CN109575906A - The polymer composite proppant particles and its preparation method of resin film cladding and application - Google Patents
The polymer composite proppant particles and its preparation method of resin film cladding and application Download PDFInfo
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- CN109575906A CN109575906A CN201710897128.6A CN201710897128A CN109575906A CN 109575906 A CN109575906 A CN 109575906A CN 201710897128 A CN201710897128 A CN 201710897128A CN 109575906 A CN109575906 A CN 109575906A
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- resin
- proppant
- powder
- prepolymer
- proppant particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
Abstract
The present invention provides the polymer composite proppant particles that resin film coats and its preparation method and application, the proppant particles of resin film cladding, and apparent density is 1.00~1.08g/cm3；The proppant to be coated is the particle of 20~100 mesh, and apparent density is 1.00~1.10g/cm3, bulk density is 0.40~0.50g/m3；The proppant to be coated includes the first resin mutually bonded and the powder Jing Guo chemical modification, and the powder by chemical modification includes the first powder by chemical modification and the second powder Jing Guo chemical modification.The proppant particles that the present invention coats can be under the premise of density be basically unchanged before and after maintaining overlay film, significantly reduce the percentage of damage of proppant, solubility in mud acid, fine particle generation is advantageously reduced, to improve the flow conductivity of hydraulic fracture to be supported in hydraulic fracturing transformation and improve oil and gas production.
Description
Technical field
The present invention relates to the polymer composite proppant particles of resin film cladding and its preparation method and applications, in particular to
The polymer composite super-low-density proppant particle and its preparation method of resin film cladding and application, belong in hydraulic fracturing technology
Christmas auxiliary agent technical field.
Background technique
Hydraulic fracturing transformation is hypotonic one of the core technology with the exploitation of unconventional oil and gas field economical and effective of hypotonic spy.Support
Agent be guarantee hydraulically created fracture have high flow conductivity critical material, it in crack it is efficient filling to guarantee pressure break imitate
Fruit is most important.In fracturing reform work progress, fracturing fluid is injected in underground reservoir under high speed, high pressure and is allowed to split
It opens.Before Reservoirs closure, the fracturing fluid for carrying proppant enters Reservoirs and supports crack, gas stream
Body, by the gap discharge between proppant stages, finally realizes oil-gas mining under the action of strata pressure.
Quartz sand compression strength is not high, is being more than certain clossing pressure (generally 35MPa), can have more than 15% stone
Sand is broken, generates fine particle blocking Reservoir Fracture and hole.In addition, quartz sand solubility in mud acid is generally more than
10%., can be to the resin-coated film of quartz sand in order to improve the compression strength and anti-mud acid solvability of quartz sand, quartz sand at present
Film covering method there are mainly two types of:
First method is to impregnate quartz sand in resin solution, then the infusion process of dry solidification.The production method
Energy consumption is high, production efficiency is low, has not used substantially.
Second method is that heat covers method, i.e., quartz sand and powdered resin are heated to resin in melting jointly under stirring
State (200~250 DEG C) is then added resin curing agent and solidifies the resin film of cladding.As CN102942334B discloses one
Kind is using hot coating process to the method for quartz sand overlay film.
On the other hand, the apparent density of quartz sand is generally 2.60~2.70g/cm3, need high viscosity fracturing fluid carry and it is defeated
It send, high viscosity fracturing fluid breaks glue and is not thorough, and absorption of the high polymer therein in reservoir rocks easily causes reservoir damage.And when pressure
Split fluid viscosity it is low when, it is difficult to suspend conventional high density proppant, leads to difficulty of transportation, easily settles in crack, crack is effectively propped up
It is smaller to support area.In contrast, super-low-density proppant is since density can be down to 1.0~1.2g/cm3, basic with the density of water
Quite, a minimal flow speed quantity lower than conventional proppants needed for keeping proppant super-low-density proppant suspension conveying
Grade, it is only necessary to which clear water or the fracturing fluid of low viscosity can convey, and convey, crack effective bearing area high with pack effectiveness
Greatly, clear water or the fracturing fluid of low viscosity are not thorough there is no broken glue adsorbs injury reservoir problem with high polymer, can significantly reduce pressure
The injury to reservoir and man-made fracture is split, is conducive to improve fracture condudtiviy, further increases oil and gas production.
Heat as described above is covered method and is not particularly suited for polymer composite super-low-density proppant overlay film, the reason is that
200~250 DEG C of temperature softens high molecular material, glues between polymer composite super-low-density proppant particle
Even, or even high molecular material therein is destroyed, is allowed to that overaging occurs, reduces polymer composite super-low-density proppant
Various aspects of performance index；Moreover, the product that heat covers method production is easy to consolidate agglomerating, unstable quality.Therefore it needs lower
To polymer composite super-low-density proppant overlay film at temperature (such as 50~120 DEG C), but in actual mechanical process, due to
Resin used in overlay film can not solidify rapidly under lower temperature (such as 50~120 DEG C), lead to stick to each other group between proppant particles
It is poly-, or stick on fluidized bed inner wall, and then cannot achieve fluidisation, cause production that can not carry out when serious.
In addition, 103275694 A of CN discloses a kind of natural minerals (silicon powder, kaolin, diatomite or angstrom Lip river
Stone) with the polyolefin polymer composite proppant being combined and the method that overlay film is carried out to it, the patent using
Infusion process.It is low to be as previously mentioned infusion process production efficiency, is not suitable for industrialized production.
Therefore, this field needs to develop a kind of be applicable to the method for super-low-density proppant overlay film and prepared therefrom
Proppant, to be conducive to well fracturing transformation.
Summary of the invention
In view of above-mentioned needs, one of the objects of the present invention is to provide a kind of proppant particles of resin film cladding,
Have the advantages that percentage of damage is low and solubility in mud acid is small in being applied to fracturing reform.
Another object of the present invention is to provide the preparation method of the proppant particles of aforementioned resin film cladding, the overlay film sides
Method is simple, strong operability, easy to industrialized production.
