CN110746956B - Self-suspension hydraulic fracturing coated proppant with targeting function and preparation and application thereof - Google Patents
Self-suspension hydraulic fracturing coated proppant with targeting function and preparation and application thereof Download PDFInfo
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
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Abstract
The invention provides a self-suspension hydraulic fracturing coated proppant with a targeting function, and preparation and application thereof. The proppant comprises: A. a nanoparticle reinforced porous composite coating coated on the surface of a particle and present in an amount of 0.01 to 30% based on the total weight of the proppant, the nanoparticle reinforced porous composite comprising nanoparticles (preferably the weight of the nanoparticles is 1 to 50% (preferably 10 to 20%) of the total weight of the nanoparticle reinforced porous composite coating) and a porous composite. Compared with the functional film-coated proppant produced by the traditional process, the resin and other materials used by the method are from industrial production, the nano particles are creatively added to improve the performance of the proppant, and the method has a simpler operation process and saves the production cost.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a self-suspension hydraulic fracturing coated proppant with a targeting function, and preparation and application thereof.
Background
With the exploitation of a large amount of energy sources such as petroleum and natural gas, people gradually turn their eyes to the development and utilization of unconventional energy sources such as shale gas. Although the reserves of unconventional energy sources in China are huge, the unconventional energy sources are not fully utilized due to the limitation of the mining process.
Most unconventional reservoirs have the characteristics of low porosity and low permeability, so that the reservoir transformation is required to be carried out through hydraulic fracturing, fracturing fluid is required to be used for carrying a large amount of propping agent and pumping the propping agent into the underground through high pressure and high speed to fill all parts of a crack, the crack is supported to prevent the crack from being closed, crude oil flows into a well bottom through a propping agent gap, an oil and gas transportation channel is developed, the oil and gas yield is increased, the service life of an oil well is prolonged, and the purpose of improving the recovery ratio is achieved.
The film covering means that a high polymer material is artificially coated outside the traditional propping agent. Compared with the traditional proppant, the tectorial membrane proppant has the characteristics of high strength, low density, corrosion resistance, high flow conductivity and the like, but the resin membrane of the tectorial membrane on the proppant is generally very thin, the interface between the aggregate and the resin membrane is easily damaged when the tectorial membrane is incomplete, and in addition, the cost is higher due to the fast sedimentation of the tectorial membrane proppant, so the on-site requirement cannot be well met.
Therefore, the development of a proppant for unconventional reservoir fracturing, which is relatively cheap, has the characteristics of strong suspension capacity, high strength, low density, multiple functions, adaptation to unconventional reservoir fracturing and the like, is still needed in the industry.
Disclosure of Invention
One object of the present invention is to provide a self-suspending hydraulic fracturing coated proppant with targeting function;
the invention also aims to provide a preparation method of the proppant;
it is a further object of the invention to provide the use of said proppant.
To achieve the above object, in one aspect, the present invention provides a self-suspending hydraulic fracturing coated proppant with a targeting function, wherein the proppant comprises:
A. particles present in an amount of 70-99.99% based on the total weight of the proppant, and
B. a coating of a nanoparticle-reinforced porous composite comprising nanoparticles and a porous composite coated on the surface of particles and present in an amount of 0.01 to 30% based on the total weight of the proppant.
Due to the nanoparticles mixed in the gaps between the aggregates and the resin film, the mechanical strength of the proppant is greatly increased, and the proppant can be protected from the closing stress applied by the stratum.
In addition, due to the action of the added nanoparticles, the adhesive force between the aggregate and the resin film is stronger, the affinity is better, and the sphericity of the coated proppant is closer to 1.
The external part of the propping agent is provided with a polymer membrane structure, so that the hydrophilic and oleophobic conversion of surface free radicals can be realized. The suspension capacity is strong when the water-based oil-gas composite material is injected into a stratum, the strength after sedimentation is enough to support a new crack, the oil-gas composite material is beneficial to discharge of oil gas, and the flowback rate is low during flowback.
The special nanoparticles used in the process of coating the film on the proppant can enable the proppant to respond to specific external temperature, have excellent targeting capability, and can change the suspension capability of the proppant by adjusting the attachment amount of the polymer on the surface of the proppant particle.
The proppant can respond to external light stimulation due to the multifunctional film coating structure, and can realize expected conversion of adhesiveness, wettability, thermosetting property and the like according to the strength and type of the stimulation.
