in the comparative example has the viscosity reduced to below 50mPa & s after being sheared for 60 min; the guar gum grafted copolymer nano composite gel fracturing fluid prepared by the invention has better temperature resistance and shearing resistance, and the viscosity of the guar gum grafted copolymer nano composite gel fracturing fluid is still kept above 100mPa & s after shearing for 120 min. The guar gum is a semi-rigid macromolecule, the affinity, adsorption, entanglement and other interactions between the guar gum and flexible cellulose nanofibers are limited to a certain extent, and after a flexible hydrophilic polymer chain is grafted on a semi-rigid macromolecule chain of the guar gum, the guar gum has larger molecular space volume, a flexible polymer branched chain is easier to be entangled with the cellulose nanofibers, the interaction between active groups of the guar gum and the cellulose nanofibers is increased, the nanofibers can be more favorably used as physical crosslinking points, and the prepared gel fracturing fluid has better temperature resistance and shear resistance.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (10)
1. The guar grafted copolymer nano composite gel fracturing fluid is characterized by comprising the following components in percentage by mass: guar gum graft copolymer thickener 0.4-1.2%, nanometer material 0.05-0.5%, cross-linking agent 0.2-1%, and water in balance.
2. The guar graft copolymer nanocomposite gel fracturing fluid of claim 1, wherein the guar graft copolymer viscosifier is synthesized from the following components in parts by weight: 2-10 parts of guar gum or guar gum derivative, 5-25 parts of acrylamide monomer, 0.1-2 parts of initiator and 800-1500 parts of water.
3. The guar graft copolymer nanocomposite jelly fracturing fluid of claim 2, wherein the guar derivative is hydroxypropyl guar, carboxymethyl guar or carboxymethylhydroxypropyl guar.
4. The guar graft copolymer nanocomposite gel fracturing fluid of claim 2, wherein the acrylamide-based monomer is acrylamide or a mixture of acrylamide and at least one of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
5. The guar graft copolymer nanocomposite gel fracturing fluid of claim 4, wherein when the acrylamide-based monomer is a mixture of acrylamide and acrylic acid, the acrylic acid comprises 5 to 30 mole percent of the mixture;
when the acrylamide monomer is a mixture of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid, the molar percentage of the 2-acrylamido-2-methylpropanesulfonic acid in the mixture is 10 to 60%;
when the acrylamide monomer is a mixture of acrylamide, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, the acrylic acid accounts for 5-30 mol% of the mixture, and the 2-acrylamido-2-methylpropanesulfonic acid accounts for 10-60 mol% of the mixture.
6. The guar graft copolymer nanocomposite gel fracturing fluid of claim 2, wherein the initiator is cerium ammonium nitrate or potassium persulfate.
7. The guar graft copolymer nanocomposite gel fracturing fluid of claim 1 or 2, wherein the guar graft copolymer viscosifier is synthesized by the following method:
(1) adding guar gum or guar gum derivative powder under the water bath condition of 30-50 ℃ and 500-;
(2) dissolving acrylamide monomers in water, and adjusting the pH value to 7 +/-0.5 by using 20-30 wt% of sodium hydroxide solution to obtain a monomer solution;
(3) adding the monomer solution obtained in the step (2) into the guar gum water solution obtained in the step (1), stirring for 20-40min under the condition of 200-600r/min, introducing nitrogen to remove oxygen for 30-60min, then heating in a water bath to 30-65 ℃, adding an initiator, stirring and reacting for 12-24h under the condition of 200-600r/min under the protection of nitrogen, introducing oxygen, cooling to room temperature, precipitating with acetone, filtering, and finally drying in vacuum at 40-50 ℃ to constant weight to obtain a crude guar gum graft copolymer product;
(4) heating, refluxing and dissolving the crude product of the guar gum graft copolymer obtained in the step (3) by using a mixed solvent formed by mixing glacial acetic acid and formamide according to the volume ratio of 1:1, adding cooled reflux liquid into acetone until no precipitate is separated out, and then drying in vacuum at 40-50 ℃ to constant weight to obtain the thickening agent of the guar gum graft copolymer.
8. The guar grafted copolymer nanocomposite jelly-gel fracturing fluid of claim 1, wherein the nanomaterial is at least one of nanosilica, cellulose nanofibers, and montmorillonite.
9. The guar graft copolymer nanocomposite gel fracturing fluid of claim 1, wherein the crosslinker is a boron crosslinker and/or a transition metal crosslinker.
10. A method of preparing the guar graft copolymer nanocomposite gel fracturing fluid of any one of claims 1 to 9, comprising the steps of:
(1) adding the nanometer material into water, and high-speed shearing and dispersing for 10-15min by using a homogenizer to obtain solution A;
(2) adding the guar gum graft copolymer thickening agent into water, stirring and dissolving completely to obtain solution B;
(3) and (3) stirring the solution A obtained in the step (1) and the solution B obtained in the step (2) for 1-2h under the condition of 1000r/min, then adding a cross-linking agent and uniformly stirring to obtain the guar gum graft copolymer nano composite gel fracturing fluid.
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