A further object of the present invention is to provide the applications of the proppant particles of aforementioned resin film cladding.
To achieve the above object, on the one hand, the present invention provides a kind of proppant particles of resin film cladding, and apparent density is
1.00~1.10g/cm3；The proppant to be coated is the particle of 20~100 mesh, and apparent density is 1.00~1.08g/cm3, volume
Density is 0.40~0.50g/m3；The proppant to be coated includes the first resin mutually bonded and process chemical modification
Powder；
The powder by chemical modification includes the first powder by chemical modification and second Jing Guo chemical modification
Powder；
First powder by chemical modification is chemically modified by the first powder body material and obtains, the first powder material
The apparent density of material is 0.35~0.70g/cm3, particle size distribution range is 10~90 μm, median particle diameter D50It is 48 μm, compression strength
For 40~110MPa；
Second powder by chemical modification is chemically modified by the second powder body material and obtains, the second powder material
The apparent density of material is 2.30~3.90g/cm3, the particle size distribution range before chemical modification is 2~13 μm, median particle diameter D50For 8 μ
m；
First resin, first powder by chemical modification and second powder by chemical modification
Mass ratio is 40~60:25~38:15~20；
It is described by chemical modification refer to using modifying agent alkali and dialdehyde to the first powder body material or the second powder body material into
Row processing.
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide, and the dialdehyde includes glutaraldehyde and/or butanedial.
It is further preferred that the mass ratio of alkali and dialdehyde is 1~3:3~1.
The present invention proppant to be coated is super-low-density proppant (polymer composite proppant), and apparent density is
1.00~1.08g/cm3, bulk density is 0.40~0.50g/cm3.Experiments indicate that the proppant to be coated uses warp
Cross the mixed powder material (performance that the mixed powder material has heat resisting and pressure resisting) and thermosetting resin adhesive of chemical modification
Prepolymer can effectively improve the heat resistance of proppant, long-term (up to 30 days) operating temperature >=160 DEG C can satisfy deep layer
The demand of high temperature oil gas well fracturing clear water or slippery water pressing crack construction；Mixed powder material in proppant Jing Guo chemical modification is
Bulk composition, the prepolymer of thermosetting resin adhesive are auxiliary element, the proppant deflection under 10~60MPa clossing pressure
Small, percentage of damage is small, is conducive to proppant filled layer and keeps higher flow conductivity.Further experiment of the present invention shows tree of the present invention
The proppant particles of adipose membrane cladding are similarly super-low-density proppant, and the solubility under 52MPa in percentage of damage and mud acid is equal
It can be remarkably decreased, the former is dropped to about 8%~9% after cladding by about 15%~18% before coating, before the latter is by coating
About 13%~14% drops to about 4%~5% after cladding.
In the above-mentioned supporting agent particle to be coated, it is preferable that first powder body material includes the powder by chemical modification
One of coal ash, hollow glass microballoon are a variety of；It is highly preferred that its heat resisting temperature >=500 DEG C.
In the above-mentioned supporting agent particle to be coated, it is preferable that second powder body material includes the silicon by chemical modification
One of micro mist, bauxite are a variety of；It is highly preferred that its heat resisting temperature >=500 DEG C.
In the above-mentioned supporting agent particle to be coated, it is preferable that first resin includes epoxy resin, phenolic resin and gathers
One of urethane resin is a variety of.
In the above-mentioned supporting agent particle to be coated, it is preferable that the proppant to be coated is prepared as follows to obtain:
First powder body material and the second powder body material are uniformly mixed, mixed powder material is obtained；
The modifying agent is added into the mixed powder material, is then changed under predetermined temperature and predetermined time
Property, obtain the mixed powder of chemically modified the first powder and the second chemically modified powder；
The prepolymer and the first organic solvent of the mixed powder and first resin are added in pelletizer and bonded
It is granulated, obtains particle；
Gained particle is dried, solidify, cool down, is sieved, the proppant to be coated is obtained.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that the total weight of the modifying agent and institute
The weight ratio for stating the first powder body material or the second powder body material is (1:200)~(1:10)；
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that first organic solvent includes first
One or more of alcohol, ethyl alcohol and acetone.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that the prepolymer of first resin with
The weight ratio of first organic solvent is 15~20:1~2.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that the predetermined temperature is 60~120
℃.More preferably 60~100 DEG C, further preferably 70~90 DEG C.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that the predetermined time is 1~6 hour.
More preferably 1~4 hour, further preferably 2~3 hours.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that when the particle is dried, do
Dry temperature is 60~100 DEG C, and the dry time is 10~30 minutes.It is highly preferred that when the particle is dried, it is dry
Temperature be 80~100 DEG C, the dry time be 20~30 minutes.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that the prepolymer of first resin and
The first organic solvent mixing, is added in the mixed powder in batches under 1200~3600 revs/min of mixing speed.
Preferably, after the prepolymer of first resin and first organic solvent mix, in 1200~1500 revs/min of stirring
It is added in the mixed powder in batches under speed.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that the cured temperature be 150~
200 DEG C, the cured time is 5~30 minutes；It is highly preferred that the cured temperature is 180~200 DEG C, the solidification
Time be 5-15 minutes.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that it is described bonding be granulated time be 5~
10 minutes, preferably 8~10 minutes.
In a specific embodiment, the proppant to be coated preparation the following steps are included:
By in the first powder body material and the second powder body material investment pelletizer, stirred with 600~1200 revs/min of speed
Uniformly, mixed powder material is obtained；
Modifying agent is added into the mixed powder material, after mixing, is activated at a temperature of 60~120 DEG C and dry
1~6 hour, obtain the mixed powder of chemically modified the first powder and the second chemically modified powder；
Gained mixed powder is put into pelletizer, is stirred evenly with 1200~3600 revs/min of speed；Then by
After the prepolymer of one resin and the mixing of the first organic solvent, it is added in the pelletizer in batches, and stirring the pelletizer
It mixes speed and is promoted to 3000~6000 revs/min, carry out bonding granulation, obtain particle；
The particle is dried, solidify, cool down, is sieved, the proppant to be coated is obtained.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that by the mixed powder after activation and drying
Body is put into pelletizer, is stirred evenly with 2500~3000 revs/min of speed.