According to some embodiments of the invention, the weight of the nanoparticles is 1-50% of the total weight of the nanoparticle reinforced porous composite coating.
According to some embodiments of the invention, the weight of the nanoparticles is 10-20% of the total weight of the nanoparticle reinforced porous composite coating.
According to some embodiments of the invention, the material of the particles is selected from one or more of rock, bauxite, kaolin, mica, ceramsite sand, quartz sand, minerals, nut shells, seed shells, walnut shells, fruit stones, coal gangue, diatomite, glass balls, crushed charcoal, fly ash, red mud, slag, sawdust, wood chips, resin particles, and date powder.
According to some embodiments of the invention, wherein the particle size ranges from 10 mesh to 100 mesh.
According to some embodiments of the invention, the nanoparticle is selected from one or more of nanoparticle plasma metamaterial, nano silicon powder, amino/carboxyl silver nanoparticle, nano aluminum oxide, nano titanium oxide, nano holmium oxide, magnetic graphene, single-walled carbon nanotube, double-walled carbon nanotube, multi-walled carbon nanotube, nano barium titanate, nano strontium titanate, hydroxyl/carboxyl/amino fluorescent quantum dot, two-dimensional transition metal carbide, two-dimensional transition metal nitride, two-dimensional transition metal carbonitride, carboxyl/amino polystyrene microsphere, graphene, carbon nanofiber, nano diamond, and nano diamond powder.
According to some embodiments of the invention, the nanoparticle plasma metamaterial is a combination of one or more of nanogold, nanosilver and nanocarbon.
According to some embodiments of the present invention, the carbon-containing nanoparticles comprise at least 5% by weight of the total nanoparticles weight as 100%.
According to some specific embodiments of the present invention, the two-dimensional transition metal nitride or the magnetic graphene is added in an amount of 5 wt% or more based on the total weight of the nanoparticles as 100 wt%.
According to some specific embodiments of the present invention, the two-dimensional transition metal nitride or the magnetic graphene is added in an amount of 30 wt% or less based on the total weight of the nanoparticles as 100 wt%.
According to some embodiments of the invention, the porous composite material is selected from one or more of organic solvent soluble and water insoluble polymer materials at normal temperature; and the porous composite material at least contains one polymer material.
According to some embodiments of the invention, the organic solvent is acetone or an alcoholic organic solvent.
According to some embodiments of the invention, the alcoholic organic solvent is a linear or branched alkyl alcohol having 1 to 5 carbon atoms.
According to some embodiments of the invention, the alcoholic organic solvent is ethanol.
According to some embodiments of the present invention, the polymer material is polymethyl methacrylate and alcohol-soluble resin.
According to some embodiments of the invention, the alcohol-soluble resin is selected from melamine resin, polyurethane, polybutadiene phenolic resin or epoxy resin.
According to some specific embodiments of the present invention, wherein the nanoparticle-reinforced porous composite coating further comprises a combination of one or more of the following auxiliary materials: the coating comprises a curing agent accounting for 1-5% of the total mass of the coating, a surface modifier accounting for 2-10% of the total mass of the coating and an amine additive accounting for 1-5% of the total mass of the coating.
According to some embodiments of the invention, wherein the thickening agent is selected from the group consisting of sodium alginate, guar gum and carboxymethylcellulose.
According to some embodiments of the invention, the surface modifier is selected from the group consisting of sodium stearate, sodium dodecylbenzenesulfonate and a combination of one or more silane coupling agents.
According to some embodiments of the invention, the amine additive is selected from ethylenediamine and/or triethanolamine.
The surface modifier can enhance the connection between the aggregate and the coating, so that the coating and the aggregate are combined more tightly and completely.
According to some embodiments of the invention, the dispersed phase of the nanoparticles is one-dimensional or multi-dimensional, and the nanoparticles have a particle size of 0.1 to 500 nm.
According to some embodiments of the invention, wherein the proppant bulk density is less than 1.7g/cm3。
According to some embodiments of the invention, wherein the proppant has a fracture rate of less than 10% in the crush resistance test at 69 Mpa.
The nanoparticle reinforced composite of the present invention has a temperature response capability.
The response capability includes, but is not limited to, the ability to respond to changes in the formation environment or actively applied external stimuli to change its own wettability, adhesiveness, thermosetting properties, etc.
