阅读说明：本技术 一种压裂用支撑剂的制备方法 (Preparation method of proppant for fracturing ) 是由 熊帆 熊鹰 于 2021-11-10 设计创作，主要内容包括：本发明涉及石油、天然气及页岩气等流体矿产开采技术领域,具体公开了一种压裂用支撑剂的制备方法,包括以下步骤：S1、制作水相；去离子水中加入分散剂和阻聚剂,混合均匀则形成水相；S2、制作油相；取共聚单体100份、过氧化引发剂0.5-7份、二茂铁修饰的二氧化硅纳米颗粒0.04-10份混合均匀形成油相,其中共聚单体包括苯乙烯和二乙烯苯；S3、制作液滴状支撑剂；在水相搅拌状态下加入油相,形成液滴状支撑剂；S4、熟化并固化支撑剂；S5、对S4步骤得到的固态支撑剂进行干燥得到压裂用支撑剂。本方法制得的支撑剂颗粒强度和最大使用温度均大幅度提高,解决了现有技术中在深井中压裂的支撑剂存在的支撑剂破碎和支撑剂粘连的问题。(The invention relates to the technical field of mining of fluid mineral products such as petroleum, natural gas, shale gas and the like, and particularly discloses a preparation method of a proppant for fracturing, which comprises the following steps: s1, preparing a water phase; adding a dispersant and a polymerization inhibitor into deionized water, and uniformly mixing to form a water phase; s2, preparing an oil phase; uniformly mixing 100 parts of comonomer, 0.5-7 parts of peroxidation initiator and 0.04-10 parts of ferrocene-modified silicon dioxide nano-particles to form an oil phase, wherein the comonomer comprises styrene and divinylbenzene; s3, preparing a liquid drop-shaped proppant; adding an oil phase under the stirring state of a water phase to form a liquid drop-shaped proppant; s4, curing and solidifying the propping agent; and S5, drying the solid propping agent obtained in the step S4 to obtain the propping agent for fracturing. The strength and the maximum use temperature of the proppant particles prepared by the method are both greatly improved, and the problems of proppant crushing and proppant adhesion of the proppant fractured in a deep well in the prior art are solved.)

1. The preparation method of the proppant for fracturing is characterized by comprising the following steps:

s1, preparing a water phase; adding a dispersant and a polymerization inhibitor into deionized water, and uniformly mixing to form a water phase;

s2, preparing an oil phase; uniformly mixing 100 parts of comonomer, 0.5-7 parts of peroxide initiator and 0.04-10 parts of ferrocene-modified silicon dioxide to form an oil phase, wherein the ferrocene-modified silicon dioxide adopts nanoparticles, and the comonomer comprises styrene and divinylbenzene;

s3, preparing a liquid drop-shaped proppant; adding an oil phase under the stirring state of a water phase to form a liquid drop-shaped proppant;

s4, curing and solidifying the propping agent; continuously stirring and heating the formed liquid drop-shaped proppant until the proppant is cured to form a solid state;

and S5, drying the solid propping agent obtained in the step S4 to obtain the propping agent for fracturing.

2. The method for preparing the proppant for fracturing as set forth in claim 1, characterized in that: the ferrocene modified silicon dioxide is prepared by reacting acyl chlorinated silicon dioxide and methyl alcohol ferrocene.

3. The method for producing the proppant for fracturing as set forth in claim 2, characterized in that: the acyl-chlorinated silica and the methanol ferrocene are reacted by taking dichloromethane as a solvent and adding a catalyst to promote the reaction.

4. The method for producing the proppant for fracturing as set forth in claim 3, characterized in that: after the reaction of the acyl chloride silicon dioxide and the methyl ferrocene is finished, removing dichloromethane through reduced pressure suction filtration, removing triethylamine through ethanol washing, and obtaining the silicon dioxide modified by the methyl ferrocene after water washing and drying.

5. The method for producing the proppant for fracturing as set forth in claim 2, characterized in that: the acyl-chlorinated silicon dioxide is obtained by reacting carboxylated nano-silicon dioxide with thionyl chloride.