In the above-mentioned method for preparing the supporting agent particle to be coated, it is preferable that by the prepolymer of the first resin and
After pelletizer is added in batches in one organic solvent, the mixing speed of the pelletizer is promoted to 4000~5000 revs/min.
In the proppant particles of above-mentioned resin film cladding, it is preferable that the resin film and the proppant to be coated
The mass ratio of grain is 1:50~3:50.
In the proppant particles of above-mentioned resin film cladding, it is preferable that the material of the resin film is the pre-polymerization of the second resin
The reactant of object and solidified resin promoter.
In the proppant particles of above-mentioned resin film cladding, it is preferable that the prepolymer and the resin of second resin are solid
The mass ratio for changing promotor is 70~88:2~5.
In the proppant particles of above-mentioned resin film cladding, it is preferable that the prepolymer of second resin includes phenolic resin
One of prepolymer, epoxy prepolymer and polyurethane prepolymer are a variety of.
In the proppant particles of above-mentioned resin film cladding, it is preferable that the solidified resin promoter includes ammonium chloride, positive third
Amine, benzene sulfonic acid, 2,4,6- tri- (dimethylamino methyl)-one of phenol and propene carbonate or a variety of.
On the other hand, the present invention provides the preparation method of the proppant of above-mentioned resin film cladding comprising following steps:
In the softening point of the proppant particles to be coated temperature hereinafter, second will be dissolved in the second organic solvent
The spray solution of resin prepolymer and solidified resin promoter is subsequently dried on the surface for the proppant particles to be coated, is solid
Change, sieving obtains the proppant particles of the resin film cladding.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that use spray-fluidized equipment first with fluid
By the proppant particles the to be coated fluidisation, then fluid temperature (F.T.) is increased, it is organic molten to be dissolved in second using compressed gas
The spray solution of the second resin prepolymer and solidified resin promoter in agent is on the surface of the proppant particles to be coated；Spray
After having spilt, improves the fluid temperature (F.T.) and carry out fluidizing the proppant particles solidified to get resin film cladding.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that when first resin is epoxy resin, phenol
One of urea formaldehyde and polyurethane resin or it is a variety of when, it is described by fluid temperature (F.T.) raising be fluid temperature (F.T.) is increased to 60~
100 DEG C (can be by the probe displays temperature of spray-fluidized equipment)；It is by temperature that described raising fluid temperature (F.T.), which carries out fluidisation solidification,
It improves to 150~180 DEG C (can be by the probe displays temperature of spray-fluidized equipment) and carries out 2~10min of fluidisation solidification.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that it is described with fluid by the branch to be coated
It is the proppant particles to be wrapped up that formula ratio is disposably put into the fluidization spray equipment that it is grain fluidized, which to support agent, with 10
The air velocity of~50L/min is fluidized.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that described to be dissolved in second using compressed gas
The spray solution of the second resin prepolymer and solidified resin promoter in organic solvent is in the proppant particles to be coated
Surface is that use pressure be the compressed air of 0.2~0.5MPa by the second resin prepolymer being dissolved in the second organic solvent and tree
The spray solution of rouge curing accelerator is on the surface of the proppant particles to be coated.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that be dissolved in the second organic solvent second
The prepolymer of resin and the total solution weight of solidified resin promoter comprising the second resin of 70wt.%~88wt.% is pre-
Polymers, the second organic solvent of 10wt.%~28wt.% and the solidified resin promoter of 2wt.%~5wt.%.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that the prepolymer of second resin includes phenol
One of urea formaldehyde prepolymer, epoxy prepolymer and polyurethane prepolymer are a variety of.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that the solidified resin promoter includes chlorination
Ammonium, n-propylamine, benzene sulfonic acid, 2,4,6- tri- (dimethylamino methyl)-one of phenol and propene carbonate or a variety of.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that second organic solvent includes ethyl alcohol, first
One of alcohol and acetone are a variety of.
In the preparation method of the proppant of above-mentioned resin film cladding, it is preferable that the be dissolved in the second organic solvent
The mass ratio of the prepolymer of two resins and the solution of solidified resin promoter and the proppant particles to be coated is 1~4:45
~55.
On the other hand, the proppant particles that the present invention provides above-mentioned resin film cladding are transformed as proppant in hydraulic fracturing
In application.
As previously described the proppant particles of resin film provided by the invention cladding can before and after maintaining overlay film density it is basic
Under the premise of constant, the solubility in the percentage of damage and mud acid of proppant is significantly reduced, advantageously reduces fine particle generation, from
And it improves the flow conductivity for supporting hydraulic fracture in hydraulic fracturing transformation and improves oil and gas production.
It in summary, should invention broadly provides the proppant particles and the preparation method and application thereof of resin film cladding
Proppant particles can significantly reduce in the percentage of damage and mud acid of proppant under the premise of density is constant before and after maintaining overlay film
Solubility.Softening temperature of the processing temperature that the method for the present invention uses lower than high molecular material in composite material super-low-density proppant
Degree, will not damage composite material super-low-density proppant, the film covering method is simple, strong operability, is easy to industrial metaplasia
It produces.