In another aspect, the present invention also provides a preparation method of the proppant, wherein the method comprises the following steps:
(1) mixing the porous composite material with acetone or an alcohol organic solvent according to a mass ratio of 1: (7-9), stirring uniformly at normal temperature, adding nanoparticles accounting for 2-6% of the added mass of the porous composite material, and stirring uniformly to obtain a mixed solution;
(2) adding the particles into the mixed solution obtained in the step (1) under stirring, and uniformly stirring at normal temperature;
(3) separating solid matters in the solution in the step (2) from the solution, uniformly filtering the solid matters into water through a 20-40-mesh screen, and then carrying out solid-liquid separation to obtain water-containing precoated sand;
(4) and (4) drying the water-containing precoated sand obtained in the step (3) and then sieving to obtain the hydraulic fracturing precoated proppant with the targeting function.
According to some embodiments of the invention, the alcoholic organic solvent is a linear or branched alkyl alcohol having 1 to 5 carbon atoms.
According to some embodiments of the invention, the alcoholic organic solvent is ethanol.
According to some specific embodiments of the present invention, in the step (1), the porous composite material and the acetone or the alcohol organic solvent are mixed in a mass ratio of 1: (7-9), stirring uniformly at normal temperature, adding the nano particles accounting for 4% of the added mass of the porous composite material, and stirring uniformly to obtain a mixed solution.
According to some specific embodiments of the present invention, step (1) comprises mixing the porous composite material with acetone or an alcohol organic solvent in a mass ratio of 1: (7-9) stirring at the rotation speed of 600-1000rpm for 10-15 min at normal temperature.
According to some specific embodiments of the present invention, the step (1) includes mixing the porous composite material with acetone or an alcohol organic solvent at a ratio of 50g:500ml, stirring the mixture uniformly at normal temperature, adding nanoparticles in an amount of 4% of the added mass of the porous composite material, and stirring the mixture for 2 to 5min at 600 to 1000 rpm.
According to some specific embodiments of the present invention, the step (2) includes adding the particles into the mixed solution obtained in the step (1) under stirring, and mechanically stirring at 600 to 800rpm for 2 to 5min at normal temperature.
According to some embodiments of the present invention, the amount of water used in step (3) is 10 to 20 times the mass of the porous composite material.
According to some specific embodiments of the invention, the step (4) comprises standing the water-containing coated sand obtained in the step (3) at normal temperature for 5-10 min, drying at 60-80 ℃ for 4-6h, and sieving to obtain the hydraulic fracturing coated proppant with the targeting function.
According to some specific embodiments of the invention, the step (4) comprises standing the water-containing coated sand obtained in the step (3) at normal temperature for 5-10 min, drying at 60-80 ℃ for 5h, and sieving to obtain the hydraulic fracturing coated proppant with the targeting function.
According to some embodiments of the invention, the sieving in step (4) is 20-40 mesh sieving.
According to some embodiments of the present invention, step (1) comprises mixing the porous composite material with acetone or an alcohol organic solvent, adding one or more of the auxiliary materials of the present invention, and stirring at room temperature.
According to some embodiments of the invention, the method comprises the following steps:
(1) the preparation method comprises the steps of proportioning a resin solution by phenolic resin and ethanol according to the proportion of 50g to 500ml, adding a thickening agent, mechanically stirring at 800rpm for 10min at normal temperature, adding carbon quantum dot particles and graphene according to 4% of the added amount of the phenolic resin, and continuously stirring at 600rpm for 2 min. Sealing the beaker in the stirring process to reduce ethanol volatilization;
(2) pouring the ceramsite sand into the resin solution while stirring, and mechanically stirring at 600rpm for 2min at normal temperature so as to uniformly distribute the ceramsite sand in the resin solution;
(3) uniformly filtering the precoated sand into water through a 40-mesh screen;
(4) standing the precoated sand for 5min at normal temperature, putting the precoated sand into an air box, drying the precoated sand for 5h at 80 ℃, taking out the precoated sand, sieving the precoated sand (40 meshes), and packaging the precoated sand to obtain the precoated sand.
The proppant can enable the aggregate to be tightly combined with the outer resin film due to the film covering process in the preparation process, so that a large number of bubbles are left in the inner part and the outer surface of the resin film, thereby increasing the surface area of the film-covered proppant and improving the self-suspension performance of the film-covered proppant.
In another aspect, the invention also provides the application of the proppant in the supporting and diversion of unconventional reservoir hydraulic fracturing and conventional fractured rock fractures.
