CN115746823A - Epoxy resin-based composite proppant and preparation method thereof - Google Patents
Epoxy resin-based composite proppant and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- 238000006243 chemical reaction Methods 0.000 claims description 24
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- KGLLUXBCZIVSQO-UHFFFAOYSA-N C(=C)C(CCN)C=C Chemical compound C(=C)C(CCN)C=C KGLLUXBCZIVSQO-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002156 mixing Methods 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of fracturing propping agents, and particularly relates to an epoxy resin-based composite propping agent and a preparation method thereof. An epoxy resin-based composite proppant comprises an epoxy resin matrix and nano SiO uniformly distributed in the epoxy resin matrix 2 Particles of the nano SiO 2 The surface of the particle is modified by amino or epoxy group and is connected with the epoxy resin matrix through chemical bond, the particle size range of the epoxy resin matrix is 60um to 5mm, and the nano SiO is 2 The particle size range of the particles is 5nm to 500 nm, and the breaking rate of the epoxy resin-based composite propping agent is less than or equal to 3.8 percent under the indoor experiment test under the pressure of 28 Mpa. The epoxy resin-based composite proppant prepared by the invention utilizes nano SiO 2 The particles are used as a toughening agent, so that the toughness of the epoxy resin-based composite propping agent can be improved, the breaking rate of the propping agent is reduced, the flow conductivity of cracks generated by fracturing is improved, and the fracturing construction quality is further improved.
Description
Technical Field
The invention belongs to the technical field of fracturing propping agents, and particularly relates to an epoxy resin-based composite propping agent and a preparation method thereof.
Background
When oil and gas are exploited, after fracturing treatment is carried out on a high-closure-pressure low-permeability deposit, an oil-gas-containing rock stratum is cracked, oil and gas are gathered from a channel formed by the cracks, at the moment, fluid is required to be injected into a rock base layer so as to exceed the pressure of the fracture strength of the stratum, the rock stratum around a shaft is cracked, a channel with high laminar flow capacity is formed, and in order to keep the crack formed after fracturing open, oil and gas products can smoothly pass through. When the fracturing of the oil and gas field is transformed, the fractured stratum fracture needs to be propped by using a propping agent to improve the flow conductivity of the fracture.
The conventional propping agents are quartz sand and ceramsite, and because the density is high, high-viscosity fracturing fluid needs to be carried into a stratum during construction. The pumping process of the sand carrying fluid has high energy consumption, and meanwhile, the propping agent can cause serious erosion and abrasion to fracturing equipment and downhole tools. In addition, conventional proppants have difficulty accessing microfractures smaller than their size for effective propping. U.S. Pat. No. 3,10619089 proposes that epoxy resin is dispersed in a water phase to prepare an emulsion, the emulsion is used as a fracturing fluid, and a method of in-situ curing the epoxy resin under a stratum condition is utilized to prepare a proppant, but the brittleness after curing is more obvious, so that the resin particle breakage rate is higher, the service performance of the proppant can be obviously reduced, and the fracturing construction effect is influenced.
Disclosure of Invention
Aiming at the problems, the invention aims to provide an epoxy resin-based composite proppant and a preparation method thereof, and nano SiO is utilized 2 The particles are used as a toughening agent, so that the toughness of the epoxy resin-based composite proppant is improved, the breakage rate of the proppant is reduced, the flow conductivity of cracks generated by fracturing is improved, and the fracturing construction quality is further improved.
The technical scheme of the invention is as follows: an epoxy resin-based composite proppant comprises an epoxy resin matrix and nano SiO uniformly distributed in the epoxy resin matrix 2 Particles of the nano SiO 2 The surface of the particle is modified by amino or epoxy group, and is connected with the epoxy resin matrix through chemical bonds.
The particle size range of the epoxy resin matrix is 60um to 5mm, and the nano SiO 2 The particle size range of the particles is 5nm to 500 nm.
The breaking rate of the epoxy resin-based composite propping agent is less than or equal to 3.8 percent in an indoor experimental test under the pressure of 28 Mpa.