Specific embodiment
Technical solution of the present invention is clearly and completely described below with reference to embodiment, it is clear that the embodiment described
It is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Embodiment 1
Present embodiments provide a kind of preparation method of proppant comprising following steps:
(apparent density of flyash is the flyash and the silicon powder of 1000g that 1500g is disposably put into mixed granulation machine
0.35-0.60g/cm3, particle size distribution range is 10-90 μm, median particle diameter D50It is 48 μm, heat resisting temperature >=500 DEG C, pressure resistance
Degree is 83-110MPa；The apparent density of silicon powder is 2.30-3.90g/cm3, particle size distribution range is 2-13 μm, median particle diameter D50
It is 8 μm, heat resisting temperature >=500 DEG C, compression strength is not less than flyash), it is stirred 1 minute with 900 revs/min of speed；
The sodium hydroxide that point 10 batches of addition 200g mass percent concentrations are 12.5% into mixed granulation machine in 5 minutes
Aqueous solution continues stirring 2 minutes later, then divides 5 batches of addition 50g mass percent concentrations into pelletizer in 2.5 minutes
For 50% glutaraldehyde water solution, continue stirring 1 minute later；Material taking-up in mixed granulation machine is put into baking oven, in 80
It is activated at DEG C and 2 hours dry；
The above-mentioned chemically modified mixed powder material of 1275g is put into, disposably into mixed granulation machine with 2500 revs/min
The speed of clock stirs 1 minute；
Mixed granulation machine mixing speed is improved most 3600 revs/min, divides 10 batches and mixed liquor is added thereto, the mixing
Liquid is mixed by the prepolymer of 28g acetone and 280g thermosetting phenolic resin；
The mixing speed of mixed granulation machine is increased to 4000 revs/min, bonding is granulated 8 minutes, is of moderate size
Particle；
Obtained particle will be granulated and be put into drying oven, it is 20 minutes dry at 90 DEG C, then solidify 10 minutes in 195 DEG C
Afterwards, it takes out cooling and is sieved, obtain the proppant particles of 20-100 mesh.
Proppant provided in this embodiment is a kind of proppant of extremely-low density, and the apparent density of the proppant is 1.07g/
cm3, bulk density 0.49g/cm3。
Embodiment 2
Present embodiments provide a kind of preparation method of proppant comprising following steps:
(hollow glass is micro- for the hollow glass microballoon and the silicon powder of 1000g that 1200g is disposably put into mixed granulation machine
The apparent density of ball is 0.35-0.60g/cm3, particle size distribution range is 10-90 μm, median particle diameter D50It is 48 μm, heat resisting temperature >=
500 DEG C, compression strength 83-110MPa；The apparent density of silicon powder is 2.30-3.90g/cm3, particle size distribution range is 2-13 μ
M, median particle diameter D50It is 8 μm, heat resisting temperature >=500 DEG C, compression strength is not less than hollow glass microballoon), with 900 revs/min
Speed stirs 1 minute；
The potassium hydroxide that point 10 batches of addition 176g mass percent concentrations are 12.5% into mixed granulation machine in 5 minutes
Aqueous solution continues stirring 2 minutes later, then divides 5 batches of addition 88g mass percent concentrations into pelletizer in 2.5 minutes
For 25% butanedial aqueous solution, continue stirring 1 minute later；Material taking-up in mixed granulation machine is put into baking oven, in 90
It is activated at DEG C and 1.5 hours dry；
The above-mentioned chemically modified mixed powder material of 1122g is put into, disposably into mixed granulation machine with 2500 revs/min
The speed of clock stirs 1 minute；
Mixed granulation machine mixing speed is improved most 3600 revs/min, divides 10 batches and mixed liquor is added thereto, the mixing
Liquid is mixed by the prepolymer of 26g ethyl alcohol and 260g thermosetting epoxy resin；
The mixing speed of mixed granulation machine is increased to 4500 revs/min, bonding is granulated 8 minutes, is of moderate size
Particle；
Obtained particle will be granulated and be put into drying oven, it is 20 minutes dry at 90 DEG C, then solidify 10 minutes in 195 DEG C
Afterwards, it takes out cooling and is sieved, obtain the proppant particles of 20-100 mesh.
Proppant provided in this embodiment is a kind of proppant of extremely-low density, and the apparent density of the proppant is 1.05g/
cm3, bulk density 0.46g/cm3。
Embodiment 3
Present embodiments provide a kind of preparation method of proppant comprising following steps:
(hollow glass is micro- for the hollow glass microballoon and the bauxite of 1100g that 1500g is disposably put into mixed granulation machine
The apparent density of ball is 0.35-0.60g/cm3, particle size distribution range is 10-90 μm, median particle diameter D50It is 48 μm, heat resisting temperature >=
500 DEG C, compression strength 83-110MPa；The apparent density of bauxite is 2.30-3.90g/cm3, particle size distribution range is 2-13 μ
M, median particle diameter D50It is 8 μm, heat resisting temperature >=500 DEG C, compression strength is not less than hollow glass microballoon), with 900 revs/min
Speed stirs 1 minute；
The sodium hydroxide that point 10 batches of addition 208g mass percent concentrations are 12.5% into mixed granulation machine in 5 minutes
Aqueous solution continues stirring 2 minutes later, then divides 5 batches of addition 52g mass percent concentrations into pelletizer in 2.5 minutes
For 50% glutaraldehyde water solution, continue stirring 1 minute later；Material taking-up in mixed granulation machine is put into baking oven, in 80
It is activated at DEG C and 2 hours dry；
The above-mentioned chemically modified mixed powder material of 1326g is put into, disposably into mixed granulation machine with 1800 revs/min
The speed of clock stirs 1 minute；
Mixed granulation machine mixing speed is improved most 3600 revs/min, divides 10 batches and mixed liquor is added thereto, the mixing
Liquid is mixed by the prepolymer of 30g ethyl alcohol and 300g thermosetting phenolic resin；
Mixed granulation machine mixing speed is increased to 5000 revs/min, bonding is granulated 8 minutes, being of moderate size
Grain；
Obtained particle will be granulated and be put into drying oven, it is 20 minutes dry at 90 DEG C, then solidify 10 minutes in 190 DEG C
Afterwards, it takes out cooling and is sieved, obtain the proppant particles of 20-100 mesh.