In conclusion, the invention provides a self-suspension hydraulic fracturing coated proppant with a targeting function, and preparation and application thereof. The proppant of the invention has the following advantages:
(1) due to the extraction process in the preparation engineering, a large number of bubbles can be reserved in the gap between the aggregate and the resin film, a porous structure is formed, the surface area of the porous structure is increased, and the self-suspension performance of the porous structure is improved. In addition, due to the nanoparticle reinforced composite coating coated on the surface, the mechanical strength of the proppant is greatly increased, and the proppant can be protected from the closing stress applied by the stratum.
(2) Due to the action of the added nano particles, the adhesive force between the aggregate and the resin film is stronger, the affinity is better, and the sphericity of the coated proppant is closer to 1.
(3) The external part of the propping agent is provided with a polymer membrane structure, so that the hydrophilic and oleophobic conversion of surface free radicals can be realized. The suspension capacity is strong when the water-based oil-gas composite material is injected into a stratum, the strength after sedimentation is enough to support a new crack, the oil-gas composite material is beneficial to discharge of oil gas, and the flowback rate is low during flowback.
(4) The special nanoparticles used in the process of coating the film on the proppant can enable the proppant to respond to specific external temperature, have excellent targeting capability, and can change the suspension capability of the proppant by adjusting the attachment amount of the polymer on the surface of the proppant particle.
(5) The proppant can respond to external light stimulation due to the multifunctional film coating structure, and can realize expected conversion of adhesiveness, wettability, thermosetting property and the like according to the strength and type of the stimulation.
(6) Compared with the functional film-coated proppant produced by the traditional process, the resin and other materials used by the method are from industrial production, the nano particles are creatively added to improve the performance of the proppant, and the method has a simpler operation process and saves the production cost.
Drawings
FIG. 1 is a graph of the settling of the coated proppant of comparative example 1 in deionized water for 100 minutes (top view on the left and side view on the right).
FIG. 2 is a graph of the coated proppant of example 1 settling in deionized water for 100 minutes (top view on the left and side view on the right).
FIG. 3 is a schematic representation of a coated proppant made in example 1; wherein 1 is a resin film; 2 is a gap between the resin film and the framework; 3 is a framework; 4 is a bubble; 5 is a nanoparticle.
FIG. 4 is a schematic magnetic representation of the targeting of the coated proppant prepared in example 5.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Examples the starting materials:
the raw materials used in this example were all commercially available:
phenolic resin CAS No.: 9003-35-4, formula: c7H6O2Molecular weight: 122.12134.
single layer graphene powder: CAS number: 7440-44-0, diameter: 0.5 to 5 μm, thickness: 0.8nm, monolayer rate: 80% and purity: 99% of specific surface area (m)2(iv)/g): 500 to 1000, and the resistivity (omega. cm) is less than or equal to 0.30.
Carbon quantum dot particles: the double-emission co-doped carbon dots (N, S-cds) with long emission wavelength are synthesized by a solvothermal method. L-cystine (0.125g) and O-phenylenediamine (0.5g) were first dissolved in 20ml of ethanol and transferred to a 50ml stainless steel autoclave. The autoclave was then baked in an oven at 220 ℃ for 12 hours and then allowed to cool to room temperature. Thereafter, 2 ml of N, S-CDs were added to 4 ml of sodium hydroxide solution (1.25mol/L), the mixture was centrifuged at 10000 rpm for 10 minutes, the precipitate was dissolved with ethanol, and the solution was filtered twice with a cylindrical filter (0.22 μm). The solution was then spin dried in a rotary apparatus to obtain carbon dots. The prepared N, S-CDs with double emission peaks (595 nm and 648nm) do not need to be further modified under the condition of single excitation, and can be used as fluorescent probes for strong acid sensing and Ag + detection. The N, S-CDs have good pH reversible performance and can be used for detecting extreme acids. In addition, the prepared N, S-CDs are in a quasi-spherical shape, the average size is 2.97nm, the size distribution is narrow, the solution dispersibility is high, strong excitation independent emission is shown at 595nm, and the quantum yield is 35.7%.
Aggregate: provided by Chongqing geological mineral research institute.
Example 1
(1) The following materials were prepared: 300 parts of aggregate, 5 parts of phenolic resin, 40 parts of ethanol, 0.2 part of carbon quantum dot particles and 0.2 part of single-layer graphene powder.