The preparation method of the epoxy resin-based composite proppant is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing nano SiO 2 The surface modification of the particles comprises the following specific processes:
according to the parts by weight, 0.1 to 1 part of nano SiO 2 Drying the particles at 90-120 ℃ for 10-36 h, adding 70-90 parts of toluene solvent, then adding 10-20 parts of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 5-20 min, stirring, heating to 100-130 ℃, continuously reacting for 12-36h, after the reaction is finished, washing with alcohol, and centrifugally drying to obtain white powdery amino or epoxy-modified SiO 2 A nanoparticle;
s2: the preparation method of the epoxy resin emulsion comprises the following specific steps:
s21: adding 1 to 10 parts of diluent into 10 to 40 parts of epoxy resin according to parts by weight, and stirring and diluting for later use;
s22: according to the parts by weight, sequentially stirring 38.9 to 87.99 parts of deionized water, 0.5 to 6 parts of emulsifier, 0.5 to 5 parts of NaOH and 0.01 to 0.1 part of organic silicon defoamer at 30 to 90 ℃, adding the diluted epoxy resin in S21, and continuously stirring to prepare an epoxy resin emulsion;
s3: 0.001 to 0.1 part of modified nano SiO by weight 2 The particles, 10 to 30 parts of curing agent and 0.5 to 2 parts of curing accelerator are sequentially added into 67.9 to 89.499 parts of epoxy resin emulsion, stirred, stood and cured to obtain the nano SiO 2 The particles are uniformly distributed in an epoxy resin matrix generated after the curing reaction to obtain the epoxy resin-based composite proppant.
In the step S1, the silane coupling agent is one of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and gamma-aminopropyl triethoxy silane.
In the step S2, the diluent is one of n-butyl glycidyl ether, ethyl acetate, and acetone.
In the step S2, the emulsifier is one of alkylphenol ethoxylates and lauramidopropyl hydroxysulfobetaine.
In the step S3, the modified nano SiO 2 Adding the particles, the curing agent and the curing accelerator into the epoxy resin emulsion, stirring at the temperature of 40-80 ℃ and the stirring speed of 600-1200 r/min for 5-25 min, and then stirring or standing at the stirring speed of 100-300 r/min for 2 h.
In the step S3, the curing agent is one of aliphatic amine curing agents tetraethylenepentamine and divinylpropylamine.
In the step S3, the curing accelerator is one of 2,4, 6-tris (dimethylaminomethyl) phenol, diethylenetriamine, and triethylenetetramine.
The invention has the technical effects that: 1. the invention utilizes nano SiO 2 The particles being as toughening agents, siO 2 The nano particles have the characteristics of uniform particle size and high surface activity, can be uniformly dispersed in a resin matrix,the surface functional group can fully react with the epoxy matrix, and simultaneously SiO 2 The nano particles can influence cross-linking sites in the resin matrix, change the local microstructure of the proppant and increase the toughness of the proppant; 2. in the preparation process of the epoxy resin emulsion, the viscosity of the epoxy resin can be reduced by adding the diluent, the dispersibility of the epoxy resin in water is improved, the epoxy resin is convenient to solidify into balls, the interference of impurity ions in tap water can be avoided by using deionized water, so that the reaction is normally carried out, the oil-water interfacial tension can be reduced by using the emulsifier, the emulsion is favorable for preparing, the pH value is adjusted by NaOH, the epoxy resin is favorable for solidifying, a large amount of bubbles can be generated in the stirring process of the emulsion, and the bubbles can be avoided by using the defoaming agent, so that the operation and the actual production are convenient; 3. the particle size of the epoxy resin-based composite proppant can be effectively controlled by the speed of a high-speed stirring stage, and the particle size of the epoxy resin-based composite proppant can be controlled between 60 mu m and 5mm by controlling different stirring speeds to be 600-1200 r/min, so that the epoxy resin-based composite proppant is convenient and simple and is convenient for large-scale production; 4. the invention utilizes nano SiO 2 The particles are used as a toughening agent, and the nano SiO is used 2 The epoxy resin-based composite propping agent is uniformly distributed in and on the surface of the epoxy resin-based composite propping agent and is connected with the matrix of the epoxy resin-based composite propping agent through chemical bonds, so that the toughness of the epoxy resin-based composite propping agent can be remarkably improved, the breakage rate of the epoxy resin-based composite propping agent is reduced, and the breakage rate is less than or equal to 3.8 percent in an indoor experiment test under the pressure of 28 MPa.