Proppant provided in this embodiment is a kind of proppant of extremely-low density, and the apparent density of the proppant is 1.08g/
cm3, bulk density 0.49g/cm3。
Embodiment 4
A kind of preparation method of proppant is present embodiments provided, method includes the following steps:
(hollow glass is micro- for the hollow glass microballoon and the silicon powder of 700g that 1500g is disposably put into mixed granulation machine
The apparent density of ball is 0.35-0.60g/cm3, and particle size distribution range is 10-90 μm, median particle diameter D50It is 8 μm, heat resisting temperature >=
500 DEG C, compression strength 83-110MPa；The apparent density of silicon powder is 2.30-3.90g/cm3, and particle size distribution range is 2-13 μ
M, median particle diameter D50It is 8 μm, heat resisting temperature >=500 DEG C, compression strength is not less than hollow glass microballoon), with 1500 revs/min
Speed stirs evenly；
The potassium hydroxide that point 10 batches of addition 176g mass percent concentrations are 12.5% into mixed granulation machine in 5 minutes
Aqueous solution continues stirring 2 minutes later, then divides 5 batches of addition 44g mass percent concentrations into pelletizer in 2.5 minutes
For 50% glutaraldehyde water solution, continue stirring 1 minute later；Material taking-up in mixed granulation machine is put into baking oven, in 85
It is activated at DEG C and 2.5 hours dry.
Above-mentioned the first chemically modified powder body material of 1122g and chemically modified is disposably put into mixed granulation machine
The second powder body material mixture, stirred 1 minute with 1800 revs/min of speed；
Mixed granulation machine mixing speed is improved most 4000 revs/min, divides 10 batches and mixed liquor is added thereto, the mixing
Liquid is mixed by the prepolymer of 20g methanol and 200g thermosetting epoxy resin；
The mixing speed of mixed granulation machine is increased to 5000 revs/min, bonding is granulated 8 minutes, is of moderate size
Particle；
Obtained particle will be granulated and be put into drying oven, it is 20 minutes dry at 90 DEG C, then solidify 10 minutes in 200 DEG C
Afterwards, it takes out cooling and is sieved, obtain the proppant particles of 20-100 mesh.
Proppant provided by the invention is a kind of proppant of extremely-low density, and the apparent density of the proppant is 1.03g/cm3,
Bulk density is 0.42g/cm3。
Embodiment 5
Present embodiments provide a kind of preparation method of proppant comprising following steps:
(hollow glass is micro- for the hollow glass microballoon and the silicon powder of 800g that 1500g is disposably put into mixed granulation machine
The apparent density of ball is 0.35-0.60g/cm3, particle size distribution range is 10-90 μm, median particle diameter D50It is 48 μm, heat resisting temperature >=
500 DEG C, compression strength 83-110MPa；The apparent density of silicon powder is 2.30-3.90g/cm3, particle size distribution range is 2-13 μ
M, median particle diameter D50It is 8 μm, heat resisting temperature >=500 DEG C, compression strength is not less than hollow glass microballoon), with 1500 revs/min
Speed stirs evenly；
The sodium hydroxide that point 10 batches of addition 184g mass percent concentrations are 12.5% into mixed granulation machine in 5 minutes
Aqueous solution continues stirring 2 minutes later, then divides 5 batches of addition 46g mass percent concentrations into pelletizer in 2.5 minutes
For 50% glutaraldehyde water solution, continue stirring 1 minute later；Material taking-up in mixed granulation machine is put into baking oven, in 80
It is activated at DEG C and 3 hours dry；
Above-mentioned the first chemically modified powder body material of 1173g and chemically modified is disposably put into mixed granulation machine
The second powder body material mixture, stirred 1 minute with 1500 revs/min of speed；
Mixed granulation machine mixing speed is improved most 3600 revs/min, divides 10 batches and mixed liquor is added thereto, the mixing
Liquid is mixed by the prepolymer of 24g acetone and 240g thermosetting phenolic resin；
The mixing speed of mixed granulation machine is increased to 5000 revs/min, bonding is granulated 8 minutes, is of moderate size
Particle；
Obtained particle will be granulated and be put into drying oven, it is 20 minutes dry at 90 DEG C, then solidify 10 minutes in 200 DEG C
Afterwards, it takes out cooling and is sieved, obtain the proppant particles of 20-100 mesh.
Proppant provided in this embodiment is a kind of proppant of extremely-low density, and the apparent density of the proppant is 1.02g/
cm3, bulk density 0.41g/cm3。
Comparative example 1
This comparative example provides a kind of preparation method of proppant comprising following steps:
The hollow glass microballoon of 750g and the silicon powder (hollow glass microballoon of 400g are disposably put into mixed granulation machine
Apparent density be 0.35-0.60g/cm3, particle size distribution range is 10-90 μm, median particle diameter D50It is 48 μm, heat resisting temperature >=500
DEG C, compression strength 83-110MPa；The apparent density of silicon powder is 2.30-3.90g/cm3, particle size distribution range is 2-13 μm, in
It is worth partial size D50It is 8 μm, heat resisting temperature >=500 DEG C, compression strength is not less than hollow glass microballoon), with 1500 revs/min of speed
It stirs evenly；
Mixed granulation machine mixing speed is improved most 3600 revs/min, divides 10 batches and mixed liquor is added thereto, the mixing
Liquid is mixed by the prepolymer of 24g acetone and 240g thermosetting phenolic resin；
The mixing speed of mixed granulation machine is increased to 5000 revs/min, bonding is granulated 8 minutes, is of moderate size
Particle；
Obtained particle will be granulated and be put into drying oven, it is 20 minutes dry at 90 DEG C, then solidify 10 minutes in 200 DEG C
Afterwards, it takes out cooling and is sieved, obtain the proppant particles of 20-100 mesh.
Proppant provided in this embodiment is a kind of proppant of extremely-low density, and the apparent density of the proppant is 1.02g/
cm3, bulk density 0.41g/cm3。
Table 1
Above-described embodiment 1-5 and comparative example 1 the proppant product provided are tested for the property, test result such as 1 institute of table
Show.