6. The method for producing the proppant for fracturing as set forth in claim 5, characterized in that: heating the acyl chlorinated silicon dioxide in an oil bath during preparation, and removing excessive thionyl chloride through reduced pressure distillation after the reaction of the nano silicon dioxide and thionyl chloride is finished to obtain the acyl chlorinated silicon dioxide.

7. The method for preparing the proppant for fracturing as set forth in claim 1, characterized in that: the comonomer also comprises an auxiliary monomer, wherein the auxiliary monomer comprises at least one of triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, the auxiliary monomer comprises three-claw type active groups, and each active group is provided with a C ═ C double bond; wherein the auxiliary monomer accounts for 1-15% of the total amount of the comonomer, divinylbenzene accounts for 1-50% of the total amount of the comonomer, and styrene accounts for 35-98% of the total amount of the comonomer.

8. The method for producing the proppant for fracturing as set forth in claim 7, characterized in that: the auxiliary monomer in the comonomer accounts for 2-10% of the total amount of the comonomer, divinylbenzene accounts for 7-40% of the total amount of the comonomer, and styrene accounts for 50-93% of the total amount of the comonomer.

9. The method for preparing the proppant for fracturing as set forth in claim 1, characterized in that: the peroxide initiator comprises 0.3-2 parts of low-temperature peroxide initiator and 0.2-5 parts of high-temperature peroxide initiator.

10. The method for preparing the proppant for fracturing as set forth in claim 9, characterized in that: the low-temperature peroxide initiator comprises at least one of benzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, dibutyl peroxydicarbonate, dilauroyl peroxide and didecanoyl peroxide; the high-temperature peroxide initiator comprises at least one of tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy2-ethylhexyl carbonate, tert-butyl peroxyacetate, 4-butyl bis (tert-butylperoxy) valerate, tert-butyl peroxybenzoate, dicumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, tert-butylperoxycumene, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, di-tert-butyl peroxide, p-menthane hydroperoxide, tert-amyl hydroperoxide and tert-butyl hydroperoxide.

Technical Field

The invention relates to the technical field of mining of fluid mineral products such as petroleum, natural gas, shale gas and the like, in particular to a preparation method of a propping agent for fracturing.

Background

Proppant is a material commonly used in fracturing operations, such as is commonly used in oil recovery processes. The proppant is filled into the rock stratum fractures of the low-permeability deposit to carry out high-closure fracturing treatment so as to support the fractures to be closed without stress release and lead oil and gas to be collected from fracture channels, thereby maintaining the high flow conductivity of the oil and the gas, increasing the yield of the oil and the gas, prolonging the service life of the oil and the gas wells and improving the economic benefits of oil and gas extraction.

The proppant used in the fracturing process at home and abroad at present mainly comprises quartz sand and ceramsite, wherein the quartz sand is a commonly used proppant at present due to low price, but the proppant has the following defects: the specific gravity is large, the viscosity of the fluid is large, the pumping pressure is high, and the energy consumption is large when the proppant is transmitted in the fracturing process; low roundness and sphericity, unsmooth surface and serious abrasion to equipment.

The Chinese patent with the patent application number of 201410181659.1 discloses a polystyrene proppant which comprises the following raw materials in parts by weight: 100 parts of monomer, 0.11-8 parts of initiator, 2-10 parts of inorganic dispersant, 2-7 parts of organic dispersant, 0.2-1 part of reinforcing agent, 200-500 parts of deionized water and 0.8-3 parts of surfactant; the monomer is styrene or a mixture of styrene and divinylbenzene; the mass of divinylbenzene in the monomer is less than or equal to 60 percent of the mass of styrene. The technical scheme has the advantages of low specific gravity, no static electricity and the like.

However, when the proppant of the technical scheme is applied to deep well fracturing, the proppant is broken and generates a large amount of fragments, and the fragments migrate in the fracture and block a flow channel, so that the flow conductivity of the fracture is reduced, and the oil and gas yield is reduced; meanwhile, the proppant is pressed and adhered under the well, so that gaps are completely blocked, and crude oil cannot seep out.