(2) And (2) mixing the phenolic resin in the step (1) and ethanol according to a ratio of 50g to 500ml to prepare a resin solution, mechanically stirring at 800rpm at normal temperature for 10min, and sealing a beaker in the stirring process to reduce ethanol volatilization.
(3) And (2) pouring the aggregate, the carbon quantum dot particles and the single-layer graphene powder in the step (1) into the resin solution while stirring, and mechanically stirring at 600rpm for 2min at normal temperature, so that the aggregates, the carbon quantum dot particles and the single-layer graphene powder are uniformly distributed in the resin solution.
(4) And (4) uniformly filtering the mixture in the step (3) into water through a 40-mesh screen, standing for 5min at normal temperature, putting into an air box, drying for 5h at 80 ℃, and taking out.
(5) After drying, because the precoated sand is partially agglomerated, after cooling, the blocky precoated sand needs to be put into a grinder for grinding, and after grinding for 1min at 2000rpm, the blocky precoated sand is packaged to obtain the precoated sand (the structure is shown in figure 3).
Example 2
(1) The following materials were prepared: 300 parts of aggregate, 5 parts of phenolic resin, 40 parts of acetone, 0.2 part of carbon quantum dot particles and 0.2 part of single-layer graphene powder.
(2) And (2) mixing the phenolic resin in the step (1) and acetone according to the proportion of 50g to 500ml to prepare a resin solution, mechanically stirring at 800rpm for 10min at normal temperature, and sealing a beaker in the stirring process to reduce acetone volatilization.
(3) And (2) pouring the aggregate, the carbon quantum dot particles and the single-layer graphene powder in the step (1) into the resin solution while stirring, and mechanically stirring at 600rpm for 2min at normal temperature, so that the aggregates, the carbon quantum dot particles and the single-layer graphene powder are uniformly distributed in the resin solution.
(4) And (4) uniformly filtering the mixture in the step (3) into water through a 40-mesh screen, standing for 5min at normal temperature, putting into an air box, drying for 5h at 80 ℃, and taking out.
(5) After drying, because the precoated sand is partially agglomerated, after cooling, the blocky precoated sand needs to be put into a grinder for grinding, and after grinding for 1min at 2000rpm, the blocky precoated sand is packaged to obtain the finished product.
Example 3
(1) The following materials were prepared: 300 parts of aggregate, 5 parts of phenolic resin, 35 parts of ethanol, 0.1 part of carbon quantum dot particles and 0.1 part of single-layer graphene powder.
(2) Mixing the phenolic resin and ethanol in the step (1) according to a mass ratio of 1: 7, mechanically stirring at 800rpm at normal temperature for 10min, and sealing the beaker during stirring to reduce ethanol volatilization.
(3) And (2) pouring the aggregate, the carbon quantum dot particles and the single-layer graphene powder in the step (1) into the resin solution while stirring, and mechanically stirring at 600rpm for 2min at normal temperature, so that the aggregates, the carbon quantum dot particles and the single-layer graphene powder are uniformly distributed in the resin solution.
(4) And (4) uniformly filtering the mixture in the step (3) into water through a 20/40-mesh screen, standing for 5min at normal temperature, putting into an air box, drying for 5h at 80 ℃, and taking out.
(5) After drying, because the precoated sand is partially agglomerated, after cooling, the blocky precoated sand needs to be put into a grinder for grinding, and after grinding for 1min at 2000rpm, the blocky precoated sand is packaged to obtain the finished product.
Example 4
(1) The following materials were prepared: 300 parts of aggregate, 5 parts of phenolic resin, 45 parts of ethanol, 0.3 part of carbon quantum dot particles and 0.3 part of single-layer graphene powder.
(2) Mixing the phenolic resin and ethanol in the step (1) according to a mass ratio of 1: 9, mechanically stirring at 800rpm at normal temperature for 10min, and sealing the beaker during stirring to reduce ethanol volatilization.
(3) And (2) pouring the aggregate, the carbon quantum dot particles and the single-layer graphene powder in the step (1) into the resin solution while stirring, and mechanically stirring at 600rpm for 2min at normal temperature, so that the aggregates, the carbon quantum dot particles and the single-layer graphene powder are uniformly distributed in the resin solution.
(4) And (4) uniformly filtering the mixture in the step (3) into water through a 20/40-mesh screen, standing for 5min at normal temperature, putting into an air box, drying for 5h at 80 ℃, and taking out.