Drawings
Fig. 1 is a schematic structural diagram of an epoxy resin-based composite proppant according to an embodiment of the invention.
FIG. 2 is an enlarged view of a cross-section of an epoxy resin-based composite proppant according to an embodiment of the present invention.
FIG. 3 is a schematic diagram showing the elemental distribution of a cross-section of an epoxy resin-based composite proppant according to an embodiment of the present invention.
FIG. 4 is a graph showing the particle size distribution of an epoxy resin-based composite proppant at different stirring rates according to an embodiment of the present invention.
FIG. 5 is an epoxy-modified epoxy-based composite proppant of an embodiment of the present inventionNano SiO 2 Schematic representation of the particles.
FIG. 6 shows amino-modified nano SiO of an epoxy resin-based composite proppant according to an embodiment of the present invention 2 Schematic representation of the particles.
FIG. 7 is a schematic diagram of the chemical reaction between the epoxy resin and the amine curing agent and the process of forming a three-dimensional structure according to an embodiment of the present invention.
FIG. 8 shows SiO in an embodiment of the present invention 2 Schematic of the chemical reaction between the epoxy or amino groups on the surface of the nanoparticles and the epoxy resin matrix.
FIG. 9 shows the particle size distribution of the epoxy resin-based composite proppant at a rotation speed of 600r/min in the example of the invention.
FIG. 10 shows the particle size distribution of the epoxy resin-based composite proppant at a rotation speed of 800r/min in the example of the invention.
Reference numerals: 1-nano SiO 2 Particles, 2-epoxy resin matrix.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present disclosure, the definition of the term provided in the present disclosure controls.
It should be noted that the implementation conditions used in the examples can be further adjusted according to the specific experimental environment, and the implementation conditions not mentioned are generally the conditions in the routine experiments. The preparation methods mentioned in the present invention are all conventional methods unless otherwise specified.
As shown in figure 1, the epoxy resin-based composite proppant comprises an epoxy resin matrix 2 and nano SiO uniformly distributed in the epoxy resin matrix 2 2 Particle 1, the nano SiO 2 The surface of the particle 1 is modified by amino or epoxy, and is connected with the epoxy resin matrix 2 through chemical bonds.
The invention utilizes nano SiO 2 The particles are used as a toughening agent, and nano SiO is added 2 The epoxy resin-based composite proppant is uniformly distributed in and on the surface of the epoxy resin-based composite proppant and is connected with the matrix of the epoxy resin-based composite proppant through chemical bonds, so that the toughness of the epoxy resin-based composite proppant can be remarkably improved, and the breakage rate of the epoxy resin-based composite proppant is reduced.
As shown in FIG. 2, the particle diameter of the epoxy resin matrix 2 is 60um to 5mm. The nano SiO 2 The particle diameter of the particle 1 is 5nm to 500 nm.
As shown in FIG. 3, the element distribution diagram of C, N, O and Si of the section of the epoxy resin-based composite proppant can be determined by the element distribution diagram of Si in the section of the proppant, and the nanometer SiO is 2 The particles are uniformly dispersed in the proppant with the epoxy resin as the matrix.
The breaking rate of the epoxy resin-based composite proppant is less than or equal to 3.8 percent in an indoor experimental test under the pressure of 28 MPa.
Indoor test shows that under the pressure of 28MPa, the nano SiO 2 The fracture rate of the toughened epoxy resin-based composite proppant is less than or equal to 3.8 percent, while the fracture rate of the pure epoxy resin proppant is 15.2 percent. It can be seen that the proppant is made by nano SiO in comparison with pure epoxy resin proppant 2 The toughness of the particle toughened epoxy resin-based composite proppant is obviously improved.