Disclosure of Invention

The invention aims to provide a preparation method of a fracturing proppant, which aims to solve the problems of proppant breakage and proppant adhesion of the fracturing proppant in a deep well in the prior art.

In order to achieve the above object, the basic scheme of the invention is as follows:

a preparation method of a proppant for fracturing comprises the following steps:

s1, preparing a water phase; adding a dispersant and a polymerization inhibitor into deionized water, and uniformly mixing to form a water phase;

s2, preparing an oil phase; uniformly mixing 100 parts of comonomer, 0.5-7 parts of peroxide initiator and 0.04-10 parts of ferrocene-modified silicon dioxide to form an oil phase, wherein the ferrocene-modified silicon dioxide adopts nanoparticles, and the comonomer comprises styrene and divinylbenzene;

s3, preparing a liquid drop-shaped proppant; adding an oil phase under the stirring state of a water phase to form a liquid drop-shaped proppant;

s4, curing and solidifying the propping agent; continuously stirring and heating the formed liquid drop-shaped proppant until the proppant is cured to form a solid state;

and S5, drying the solid propping agent obtained in the step S4 to obtain the propping agent for fracturing.

Compare the beneficial effect in prior art:

in order to obtain the proppant of the scheme, the inventor conducts analysis and research on the existing proppant, and finds that the particle strength of the existing proppant is only about 65N, so that the proppant is easy to break due to insufficient pressure resistance and further generates a large amount of fragments; the maximum use temperature of the existing proppant is only about 120 ℃, so that the temperature resistance is not high, the proppant is adhered after being flattened in a well with high temperature, gaps are completely blocked, and crude oil cannot seep out. According to the scheme, a polymer with a cross-linked network structure is formed between comonomers through a peroxide initiator, and the ferrocene modified silicon dioxide is connected to the surface of the silicon dioxide in a covalent bond mode, so that the silicon dioxide modified by the covalent bond is not easy to fall off like physical adsorption, and the ferrocene group has excellent compatibility with the comonomer, so that the ferrocene modified silicon dioxide nanoparticles can be dispersed in a large number of grid gaps of the network structure formed by crosslinking of the comonomers uniformly, a supporting effect on the polymer is achieved, the strength of the supporting agent is improved, and the compressive strength and the heat resistance of the supporting frame are greatly improved; on the other hand, the ferrocene group in the ferrocene-modified silicon dioxide nano-particle can also enhance the heat resistance and the compressive strength of the polymer; the heat resistance and the compressive strength of the polymer are further enhanced by the synergistic effect of the polymer and the polymer, so that the particle strength of the proppant prepared by the scheme reaches more than 120N, the particle strength is doubled, and meanwhile, the maximum use temperature is also increased to more than 130 ℃, and further, the problem of crushing in deep well fracturing and the problem of adhesion between the proppants cannot occur in the proppant of the scheme; in addition, the ferrocene group can absorb ultraviolet rays, so that the polymer can be effectively prevented from aging, and the service life of the proppant is further prolonged.

Further, the ferrocene modified silicon dioxide is prepared by reacting acyl chloride silicon dioxide and methyl alcohol ferrocene.

Has the advantages that: the scheme ensures that the preparation method of the ferrocene modified silicon dioxide is simple and has low requirement on a preparation device, and the preparation cost is reduced.

Further, the acyl-chlorinated silica and the methanol ferrocene are reacted by taking dichloromethane as a solvent and adding a catalyst to promote the reaction.

Has the advantages that: the addition of dichloromethane avoids splashing and explosion phenomena in the reaction process, and the existence of the catalyst ensures that the whole reaction process is uniform and rapid.

Further, after the reaction of the acyl chloride silicon dioxide and the methyl alcohol ferrocene is finished, removing dichloromethane through decompression and suction filtration, removing triethylamine through ethanol washing, and obtaining the silicon dioxide modified by the ferrocene after water washing and drying.