(5) After drying, because the precoated sand is partially agglomerated, after cooling, the blocky precoated sand needs to be put into a grinder for grinding, and after grinding for 1min at 2000rpm, the blocky precoated sand is packaged to obtain the finished product.
Example 5
(1) The following materials were prepared: 300 parts of aggregate, 5 parts of phenolic resin, 40 parts of ethanol, 0.2 part of carbon quantum dot particles, 0.2 part of single-layer graphene powder and 0.2 part of ferroferric oxide powder.
(2) Mixing the phenolic resin and ethanol in the step (1) according to a mass ratio of 1: 8, mechanically stirring at 800rpm at normal temperature for 10min, and sealing the beaker during stirring to reduce ethanol volatilization.
(3) And (2) pouring the aggregate, the carbon quantum dot particles and the single-layer graphene powder in the step (1) into the resin solution while stirring, and mechanically stirring at 600rpm for 2min at normal temperature, so that the aggregates, the carbon quantum dot particles and the single-layer graphene powder are uniformly distributed in the resin solution.
(4) And (4) uniformly filtering the mixture in the step (3) into water through a 20/40-mesh screen, standing for 5min at normal temperature, putting into an air box, drying for 5h at 80 ℃, and taking out.
(5) After drying, because the precoated sand is partially agglomerated, after cooling, the blocky precoated sand needs to be put into a grinder for grinding, and after grinding for 1min at 2000rpm, the blocky precoated sand is packaged to obtain the finished product.
Comparative example 1
(1) The following materials were prepared: 300 parts of aggregate, 5 parts of phenolic resin, 0.2 part of carbon quantum dot particles and 0.2 part of single-layer graphene powder.
(2) And (2) heating the aggregate in the step (1) to about 150 ℃, and pouring the aggregate into a sand mixing pot for sand mixing.
(3) Heating the phenolic resin, the carbon quantum dot fluorescent particles and the single-layer graphene powder to about 110 ℃, mechanically stirring at 600rpm for 2min, and uniformly mixing for later use.
(4) And (4) adding the mixture obtained in the step (3) when the temperature of the mixing pan is reduced to 80-150 ℃.
(5) And (3) discharging sand when the temperature of the mixing pan is reduced to 40 ℃, uniformly filtering the sand into water through a 40-mesh screen, standing the sand for 5min at normal temperature, putting the sand into an air box, drying the sand for 5h at 80 ℃, and taking out the sand.
(6) After drying, because the precoated sand is partially agglomerated, after cooling, the blocky precoated sand needs to be put into a grinder for grinding, and after grinding for 1min at 2000rpm, the blocky precoated sand is packaged to obtain the finished product.
Comparative example 2
(1) The following materials were prepared: 100 parts of aggregate, 5 parts of epoxy resin, 1 part of curing agent dibenzoyl peroxide, 0.2 part of magnetic graphene, 0.3 part of polystyrene microsphere, 0.003 part of catalyst dialkyl stannene and 2.5 parts of surface modifier silane coupling agent.
(2) And (2) heating the aggregate in the step (1) to about 250 ℃, and pouring the aggregate into a sand mixing pot for sand mixing.
(3) And (2) adding the epoxy resin obtained in the step (1) into an earthen mixing pot, and adding a curing agent for laminating when the temperature is reduced to be lower than 210 ℃.
(4) When the temperature is reduced to 150 ℃, the surface modifier added with water is sprayed into the marmite.
(5) And when the temperature of the sand mixing pot is reduced to 120 ℃, adding the ultrapure water solution of the magnetic graphene and the ultrapure water solution of the polystyrene microspheres into the sand mixing pot in a hot air blowing mode, wherein the rotating speed of the sand mixing pot is not lower than 150 revolutions per minute.
(6) And (4) sand removal and air drying at 40-70 ℃.
Test example 1
The roundness, sphericity, volume density, apparent density, turbidity and breakage rate of the uncoated ceramsite sand and the coated ceramsite sand prepared in the above examples and comparative examples are respectively tested according to a recommended performance test method of a standard SY/T5108-2006 fracturing proppant, and the performance indexes of the proppant are shown in the following table 1:
table 1:
the suspension time in table 1 is the maximum time the proppant can freely suspend in the guar solution.