A preparation method of an epoxy resin-based composite propping agent comprises the following steps:
s1: mixing nano SiO 2 The surface modification of the particles comprises the following specific processes:
according to the weight portion, 0.1 to 1 portion of nano SiO 2 Drying the particles at 90-120 ℃ for 10-36 h, adding 70-90 parts of toluene solvent, then adding 10-20 parts of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 5-20 min, stirring, heating to 100-130 ℃, continuously reacting for 12-36h, after the reaction is finished, washing with alcohol, and centrifugally drying to obtain white powdery amino or epoxy-modified SiO 2 A nanoparticle;
s2: the preparation method of the epoxy resin emulsion comprises the following specific steps:
s21: adding 1 to 10 parts by weight of diluent into 10 to 40 parts by weight of epoxy resin, and stirring and diluting for later use;
s22: according to the parts by weight, sequentially stirring 38.9 to 87.99 parts of deionized water, 0.5 to 6 parts of emulsifier, 0.5 to 5 parts of NaOH and 0.01 to 0.1 part of organic silicon defoamer at 30 to 90 ℃, adding the diluted epoxy resin in S21, and continuously stirring to prepare an epoxy resin emulsion;
s3: 0.001 to 0.1 part of modified nano SiO by weight 2 The particles, 10 to 30 parts of curing agent and 0.5 to 2 parts of curing accelerator are sequentially added into 67.9 to 89.499 parts of epoxy resin emulsion, stirred, stood and cured to obtain the nano SiO 2 The particles are uniformly distributed in an epoxy resin matrix generated after the curing reaction, and the epoxy resin-based composite proppant is obtained.
In the practical use process, the step S1 is to use nano SiO 2 The reaction schematic diagrams of the surface modification of the particles are shown in fig. 5 and 6, and fig. 5 shows epoxy-modified nano SiO 2 Principle of particle reaction, FIG. 6 is amino-modified nano-SiO 2 Particle reaction principle; the addition of the diluent in the step S21 can reduce the viscosity of the epoxy resin, improve the dispersibility of the epoxy resin in water, and facilitate the curing into balls, and the use of the deionized water in the step S22 can avoid the interference of impurity ions in tap water. The emulsifier can reduce the tension of an oil-water interface, is beneficial to preparing emulsion, naOH plays a role in regulating the pH value, is beneficial to curing epoxy resin, can generate a large amount of bubbles in the stirring process of the emulsion, and can avoid the generation of bubbles by using the defoaming agent, thereby being convenient for operation and actual production; the schematic process of the epoxy resin curing reaction in step S3 and the formation of the three-dimensional network structure is shown in fig. 7.
In the step S1, the silane coupling agent is one of γ - (2, 3-epoxypropoxy) propyltrimethoxysilane and γ -aminopropyltriethoxysilane. SiO with surface modified by epoxy or amino 2 The nanoparticles can chemically react with the epoxy matrix to chemically bond with the matrix, the reaction mechanism of which is shown in fig. 8.
In the step S2, the diluent is one of n-butyl glycidyl ether, ethyl acetate, and acetone.
In the step S2, the emulsifier is one of alkylphenol ethoxylates and lauramidopropyl hydroxysulfobetaine.
In the step S3, the modified nano SiO is treated 2 Adding the particles, the curing agent and the curing accelerator into the epoxy resin emulsion, stirring at the temperature of 40-80 ℃ and the stirring speed of 600-1200 r/min for 5-25 min, and then stirring or standing at the stirring speed of 100-300 r/min for 2 h.
In practical use, as shown in fig. 4, the particle size of the epoxy resin-based composite proppant can be effectively controlled by the speed of the high-speed stirring stage, and the particle size of the epoxy resin-based composite proppant can be controlled between 60 μm and 5mm by adopting different stirring speeds.
In the step S3, the curing agent is one of aliphatic amine curing agents tetraethylenepentamine and divinylpropylamine.
In the step S3, the curing accelerator is one of 2,4, 6-tris (dimethylaminomethyl) phenol, diethylenetriamine, and triethylenetetramine.