Has the advantages that: the method can improve the purity of the prepared ferrocene modified silicon dioxide.

Further, the acyl-chlorinated silicon dioxide is obtained by reacting carboxylated nano-silicon dioxide with thionyl chloride.

Has the advantages that: the scheme ensures that the preparation method of the acyl chlorinated silicon dioxide is simple, has low requirement on a preparation device and reduces the preparation cost.

Further, heating the acyl chlorinated silicon dioxide in an oil bath during the preparation process, and removing excessive thionyl chloride through reduced pressure distillation after the reaction of the nano silicon dioxide and thionyl chloride is finished to obtain the acyl chlorinated silicon dioxide.

Has the advantages that: the method can improve the purity of the prepared acyl chloride silicon dioxide.

The comonomer further comprises an auxiliary monomer, wherein the auxiliary monomer comprises at least one of triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, the auxiliary monomer comprises three-claw type active groups, and each active group is provided with a C ═ C double bond; wherein the auxiliary monomer accounts for 1-15% of the total amount of the comonomer, divinylbenzene accounts for 1-50% of the total amount of the comonomer, and styrene accounts for 35-98% of the total amount of the comonomer.

Has the advantages that: when the scheme is adopted, if only divinylbenzene is taken as the crosslinking agent, the compressive strength and the heat resistance are relatively insufficient when the crosslinking degree is low, and the polymer becomes very brittle when the crosslinking degree is high, so that the compressive strength is relatively reduced; in the scheme, the auxiliary monomers comprise three-jaw active groups, each active group is provided with a C ═ C double bond, a certain steric hindrance is provided for the polymer through the three-jaw active groups with the C ═ C double bonds, the crosslinking degree is increased, the thermal motion of the three-dimensional reticular molecules of the polymer is limited (namely, the heat resistance and the compressive strength are improved), and meanwhile, on a local microcosmic level, a molecular chain has a certain moving space, so that the toughness is provided for the polymer; on the other hand, the ferrocene modified silicon dioxide nano-particles are filled in the molecular chain activity space on the local microcosmic, so that the activity space is supported, the deformation of the polymer due to toughness when the polymer is pressed is reduced, and the particle strength and the maximum use temperature of the proppant are further improved.

Furthermore, the auxiliary monomer in the comonomer accounts for 2-10% of the total amount of the comonomer, divinylbenzene accounts for 7-40% of the total amount of the comonomer, and styrene accounts for 50-93% of the total amount of the comonomer.

Has the advantages that: because the price of the auxiliary monomer is high, the scheme considers the contents of the other components in the auxiliary monomer and the comonomer, so that the preparation of the proppant can simultaneously consider low cost and high performance.

Further, the peroxide initiator comprises 0.3-2 parts of low-temperature peroxide initiator and 0.2-5 parts of high-temperature peroxide initiator.

Has the advantages that: when the scheme is adopted, the low-temperature peroxide initiator mainly enables styrene to form a preliminary cross-linking structure through divinylbenzene, and meanwhile, the low-temperature peroxide initiator can also promote the three-claw type active group to preliminarily cross-link the long-distance carbon chain in the polymer; the high-temperature peroxide initiator further crosslinks the long-distance carbon chains mainly through the three-claw type active groups, and simultaneously uniformly disperses the ferrocene modified silicon dioxide nanoparticles in the grid gaps of the polymer, thereby greatly increasing the compressive strength, heat resistance and toughness of the polymer.

Further, the low-temperature peroxide initiator comprises at least one of benzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, dibutyl peroxydicarbonate, dilauroyl peroxide and didecanoyl peroxide; the high-temperature peroxide initiator comprises at least one of tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy2-ethylhexyl carbonate, tert-butyl peroxyacetate, 4-butyl bis (tert-butylperoxy) valerate, tert-butyl peroxybenzoate, dicumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, tert-butylperoxycumene, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, di-tert-butyl peroxide, p-menthane hydroperoxide, tert-amyl hydroperoxide and tert-butyl hydroperoxide.