As can be seen from table 1, the proppant added with the nanoparticle reinforcing material during the coating process has a sphericity close to 1, and the bulk density and the apparent density are lower than those of the proppant coated with general resin. As can be seen from the results of the fracture experiment, the addition of the nano reinforcing material improves the strength of the proppant and has lower fracture rate compared with the conventional film.
Compared with the uncoated quartz sand, the proppant in the comparative example and the example has obviously improved performance, and the example is obviously superior to the comparative example (shown in figures 1 and 2) in the sedimentation time index, so that the proppant disclosed by the invention has stronger suspension capacity and stronger applicability than the conventional proppant and the coated proppant under the same condition. The targeting magnetic effect of the coated proppant prepared in example 5 is shown in fig. 4.
Claims (15)
1. A self-suspending hydraulic fracturing coated proppant with targeting function, wherein the proppant comprises:
A. particles present in an amount of 70-99.99% based on the total weight of the proppant, and
B. a coating of a nanoparticle-reinforced porous composite coated on the surface of a particle and present in an amount of 0.01 to 30% based on the total weight of the proppant, the nanoparticle-reinforced porous composite comprising a nanoparticle and a porous composite; the weight of the nano particles is 1-50% of the total weight of the nano particle reinforced porous composite material coating; the nanoparticles are selected from carbon quantum dots and graphene; the porous composite material is selected from one or more of polymethyl methacrylate, melamine resin, polyurethane, polybutadiene phenolic resin or epoxy resin; the volume density of the proppant is less than 1.7g/cm3；
The proppant is prepared by a method comprising the following steps:
(1) mixing the porous composite material with acetone or an alcohol organic solvent according to a mass ratio of 1: (7-9), stirring uniformly at normal temperature, adding nanoparticles accounting for 2-6% of the added mass of the porous composite material, and stirring uniformly to obtain a mixed solution; the alcohol organic solvent is straight-chain or branched-chain alkyl alcohol with the carbon atom number of 1-5;
(2) adding the particles into the mixed solution obtained in the step (1) under stirring, and uniformly stirring at normal temperature;
(3) separating solid matters in the solution in the step (2) from the solution, uniformly filtering the solid matters into water through a 20-40-mesh screen, and then carrying out solid-liquid separation to obtain water-containing precoated sand; the mass consumption of the water is 10-20 times of the mass of the porous composite material;
(4) and (4) drying the water-containing precoated sand obtained in the step (3) and then sieving to obtain the hydraulic fracturing precoated proppant with the targeting function.
2. A proppant according to claim 1 wherein the weight of the nanoparticle is from 10 to 20% of the total weight of the nanoparticle reinforced porous composite coating.
3. A proppant according to claim 1 wherein said particle is of a material selected from the group consisting of rock, bauxite, kaolin, mica, ceramsite sand, quartz sand, minerals, nut shells, seed shells, walnut shells, fruit pits, coal gangue, diatomaceous earth, glass spheres, crushed charcoal, fly ash, red mud, smelter slag, sawdust, wood chips, resin particles, wild jujube powder, and combinations thereof.
4. A proppant as set forth in any one of claims 1-3 wherein said nanoparticle-reinforced porous composite coating further comprises a combination of one or more of the following auxiliary materials: the coating comprises 1-5% of a thickening agent, 2-10% of a surface modifier and 1-5% of an amine additive in the total mass ratio of the coating.
5. A proppant as set forth in claim 4 wherein said thickening agent is selected from the group of one or more of sodium alginate, guar gum, and carboxymethylcellulose; the surface modifier is selected from one or more of sodium stearate, sodium dodecyl benzene sulfonate and silane coupling agent; the amine additive is selected from ethylenediamine and/or triethanolamine.
6. A proppant as set forth in any one of claims 1 to 3 wherein said dispersed phase of nanoparticles is one-dimensional or multi-dimensional and said nanoparticles have a particle size of from 0.1 to 500 nm.
7. A proppant as set forth in any one of claims 1-3 wherein said proppant has a crush resistance of less than 10% in the crush resistance test at 69 Mpa.