In table 1, the test of percentage of damage is referring to according to People's Republic of China's oil and gas industry standard SY/T5108-
2006 " fracturing propping agents and performance indicator and test recommended methods "；It is 0.98g/cm to concentration is laid2Proppant filled layer
The test of compressed shape variable under 35MPa and 52MPa is referred to the progress of the test method in US 6330916B1, main mistake
Journey is as follows:
SY/T 5108-2006 " fracturing propping agents are put into the proppant that the balance that sensibility reciprocal is 0.01g weighs constant weight
And performance indicator and test recommended method " crushing chamber (diameter 50.8mm) that is recommended to use, so that proppant filling concentration is
0.98g/cm2, it is put into piston and is rotated 180 °, the crushing chamber equipped with sample is placed on press table；
Predetermined load (35MPa or 52MPa) is at the uniform velocity added on compression crushing chamber with the constant load time of 60s, it is steady to carry
120s.The pressure head of press there is load to control and test and Bit andits control and test function, wherein load control and measurement accuracy
For 0.01MPa, Bit andits control and measurement accuracy are 0.01mm；
The displacement registration automatic clear of pressure head when load is 0.70MPa, the displacement registration of the pressure head when surely carrying 120s
For proppant filled layer deflection.Wherein, instrument used in test process is the production of Jinan Pu Ye mechanical & electrical technology Co., Ltd
Press (model DYZ-300).
As shown in Table 1, the proppant filled layer deformation quantity that embodiment 1-5 is provided is significantly lower than US 6330916B1
A kind of disclosed density is 1.05g/cm3Proppant (proppant glass transition temperature in 6330916 B1 of US is 145 DEG C,
Percentage of damage < 0.5% at 55MPa and 95 DEG C, when proppant filling concentration is 0.98g/cm2When, the compression under 35MPa and 52MPa
Deformation quantity is respectively 5.77mm and 6.17mm).The hydraulic fracture flow conductivity for having proppant to support is the clossing pressure in reservoir
Under permeability (Kf) and fracture support slit width (Wf) product, it follows that when proppant density is close and it is consistent to fill concentration
Under conditions of, proppant filled layer deformation quantity is smaller, and fracture support slit width is bigger, then fracture condudtiviy is higher, therefore implements
The proppant that example 1-5 is provided is conducive to keep higher fracture condudtiviy.
In addition, can also be known by the result in table 1, the comparative example 1 for not carrying out chemical modification to two kinds of powder body materials is provided
Proppant percentage of damage and the performance indicators such as filled layer deformation quantity significantly lower than having carried out chemical modification to two kinds of powder body materials
Embodiment 5 provide proppant.
In addition, being carried out brokenly again after the embodiment 1-5 proppant provided is placed in being heated 30 days in 160 DEG C of baking oven
Broken rate and compressed shape variable test, the results are shown in Table 2.The result shows that, the proppant that embodiment 1-5 is provided is through too long in table 2
Phase high temperature still maintains preferable performance indicator, is conducive to the subsurface environment for adapting to deep layer high temperature oil gas well.
Table 2
Embodiment 6
The present embodiment provides a kind of proppant particles and preparation method thereof of resin film cladding, wherein the support to be coated
Agent particle is the proppant that embodiment 1 is prepared, and the phenolic resin softening point in the proppant is 192~197 DEG C, the preparation
Specific step is as follows for method: by 20g phenolic resin prepolymer (Shandong holy well new material limited liability company, model
5EXPO974) and 0.6g propene carbonate is dissolved in 5g acetone, stirs evenly stand-by (calling resin solution 1 in the following text).It is set to spray-fluidized
It is 1.07g/cm that 500g density is disposably put into standby3, size be 20~100 mesh composite material super-low-density proppant
Grain, is fluidized proppant particles with the air velocity of 45L/min.Opening spray-fluidized equipment, (the refined journey instrument and equipment in Shanghai is limited
Company production model YC1000) heating unit, when be located at fluidisation position temperature probe temperature be 80 DEG C when, use pressure
Resin solution 1 is sprayed on proppant particles surface for the compressed air of 0.4MPa.After resin solution 1 is sprayed, improve
The power of the heating unit of spray-fluidized equipment starts timing simultaneously when the temperature probe temperature for being located at fluidisation position is 170 DEG C
Keep 3min.The heating unit of spray-fluidized equipment is closed later, is sieved after product is cooling, is obtained 20~100 mesh of the present embodiment
Resin film cladding super-low-density proppant.
Embodiment 7
The present embodiment provides the proppant particles and preparation method thereof of resin film cladding, wherein the proppant to be coated
Grain is the proppant that embodiment 2 is prepared, and the epoxy resin softening point in the proppant is 191~196 DEG C, the preparation method
Specific step is as follows: by 36g epoxy prepolymer (Yancheng, Jiangsu Province one plus one Electron Material Co., Ltd, model YY4150)
It is dissolved in 10g ethyl alcohol with 1.2g n-propylamine, stirs evenly stand-by (calling resin solution 2 in the following text).It is disposably thrown into spray-fluidized equipment
Entering 1000g density is 1.05g/cm3, size be 20~100 mesh composite material super-low-density proppant particle, with 40L/min
Air velocity proppant particles are fluidized.Open the spray-fluidized equipment (type of the refined journey experimental instruments and equipment limited production in Shanghai
Number be YC1000) heating unit, when be located at fluidisation position temperature probe temperature be 90 DEG C when, the pressure for being 0.5MPa with pressure
Resin solution 2 is sprayed on proppant particles surface by contracting air.After resin solution 2 is sprayed, spray-fluidized equipment is improved
Heating unit power, when be located at fluidisation position temperature probe temperature be 175 DEG C when, start timing simultaneously keep 5min.It
The heating unit of spray-fluidized equipment is closed afterwards, is sieved after product is cooling, and the resin film cladding of 20~100 mesh of the present embodiment is obtained
Super-low-density proppant.