Example 1
The preparation method of the epoxy resin-based composite proppant is adopted to prepare the epoxy resin-based composite proppant, and the specific process comprises the following steps:
s1: nano SiO2 2 Surface modification of the particles:
0.5g of nano SiO 2 Drying at 105 ℃ for 24 hours, adding the mixture into a 250 mL round-bottom flask, adding 70 g of toluene solvent, then adding 10g of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 10 min, stirring, heating to 110 ℃, continuously reacting for 24 hours, after the reaction is finished, washing with alcohol, centrifuging for 3 times, and drying to obtain white powdery amino or epoxy modified SiO2 nanoparticles;
s2: preparation of epoxy resin emulsion:
adding 12g of epoxy resin (trade name: E-51) into 2.5 g of diluent ethyl acetate for standby, then sequentially adding 50 g of deionized water, 1g of emulsifier alkylphenol polyoxyethylene ether (OP-10), 2g of NaOH and 0.05g of organic silicon defoamer into a 200 mL polytetrafluoroethylene beaker, uniformly stirring the mixture at 40 ℃, adding the diluted epoxy resin into the system, and continuously stirring to prepare epoxy resin emulsion;
s3: nano SiO2 2 Preparing a toughened epoxy resin-based composite proppant:
0.05g of nano SiO prepared in the step S1 2 And adding 8g of fatty amine curing agent tetraethylenepentamine and 0.5g of curing accelerator diethylenetriamine into a beaker, stirring uniformly, adding the mixture into the epoxy emulsion prepared by S2, stirring at a high speed of 600r/min for 5 min at 40 ℃, stirring at a low speed of 200r/min or standing for 2h, and completely curing the epoxy resin to obtain the white epoxy resin-based composite proppant particles. Stirring at 600r/min to obtain proppant with average particle size of 1790 μm and particle size distribution shown in FIG. 9.
Example 2
The preparation method of the epoxy resin-based composite proppant is adopted to prepare the epoxy resin-based composite proppant, and the specific process comprises the following steps:
s1: surface modification of nano SiO2 particles:
drying 500 mg of nano SiO2 at 105 ℃ for 24 h, adding the nano SiO2 into a 250 mL round-bottom flask, adding 80 mL of toluene solvent, then adding 10 mL of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 10 min, stirring, heating to 110 ℃, continuously reacting for 24 h, after the reaction is finished, washing with alcohol, centrifuging for 3 times, and drying to obtain white powdery amino or epoxy modified SiO2 nano particles;
s2: preparation of epoxy resin emulsion:
12g of an epoxy resin, trade name: e-51, adding 2.5 g of diluent ethyl acetate for later use, then sequentially adding 50 g of deionized water, 1g of OP-10 emulsifier, 2g of NaOH and 0.05g of organic silicon defoamer into a 200 mL polytetrafluoroethylene beaker, uniformly stirring the mixture at 40 ℃, adding the diluted epoxy resin into the system, and continuing to stir to prepare epoxy resin emulsion;
s3: preparing the nano SiO2 toughened epoxy resin-based composite proppant:
and (2) adding 0.05g of nano SiO2 prepared in the step (S1) into a beaker, sequentially adding 8g of fatty amine curing agent tetraethylenepentamine and 0.5g of curing accelerator diethylenetriamine, uniformly stirring, adding the mixture into the epoxy emulsion prepared in the step (S2), stirring at a high speed of 800r/min for 5 min at the temperature of 40 ℃, stirring at a low speed of 200r/min or standing for 2h, and completely curing the epoxy resin to obtain the white epoxy resin-based composite proppant particles. Stirring at high speed of 800r/min to obtain average particle size of 1190 μm, and particle size distribution shown in FIG. 10.
As can be seen from examples 1 and 2, the particle size of the epoxy resin-based composite proppant can be effectively controlled by the speed of the S3 high-speed stirring stage, and the particle size of the epoxy resin-based composite proppant can be controlled between 60 μm and 5mm by adopting different stirring speeds. Examples 3 and 4 further illustrate the effect of the high speed agitation stage rate on the particle size of the resulting proppant in the S3 step, with the remaining preparation conditions being the same as in examples 1 and 2.