Drawings

FIG. 1 is a schematic view of a partial configuration of a capillary rheometer used in an embodiment of the invention to measure the maximum use temperature.

Detailed Description

The following is further detailed by way of specific embodiments:

reference numerals in the drawings of the specification include: the device comprises a charging barrel 1, a hollow channel 2, a screw 3 and a pressure rod 4.

A preparation method of a fracturing propping agent needs to use raw materials of the fracturing propping agent, the raw materials comprise an oil phase and a water phase, the water phase comprises deionized water, a dispersing agent and a polymerization inhibitor, the ratio of the water phase to the oil phase is 2-5, in the embodiment, the dispersing agent adopts gelatin, the polymerization inhibitor adopts methylene blue, and the components in the water phase are as follows:

TABLE 1-Water phase composition parameters Table

The oil phase comprises the following components in parts by weight: 100 parts of a comonomer, 0.5-7 parts of a peroxide initiator and 0.04-10 parts of ferrocene-modified silica, wherein the ferrocene-modified silica adopts nanoparticles with the particle size of less than 1000nm, the comonomer comprises styrene, divinylbenzene and an auxiliary monomer, the auxiliary monomer comprises at least one of triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, the auxiliary monomer comprises three-claw type active groups, and each active group has a C ═ C double bond, in the embodiment, the auxiliary monomer takes triallyl isocyanurate as an example; wherein the triallyl isocyanurate accounts for 1-15% of the total amount of the comonomer, the divinylbenzene accounts for 1-50% of the total amount of the comonomer, and the styrene accounts for 35-98% of the total amount of the comonomer; the preferable scheme of the comonomer is that triallyl isocyanurate accounts for 2-10% of the total amount of the comonomer, divinylbenzene accounts for 7-40% of the total amount of the comonomer, and styrene accounts for 50-93% of the total amount of the comonomer.

The peroxide initiator comprises 0.3-2 parts of low-temperature peroxide initiator and 0.2-5 parts of high-temperature peroxide initiator, and the low-temperature peroxide initiator is used for enabling styrene to form a primary crosslinking structure through divinylbenzene; the high temperature peroxide initiator is used to initiate the three-jaw type active group to further crosslink the long-distance carbon chain.

The low-temperature peroxide initiator comprises at least one of benzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, dibutyl peroxydicarbonate, dilauroyl peroxide and didecanoyl peroxide; in this example, benzoyl peroxide was used as the low temperature peroxide initiator.

The high-temperature peroxide initiator comprises at least one of tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy2-ethylhexyl carbonate, tert-butyl peroxyacetate, butyl 4, 4-bis (tert-butylperoxy) valerate, tert-butyl peroxybenzoate, dicumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, tert-butylperoxycumene, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, di-tert-butyl peroxide, p-menthane hydroperoxide, tert-amyl hydroperoxide and tert-butyl hydroperoxide; in this example dicumyl peroxide was used as the high temperature peroxide initiator.

The ferrocene-modified silicon dioxide nanometer can be prepared by reacting carboxylated nanometer silicon dioxide with thionyl chloride to obtain acyl-chlorinated silicon dioxide, and then reacting the acyl-chlorinated silicon dioxide with methanol ferrocene by taking triethylamine as a catalyst.

A preparation method of a proppant for fracturing comprises the following steps:

s1, preparing a water phase; taking the raw materials of the proppant, adding a dispersant and a polymerization inhibitor into deionized water, and uniformly mixing to form a water phase;

s2, preparing an oil phase; uniformly mixing 100 parts of comonomer, 0.5-7 parts of peroxidation initiator and 0.04-10 parts of ferrocene-modified silicon dioxide nano-particles to form an oil phase;

s3, preparing a liquid drop-shaped proppant; adding an oil phase under the stirring state of a water phase to form a liquid drop-shaped proppant;

s4, curing and solidifying the propping agent; continuously stirring and heating the formed liquid drop-shaped propping agent to 80 ℃, preserving heat for 2-8 hours, then continuously heating to 95-100 ℃, preserving heat for 7-10 hours, and obtaining cured solid propping agent;

and S5, filtering and drying the solid propping agent obtained in the step S4 to obtain the propping agent for fracturing.