Embodiment 8
The present embodiment provides the proppant particles and preparation method thereof of resin film cladding, wherein the proppant to be coated
Grain is the proppant that embodiment 3 is prepared, and phenolic resin softening point is 187~191 DEG C in the proppant.Preparation method tool
Steps are as follows for body: by 20g polyurethane resin prepolymer (Shandong holy well new material limited liability company, model PUP0975) and
The 2 of 0.5g, 4,6- tri- (dimethylamino methyl)-phenol are dissolved in 5g methanol, stir evenly stand-by (calling resin solution 3 in the following text).To spray
It is 1.08g/cm that 500g density is disposably put into mist fluidizing equipment3, size be 20~100 mesh composite material extremely-low density branch
Agent particle is supportted, is fluidized proppant particles with the air velocity of 50L/min.Opening spray-fluidized equipment, (the refined gift of money for a friend going on a journey device in Shanghai is set
The model YC1000 of standby Co., Ltd's production) heating unit, when the temperature probe temperature for being located at fluidisation position is 70 DEG C,
Resin solution 3 is sprayed on proppant particles surface by the compressed air for being 0.5MPa with pressure.It is sprayed to resin solution 3
Afterwards, the power for improving the heating unit of spray-fluidized equipment is opened when the temperature probe temperature for being located at fluidisation position is 175 DEG C
Beginning timing simultaneously keeps 3min.The heating unit of spray-fluidized equipment is closed later, is sieved after product is cooling, is obtained the present embodiment 20
The super-low-density proppant of the resin film cladding of~100 mesh.
Embodiment 9
The present embodiment provides the proppant particles and preparation method thereof of resin film cladding, wherein the proppant to be coated
Grain is the proppant that embodiment 4 is prepared, and epoxy resin softening point is 193~197 DEG C in the proppant.Preparation method tool
Steps are as follows for body: by the chlorination of 25g phenolic resin prepolymer (the generous synthesis Co., Ltd in Chongqing, model PF-10) and 0.6g
Ammonium is dissolved in 5g ethyl alcohol, stirs evenly stand-by (calling resin solution 4 in the following text).600g density is disposably put into spray-fluidized equipment is
1.03g/cm3, size be 20~100 mesh composite material super-low-density proppant particle, with the air velocity of 35L/min will prop up
It is grain fluidized to support agent.Open adding for spray-fluidized equipment (the model YC1000 of the refined journey experimental instruments and equipment limited production in Shanghai)
Hot cell, when the temperature probe temperature for being located at fluidisation position is 80 DEG C, the compressed air for being 0.5MPa with pressure is molten by resin
Liquid 4 is sprayed on proppant particles surface.After resin solution 4 is sprayed, the function of the heating unit of spray-fluidized equipment is improved
Rate starts timing and keeps 3min when the temperature probe temperature for being located at fluidisation position is 180 DEG C.Spray-fluidized is closed later
The heating unit of equipment is sieved after product is cooling, obtains the extremely-low density support of the resin film cladding of 20~100 mesh of the present embodiment
Agent.
Embodiment 10
The present embodiment provides the proppant particles and preparation method thereof of resin film cladding, wherein the proppant to be coated is
The proppant that embodiment 5 is prepared, the softening point of the polyurethane resin in the proppant are 186~190 DEG C.The preparation method
Specific step is as follows: by 25g epoxy prepolymer (Yancheng, Jiangsu Province one plus one Electron Material Co., Ltd, model YY4150)
It is dissolved in 5g acetone with the benzene sulfonic acid of 0.6g, stirs evenly stand-by (calling resin solution 5 in the following text).To spray-fluidized equipment (the refined journey in Shanghai
Experimental instruments and equipment limited production model YC1000) in disposably put into 600g density be 1.02g/cm3, size be 20~
The composite material super-low-density proppant particle of 100 mesh, is fluidized proppant particles with the air velocity of 50L/min.
The heating unit for opening spray-fluidized equipment, when the temperature probe temperature for being located at fluidisation position is 80 DEG C, with pressure
Power is that resin solution 5 is sprayed on proppant particles surface by the compressed air of 0.5MPa.After resin solution 5 is sprayed, mention
The power of the heating unit of high spray-fluidized equipment starts timing when the temperature probe temperature for being located at fluidisation position is 175 DEG C
And keep 6min.The heating unit of spray-fluidized equipment is closed later, is sieved after product is cooling, is obtained the present embodiment 20~100
The composite material super-low-density proppant of purpose resin film cladding.
It is ultralow close to the polymer composite of the cladding of resin film obtained by above embodiments provided in the present invention
Degree proppant product is tested for the property, and percentage of damage and mud acid solubility are according to People's Republic of China's oil and gas industry
Standard SY/T 5108-2006 " fracturing propping agents and performance indicator and test recommended method ".Composite material super-low-density proppant
Test result before and after resin-coated film see the table below 3:
Table 3
From Table 2, it can be seen that the polymer composite proppant particles of present invention gained resin film cladding are in 52MPa
Solubility in lower percentage of damage and mud acid can be remarkably decreased, after the former drops to cladding by about 15%~18% before coating
About 8%~9%, the latter is dropped to about 4%~5% after cladding by about 13%~14% before coating.
Finally it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
It can so modify to technical solution documented by previous embodiment, or some or all of the technical features are carried out
Same replacement；And these are modified or replaceed, and corresponding technical solution is not made to be detached from the model of technical solution of various embodiments of the present invention
It encloses.
Claims (15)
1. a kind of proppant particles of resin film cladding, apparent density is 1.00~1.10g/cm3；The proppant to be coated is 20
The particle of~100 mesh, apparent density are 1.00~1.08g/cm3, bulk density is 0.40~0.50g/m3；It is described to be coated
Proppant includes the first resin mutually bonded and the powder Jing Guo chemical modification；
The powder by chemical modification includes the first powder by chemical modification and the second powder Jing Guo chemical modification；
First powder by chemical modification is chemically modified by the first powder body material and obtains, first powder body material
Apparent density is 0.35~0.70g/cm3, particle size distribution range is 10~90 μm, and compression strength is 40~110MPa；
Second powder by chemical modification is chemically modified by the second powder body material and obtains, second powder body material
Apparent density is 2.30~3.90g/cm3, the particle size distribution range before chemical modification is 2~13 μm；
The quality of first resin, first powder by chemical modification and second powder by chemical modification
Than for 40~60:25~38:15~20；
It is described to refer to using modifying agent alkali and dialdehyde to the first powder body material or the second powder body material by chemical modification
Reason；
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide, and the dialdehyde includes glutaraldehyde and/or butanedial；
It is further preferred that the mass ratio of alkali and dialdehyde is 1~3:3~1.