TABLE 1 Effect of agitation Rate on particle size of the resulting proppants
| Examples | Example 1 | Example 2 | Example 3 | Example 4 |
| Stirring speed (r/min) | 600 | 800 | 1000 | 1200 |
| Average particle diameter (μm) | 1790 | 1190 | 1772 | 1643 |
| Maximum particle size (. Mu.m) | 4583 | 2368 | 4219 | 4826 |
| Minimum particle size (. Mu.m) | 72 | 62 | 83 | 70 |
Indoor tests on the epoxy resin-based composite proppants of examples 1 to 4 show that the nano SiO is present under the pressure of 28MPa 2 The breaking rate of the toughened epoxy resin-based composite proppant is less than or equal to 3.8 percent.
Example 5
This example further illustrates the preparation of an epoxy resin-based composite proppant, which comprises the following steps:
s1: nano SiO2 2 Surface modification of the particles:
0.5g of nano SiO 2 Drying at 100 ℃ for 24 hours, adding the mixture into a 250 mL round-bottom flask, adding 70 g of toluene solvent, then adding 10g of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 10 min, stirring, heating to 110 ℃, continuously reacting for 24 hours, after the reaction is finished, washing with alcohol, centrifuging for 3 times, and drying to obtain white powdery amino or epoxy modified SiO2 nanoparticles;
s2: preparation of epoxy resin emulsion:
adding 10g of epoxy resin (trade name: E-51) into 2.5 g of diluent ethyl acetate for standby, then sequentially adding 50 g of deionized water, 1g of emulsifier alkylphenol polyoxyethylene (OP-10), 2g of NaOH and 0.05g of organic silicon defoamer into a 200 mL polytetrafluoroethylene beaker, uniformly stirring the mixture at 50 ℃, adding the diluted epoxy resin into the system, and continuously stirring to prepare epoxy resin emulsion;
s3: preparing the nano SiO2 toughened epoxy resin-based composite proppant:
and (2) adding 0.05g of nano SiO2 prepared in the step (S1) into a beaker, sequentially adding 10g of fatty amine curing agent divinyl propylamine and 0.8g of curing accelerator divinyl triamine, uniformly stirring, adding the mixture into the epoxy emulsion prepared in the step (S2), stirring at a high speed of 600r/min for 10 min at a temperature of 60 ℃, then stirring at a low speed of 200r/min or standing for 2h, and completely curing the epoxy resin to obtain the white epoxy resin-based composite proppant particles.
Example 6
This example, a comparative example to example 5, is presented to illustrate the effect of diluent dosage on proppant preparation as follows:
s1: nano SiO 2 Surface modification of the particles:
0.5g of nano SiO 2 Drying at 100 ℃ for 24 h, adding the mixture into a 250 mL round-bottom flask, adding 70 g of toluene solvent, then adding 10g of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 10 min, stirring, heating to 110 ℃, continuously reacting for 24 h, after the reaction is finished, washing with alcohol, centrifuging for 3 times, and drying to obtain white powder amino or epoxy-modified SiO 2 A nanoparticle;
s2: preparation of epoxy resin emulsion:
adding 10g of epoxy resin (trade name: E-51) into 0.25 g of diluent ethyl acetate for standby, then sequentially adding 50 g of deionized water, 1g of emulsifier alkylphenol polyoxyethylene (OP-10), 2g of NaOH and 0.05g of organic silicon defoamer into a 200 mL polytetrafluoroethylene beaker, uniformly stirring the mixture at 50 ℃, adding the diluted epoxy resin into the system, and continuously stirring to prepare epoxy resin emulsion;
S3: nano SiO 2 Preparing a toughened epoxy resin-based composite proppant:
0.05g of nano SiO prepared in the step S1 2 And adding the mixture into a beaker, sequentially adding 10g of fatty amine curing agent divinyl propylamine and 0.8g of curing accelerator divinyl triamine, uniformly stirring, adding the mixture into the epoxy emulsion prepared by the S2, stirring at a high speed of 600r/min for 10 min at the temperature of 60 ℃, and stirring at a low speed of 200r/min or standing for 2h to obtain a cementing material which is connected into a piece, wherein no propping agent particles are generated.