8. A method of making a proppant as set forth in any one of claims 1-7, wherein said method comprises the steps of:
(1) mixing the porous composite material with acetone or an alcohol organic solvent according to a mass ratio of 1: (7-9), stirring uniformly at normal temperature, adding nanoparticles accounting for 2-6% of the added mass of the porous composite material, and stirring uniformly to obtain a mixed solution; the alcohol organic solvent is straight-chain or branched-chain alkyl alcohol with the carbon atom number of 1-5;
(2) adding the particles into the mixed solution obtained in the step (1) under stirring, and uniformly stirring at normal temperature;
(3) separating solid matters in the solution in the step (2) from the solution, uniformly filtering the solid matters into water through a 20-40-mesh screen, and then carrying out solid-liquid separation to obtain water-containing precoated sand; the mass consumption of the water is 10-20 times of the mass of the porous composite material;
(4) and (4) drying the water-containing precoated sand obtained in the step (3) and then sieving to obtain the hydraulic fracturing precoated proppant with the targeting function.
9. The production method according to claim 8, wherein the alcoholic organic solvent is ethanol.
10. The preparation method according to claim 8, wherein the step (1) comprises mixing the porous composite material with acetone or an alcohol organic solvent in a mass ratio of 1: (7-9), stirring at the rotating speed of 600-1000rpm for 10-15 min at normal temperature to stir uniformly; then adding nanoparticles with the mass of 2-6% of the added mass of the porous composite material, and stirring at 600-1000rpm for 2-5 min to obtain a mixed solution.
11. The preparation method according to claim 8, wherein the step (2) comprises adding the particles into the mixed solution obtained in the step (1) under stirring, and mechanically stirring at 600-800 rpm for 2-5 min under normal temperature condition to stir uniformly.
12. The preparation method of claim 8, wherein the step (4) comprises standing the water-containing coated sand obtained in the step (3) at normal temperature for 5-10 min, drying at 60-80 ℃ for 4-6h, and sieving to obtain the hydraulic fracturing coated proppant with the targeting function.
13. The preparation method of claim 12, wherein the step (4) comprises standing the water-containing coated sand obtained in the step (3) at normal temperature for 5-10 min, drying the sand at 60-80 ℃ for 4-6h, and sieving the sand with a 20-40-mesh sieve to obtain the hydraulic fracturing coated proppant with the targeting function.
14. The preparation method according to claim 8, wherein the step (1) comprises mixing the porous composite material with acetone or an alcohol organic solvent, adding a mixture of one or more of the auxiliary materials according to claim 4, and then stirring uniformly at normal temperature.
15. Use of the proppant of any one of claims 1-7 in unconventional reservoir hydraulic fracturing and conventional fractured rock fracture propping and diversion.
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| WO2021087658A1 (en) * | 2019-11-04 | 2021-05-14 | 中国石油大学(北京) | Self-suspension hydraulic fracturing coated proppant having targeting function, and preparation and application |
| CN111808599A (en) * | 2020-07-10 | 2020-10-23 | 重庆地质矿产研究院 | Shale debris coated proppant with targeting function and preparation method and application thereof |
| CN114479823B (en) * | 2021-12-31 | 2023-06-20 | 宁波锋成先进能源材料研究院有限公司 | Fracturing propping agent and preparation method and application thereof |
| CN114437707B (en) * | 2022-02-10 | 2023-01-31 | 北京昆仑隆源石油开采技术有限公司 | Self-suspending proppant and preparation method thereof |
| CN115322765B (en) * | 2022-08-18 | 2023-06-23 | 成都劳恩普斯科技有限公司 | Microcrack propping agent with resistance reduction and microcrack laying functions |
| CN115627160A (en) * | 2022-11-08 | 2023-01-20 | 陕西君泰实业有限公司 | Petroleum fracturing propping agent and preparation method thereof |
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| US7135231B1 (en) * | 2003-07-01 | 2006-11-14 | Fairmont Minerals, Ltd. | Process for incremental coating of proppants for hydraulic fracturing and proppants produced therefrom |
| US7867613B2 (en) * | 2005-02-04 | 2011-01-11 | Oxane Materials, Inc. | Composition and method for making a proppant |
| EP2436749A1 (en) * | 2005-06-13 | 2012-04-04 | Sun Drilling Products Corporation | Thermoset particles with enhanced crosslinking, processing for their production, and their use in oil and natural gas drilling applications |
| CN102099545B (en) * | 2008-05-20 | 2015-06-10 | 环氧乙烷材料股份有限公司 | Method of manufacture and the use of a functional proppant for determination of subterranean fracture geometries |
| CN104948160A (en) * | 2014-03-28 | 2015-09-30 | 北京仁创科技集团有限公司 | Self-suspension proppant and preparation method thereof and construction method |
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