The preparation method of the ferrocene-modified silicon dioxide in the embodiment comprises the following steps:

step one, 17.5g of carboxylated nano silicon dioxide and 10mL of thionyl chloride are added into a three-neck flask and ultrasonically dispersed for 30 min. Then heating in oil bath at 70 ℃, and stirring for reaction for 8-24 h. After the reaction is finished, the excessive thionyl chloride is removed by reduced pressure distillation, and the silicon dioxide of acyl chloride is obtained.

Step two, adding 7.5g of acyl-chlorinated silica, 0.1g of methanol ferrocene and 10mL of dichloromethane into a three-neck flask, and performing ultrasonic dispersion for 30 min. Then 0.1mL of triethylamine is added as a catalyst, the mixture is heated in an oil bath at 50 ℃ and stirred to react for 8 to 24 hours. And after the reaction is finished, carrying out vacuum filtration to remove dichloromethane, washing with ethanol to remove triethylamine, washing with water, and drying to obtain the ferrocene-modified silicon dioxide.

According to the above examples, the tests and comparative examples were carried out with varying parameters in the proppant, the specific test and comparative example parameters are shown in table 2 below, and the technical indices obtained for the tests and comparative examples are shown in table 3 below:

TABLE 2-test and comparative example parameter case Table

TABLE 3 technical index Table obtained for test and comparative example

It should be noted that the maximum service temperature indicated in table 3 above is not the glass transition temperature or thermal decomposition temperature of the polymer proppant, and the thermal decomposition temperature of the polymer is only representative of the resistance of the polymer to thermal cracking, and in fact the polymer proppant loses its practical service value long before reaching the thermal decomposition temperature; the glass transition temperature is the temperature corresponding to the transition of the polymer from the glassy state to the high elastic state, and is more indicative of the heat resistance of the polymer proppant than the thermal decomposition temperature. However, there are two problems that the polymer is stuck when the temperature is lower than the glass transition temperature by tens of degrees under pressure, and the use value as a proppant is lost, and the polymer proppant with good heat resistance has a high degree of crosslinking, so that the glass transition temperature cannot be measured. For this reason, an index of maximum use temperature is proposed herein, which is a more representative index of heat resistance of polymer proppants. The maximum service temperature test method comprises the steps of heating the propping agent, pressurizing the propping agent in a direct contact manner after heating, gradually increasing the pressure in the pressurizing process until the pressure reaches a specified pressure, maintaining the pressure for a period of time under the pressure, then releasing the pressure, loosening the bottom support of the propping agent, if the propping agent can completely and naturally fall or completely fall after being slightly touched, setting the temperature as the usable temperature, and repeating the test at a higher temperature until the propping agent is adhered into blocks, wherein the set temperature is the unusable temperature.

In the embodiment, the maximum service temperature test method specifically adopts a capillary rheometer model MLW-400, the capillary rheometer comprises a charging barrel 1 capable of heating and a pressure lever 4 capable of pressing into the charging barrel 1, a hollow channel 2 (diameter 1cm) is arranged in the center of the charging barrel 1, during test, a screw 3 is inserted into the hollow channel 2 of the charging barrel 1 to seal the bottom of the charging barrel 1, the screw 3 does not completely occupy the hollow channel 2, and a propping agent is conveniently placed in the charging barrel 1; then, 1cm of propping agent with the height of 1cm is filled in the hollow channel 2 of the charging barrel 1, the temperature is raised to the set temperature, the pressure is loaded to 4000N, the pressure is released after 1 hour, the bottom screw 3 is unscrewed, and if all the propping agent naturally falls from the hollow channel 2 of the charging barrel 1 or falls completely after being touched, the set temperature is the usable temperature; repeating the test at a higher temperature until the propping agents are adhered into blocks, wherein the set temperature is the unusable temperature; the maximum value of the usable temperature in the experiment is the maximum usable temperature; none of the commercially available polymeric proppants therein have a maximum service temperature of more than 120 ℃ using the test methods herein.