Comparing example 5 with example 6, it is found that the content of the diluent below the present invention is difficult to disperse the epoxy resin in the system, resulting in insufficient reaction and failure of the preparation process, and when the content of the diluent is above the range of the present invention, the obtained proppant is soft particles, because the distance between epoxy molecules is increased due to excessive diluent, the reaction probability between the epoxy molecules and the curing agent is reduced, and the crosslinking density of the proppant is further reduced.
Example 7
This example, a comparative example to example 5, is presented to illustrate the effect of emulsifier dosage on proppant preparation as follows:
s1: nano SiO 2 Surface modification of the particles:
0.5g of nano SiO 2 Drying at 100 ℃ for 24 h, adding the mixture into a 250 mL round-bottom flask, adding 70 g of toluene solvent, then adding 10g of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 10 min, stirring, heating to 110 ℃, continuously reacting for 24 h, after the reaction is finished, washing with alcohol, centrifuging for 3 times, and drying to obtain white powdery amino or epoxy-modified SiO2 nanoparticles;
s2: preparation of epoxy resin emulsion:
adding 10g of epoxy resin (trade name: E-51) into 2.5 g of diluent ethyl acetate for standby, then sequentially adding 50 g of deionized water, 0.2g of emulsifier alkylphenol polyoxyethylene (OP-10), 2g of NaOH and 0.05g of organic silicon defoamer into a 200 mL polytetrafluoroethylene beaker, uniformly stirring the mixture at 50 ℃, adding the diluted epoxy resin into the system, and continuously stirring to prepare epoxy resin emulsion;
s3: nano SiO 2 Preparing a toughened epoxy resin-based composite proppant:
0.05g of nano SiO prepared in the step S1 2 And adding the mixture into a beaker, sequentially adding 10g of fatty amine curing agent divinyl propylamine and 0.8g of curing accelerator divinyl triamine, uniformly stirring, adding the mixture into the epoxy emulsion prepared by the S2, stirring at a high speed of 600r/min for 10 min at the temperature of 60 ℃, and then stirring at a low speed of 200r/min or standing for 2h to obtain agglutinates with different sizes, wherein propping agent particles are not generated.
It was found that, when the content of the emulsifier in comparative example 5 and example 7 is lower than that in the present invention, it is difficult to prepare an epoxy resin emulsion with good dispersibility, and the epoxy emulsion particles are bonded together by coalescence reaction at the S3 proppant preparation stage, and resin particles with mechanical strength are not formed.
Example 8
This example, a comparative example to example 5, is presented to illustrate the effect of curing temperature on proppant preparation as follows:
s1: nano SiO 2 Surface modification of the particles:
0.5g of nano SiO 2 Drying at 100 ℃ for 24 h, adding the mixture into a 250 mL round-bottom flask, adding 70 g of toluene solvent, then adding 10g of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 10 min, stirring, heating to 110 ℃, continuously reacting for 24 h, after the reaction is finished, washing with alcohol, centrifuging for 3 times, and drying to obtain white powder amino or epoxy-modified SiO 2 A nanoparticle;
s2: preparation of epoxy resin emulsion:
adding 10g of epoxy resin (trade name: E-51) into 2.5 g of diluent ethyl acetate for standby, then sequentially adding 50 g of deionized water, 1g of emulsifier alkylphenol polyoxyethylene (OP-10), 2g of NaOH and 0.05g of organic silicon defoamer into a 200 mL polytetrafluoroethylene beaker, uniformly stirring the mixture at 50 ℃, adding the diluted epoxy resin into the system, and continuing stirring to prepare epoxy resin emulsion;
s3: nano SiO2 2 Toughening ofThe preparation of the epoxy resin-based composite proppant comprises the following steps:
0.05g of nano SiO prepared in the step S1 2 And adding the mixture into a beaker, sequentially adding 10g of fatty amine curing agent divinyl propylamine and 0.8g of curing accelerator divinyl triamine, uniformly stirring, adding the mixture into the epoxy emulsion prepared by the S2, stirring at a high speed of 600r/min for 10 min at the temperature of 30 ℃, and then stirring at a low speed of 200r/min or standing for 2h to obtain the whole cementing material, wherein no proppant particles are generated.