2. the proppant particles of resin film cladding according to claim 1, wherein first powder body material includes fine coal
One of ash, hollow glass microballoon are a variety of；Preferably, median particle diameter D of first powder body material before chemical modification50
It is 48 μm；Preferably, heat resisting temperature >=500 DEG C.
3. the proppant particles of resin film cladding according to claim 1, wherein second powder body material includes that silicon is micro-
One of powder, bauxite are a variety of；Preferably, median particle diameter D of second powder body material before chemical modification50It is 8 μm；
Preferably, heat resisting temperature >=500 DEG C.
4. the proppant particles of resin film cladding according to claim 1, wherein first resin includes asphalt mixtures modified by epoxy resin
One of rouge, phenolic resin and polyurethane resin are a variety of.
5. the proppant particles of resin film cladding according to claim 1, wherein the proppant to be coated is by as follows
Method is prepared:
First powder body material and the second powder body material are uniformly mixed, mixed powder material is obtained；
The modifying agent is added into the mixed powder material, is then modified, obtains under predetermined temperature and predetermined time
To the mixed powder of chemically modified the first powder and the second chemically modified powder；
The prepolymer and the first organic solvent of the mixed powder and first resin are added in pelletizer and carry out bonding granulation,
Obtain particle；
Gained particle is dried, solidify, cool down, is sieved, the proppant to be coated is obtained；
Preferably, the weight ratio of the modifying agent total weight and first powder body material or the second powder body material be (1:
200)~(1:10)；
Preferably, first organic solvent includes one or more of methanol, ethyl alcohol and acetone；
Preferably, the weight ratio of the prepolymer of first resin and first organic solvent is 15~20:1~2；
Preferably, the predetermined temperature is 60~120 DEG C, more preferably 70~90 DEG C；
Preferably, the predetermined time is 1~6 hour, more preferably 2~3 hours；
Preferably, when the particle being dried, dry temperature is 60~100 DEG C, and the dry time is 10~30 minutes.
6. the proppant particles of resin film according to claim 1 cladding, wherein the resin film and described to be coated
The mass ratio of proppant particles is 1:50~3:50.
7. the proppant particles of resin film cladding according to claim 1, wherein the material of the resin film is the second tree
The prepolymer of rouge and the reactant of solidified resin promoter；
Preferably, the mass ratio of the prepolymer of second resin and the solidified resin promoter is 70~88:2~5；
Preferably, the prepolymer of second resin includes phenolic resin prepolymer, epoxy prepolymer and polyurethane prepolymer
One of object is a variety of；
Preferably, the solidified resin promoter includes ammonium chloride, n-propylamine, benzene sulfonic acid, 2,4,6- tri- (dimethylamino methyls)-
One of phenol and propene carbonate are a variety of.
8. the preparation method of the proppant particles of resin film cladding according to any one of claims 1 to 7 comprising following step
It is rapid:
In the softening point of the proppant particles to be coated temperature hereinafter, the second resin that will be dissolved in the second organic solvent
Prepolymer and solidified resin promoter spray solution on the surface for the proppant particles to be coated, be subsequently dried, solidify,
Sieving obtains the proppant particles of the resin film cladding.
9. preparation method according to claim 8, wherein spray-fluidized equipment is used to be coated first with fluid by described
Proppant particles fluidisation, then fluid temperature (F.T.) is increased, the second tree that will be dissolved in the second organic solvent using compressed gas
The prepolymer of rouge and the spray solution of solidified resin promoter are on the surface of the proppant particles to be coated；After having sprayed, mention
The high fluid temperature (F.T.) carries out fluidisation and solidifies to get the proppant particles of resin film cladding.
10. preparation method according to claim 9, wherein when first resin is epoxy resin, phenolic resin and is gathered
One of urethane resin or it is a variety of when, it is described by fluid temperature (F.T.) raising be that fluid temperature (F.T.) is increased to 60~100 DEG C；It is described to mention
It is to improve temperature to 150~180 DEG C to carry out 2~10min of fluidisation solidification that the high fluid temperature (F.T.), which carries out fluidisation solidification,.
11. preparation method according to claim 9, wherein it is described with fluid by the proppant particles stream to be coated
Change is the proppant particles to be wrapped up that formula ratio is disposably put into the fluidization spray equipment, with 10~50L/min
Air velocity fluidized.
12. preparation method according to claim 9, wherein described to be dissolved in the second organic solvent using compressed gas
The prepolymer of the second resin and the spray solution of solidified resin promoter on the surface of the proppant particles to be coated be to adopt
With the compressed air that pressure is 0.2~0.5MPa by the prepolymer and resin solidification of the second resin being dissolved in the second organic solvent
The spray solution of promotor is on the surface of the proppant particles to be coated.
13. according to the described in any item preparation methods of claim 8~12, wherein be dissolved in the second organic solvent second
The prepolymer of resin and the total solution weight of solidified resin promoter comprising the second resin of 70wt.%~88wt.%
Prepolymer, the second organic solvent of 10wt.%~28wt.% and the solidified resin promoter of 2wt.%~5wt.%；
Preferably, the prepolymer of second resin includes phenolic resin prepolymer, epoxy prepolymer and polyurethane prepolymer
One of object is a variety of；
Preferably, the solidified resin promoter includes ammonium chloride, n-propylamine, benzene sulfonic acid, 2,4,6- tri- (dimethylamino methyls)-
One of phenol and propene carbonate are a variety of；
Preferably, second organic solvent includes one of ethyl alcohol, methanol and acetone or a variety of.
14. preparation method according to claim 13, wherein second resin prepolymer being dissolved in the second organic solvent
The mass ratio of the solution of object and solidified resin promoter and the proppant particles to be coated is 1~4:45~55.
15. the proppant particles of the described in any item resin film claddings of claim 1~7 are transformed as proppant in hydraulic fracturing
In application.
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