From the above examples, it can be seen that the particle strength of the proppant obtained in tests 1 to 9 is 120N at the lowest, and the maximum service temperature is 130 ℃ or higher, compared with the commercial polymer proppant, the particle strength and the maximum service temperature are both improved, especially, the particle strength of some tests is 178N, and the maximum service temperature is 200 ℃, so that the particle strength and the maximum service temperature of the existing proppant are greatly broken through, and the proppant of the present scheme cannot be broken in deep well fracturing and cannot be adhered to each other.

Comparative example 1 compared to run 5, which lacks ferrocene-modified silica nanoparticles and triallyl isocyanurate in the comonomer, comparative example 1 achieved a poorer effect than comparative example 5, which is a commercially available polymeric proppant.

Comparative example 2 compared to test 5, which lacks triallyl isocyanurate in the comonomer, the particulate strength and maximum service temperature of the proppant obtained in comparative example 2 were still greatly increased compared to comparative example 5, since the other materials of this example were retained.

Comparative example 3 lacks ferrocene-modified silica nanoparticles compared to test 5, and comparative example 3 achieves little difference from comparative example 5 of a commercially available polymeric proppant, and the importance of ferrocene-modified silica nanoparticles to proppant particle strength and maximum use temperature is demonstrated in conjunction with comparative example 2, comparative example 3, and test 5.

Compared with the experiment 5, the comparative example 4 has the advantages that the amount of dicumyl peroxide serving as a high-temperature peroxide initiator is completely replaced by benzoyl peroxide serving as a low-temperature peroxide initiator, and compared with the comparative example 5, the particle strength and the maximum use temperature of the proppant obtained in the comparative example 2 are still greatly improved.

The technical indexes described in the embodiments can be achieved by the following mechanism: the low-temperature peroxide initiator enables styrene to form a primary cross-linking structure through divinylbenzene, and meanwhile, the low-temperature peroxide initiator can also promote the three-claw type active groups to perform primary cross-linking on long-distance carbon chains in the polymer; auxiliary monomers of triallyl isocyanurate all have three-jaw active groups with C ═ C double bonds, certain steric hindrance is provided for polymers through the active groups, the crosslinking degree is increased, meanwhile, the thermal motion of three-dimensional network molecules of the polymers is limited (namely, the heat resistance and the compressive strength are improved), and meanwhile, on a local microcosmic view, molecular chains have certain activity spaces, and toughness is provided for the polymers; the high-temperature peroxide initiator further crosslinks the long-distance carbon chains mainly through three-claw type active groups; then, because the ferrocene structural unit of the ferrocene modified silicon dioxide is connected to the surface of the silicon dioxide in a covalent bond mode, the silicon dioxide modified by the covalent bond is not easy to fall off like physical adsorption, and the compatibility of the ferrocene group and the comonomer is excellent, so that the silicon dioxide nano-particles modified by the ferrocene can be dispersed in a large amount and uniformly in grid gaps of a net structure formed by crosslinking of the comonomer, a supporting effect is realized on a polymer, the strength of a propping agent is improved, and the compressive strength and the heat resistance of the supporting frame are greatly improved; on the other hand, the ferrocene group in the ferrocene-modified silicon dioxide nano-particle can also enhance the heat resistance and the compressive strength of the polymer; the synergistic effect of the two components further enhances the heat resistance, compressive strength and toughness of the polymer, so that the performance of the obtained proppant is greatly improved, and the proppant of the embodiment can not be broken in deep well fracturing and adhered between the proppants.

In addition, the ferrocene group can absorb ultraviolet rays, so that the polymer can be effectively prevented from aging, and the service life of the proppant is further prolonged.

The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.