Comparing example 5 and example 8, it was found that below the cure temperature of the present invention, it is difficult to form proppant particles. This is because the reaction rate between the epoxy resin and the curing agent is slow at a low consolidation temperature, and a hard film is not rapidly formed on the surface of the latex particles, so that the latex particles are bonded to each other, and finally a block-shaped latex is formed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. An epoxy resin-based composite proppant is characterized in that: comprises an epoxy resin matrix and nano SiO uniformly distributed in the epoxy resin matrix 2 Particles of the nano SiO 2 The surface of the particle is modified by amino or epoxy group, and is connected with the epoxy resin matrix through chemical bonds.
2. The epoxy resin-based composite proppant of claim 1, wherein: the particle size range of the epoxy resin matrix is 60um to 5mm, and the nano SiO is 2 The particle size range of the particles is 5nm to 500 nm.
3. The epoxy resin-based composite proppant as set forth in claim 1, wherein: the breaking rate of the epoxy resin-based composite propping agent is less than or equal to 3.8 percent in an indoor experimental test under the pressure of 28 Mpa.
4. The method for preparing any one of the epoxy resin-based composite proppants of claims 1-3, wherein: the method comprises the following steps:
s1: mixing nano SiO 2 The surface modification of the particles comprises the following specific processes:
according to the parts by weight, 0.1 to 1 part of nano SiO 2 Drying the particles at 90-120 ℃ for 10-36 h, adding 70-90 parts of toluene solvent, then adding 10-20 parts of epoxy or amino-containing silane coupling agent, ultrasonically dispersing for 5-20 min, stirring, heating to 100-130 ℃, continuously reacting for 12-36h, after the reaction is finished, washing with alcohol, and centrifugally drying to obtain white powdery amino or epoxy-modified SiO 2 A nanoparticle;
s2: the preparation method of the epoxy resin emulsion comprises the following specific steps:
s21: adding 1 to 10 parts by weight of diluent into 10 to 40 parts by weight of epoxy resin, and stirring and diluting for later use;
s22: stirring 38.9 to 87.99 parts of deionized water, 0.5 to 6 parts of emulsifier, 0.5 to 5 parts of NaOH and 0.01 to 0.1 part of organic silicon defoamer uniformly at the temperature of 30 to 90 ℃ in sequence by weight, adding the diluted epoxy resin in S21, and continuously stirring to prepare an epoxy resin emulsion;
s3: 0.001 to 0.1 part of modified nano SiO by weight 2 The particles, 10 to 30 parts of curing agent and 0.5 to 2 parts of curing accelerator are sequentially added into 67.9 to 89.499 parts of epoxy resin emulsion, stirred, stood and cured to obtain the nano SiO 2 The particles are uniformly distributed in an epoxy resin matrix generated after the curing reaction to obtain the epoxy resin-based composite proppant.
5. The method for preparing any one of the epoxy resin-based composite proppants of claim 4, wherein: in the step S1, the silane coupling agent is one of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and gamma-aminopropyl triethoxy silane.
6. The method for preparing any one of the epoxy resin-based composite proppants according to claim 4, wherein: in the step S2, the diluent is one of n-butyl glycidyl ether, ethyl acetate, and acetone.
7. The method for preparing any one of the epoxy resin-based composite proppants according to claim 4, wherein: in the step S2, the emulsifier is one of alkylphenol ethoxylates and lauramidopropyl hydroxysulfobetaine.
8. The method for preparing any one of the epoxy resin-based composite proppants of claim 4, wherein: in the step S3, the modified nano SiO is treated 2 Adding the particles, the curing agent and the curing accelerator into the epoxy resin emulsion, stirring at the temperature of 40-80 ℃ and the stirring speed of 600-1200 r/min for 5-25 min, and then stirring or standing at the stirring speed of 100-300 r/min for 2 h.
9. The method for preparing any one of the epoxy resin-based composite proppants according to claim 4, wherein: in the step S3, the curing agent is one of aliphatic amine curing agents tetraethylenepentamine and divinylpropylamine.
10. The method for preparing any one of the epoxy resin-based composite proppants according to claim 4, wherein: in the step S3, the curing accelerator is one of 2,4, 6-tris (dimethylaminomethyl) phenol, diethylenetriamine, and triethylenetetramine.
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