CN109735321A - A kind of preparation method of pH response type intelligent proppant - Google Patents
A kind of preparation method of pH response type intelligent proppant Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of pH response type intelligent proppant, using molecule Graft Method, it is modified including proppant surface initiator, molecule Graft Method is grafted response type functional polymer, obtained intermediate product is filtered, washed, it is handled under high temperature or acidulated condition to get response type intelligent proppant.Resin cladding process also can be used to be prepared.The present invention chemically start with by molecular modification, by connecting functionalized macromolecular chain in proppant surface, realizes the intelligent response of proppant.The modified proppant of obtained intelligence has apparent pH response characteristic, at the low ph, contact angle of the oil droplet under the conditions of contact angle of modified proppant surface is than high ph-values is smaller, therefore under the conditions of high ph-values, and oil droplet is more preferable in the circulation of modified proppant surface.The present invention is suitable for different sizes, variety classes proppant, has good application potential.
Description
Technical field
The present invention relates to a kind of preparation method of pH response type intelligent proppant, belongs to oil-gas field fracturing volume increase and chemistry changes
The technical field of property proppant.
Background technique
Hydraulic fracturing is the important technical of well production increment transformation, either conventional hyposmosis, extra-low permeability oil
Gas reservoir or the shale of untraditional reservoir, tight sandstone reservoir, hydraulic fracturing all play crucial production-increasing function, especially
Unconventional reservoir, without hydraulic fracturing, the oil gas of underground is difficult to mined.Hydraulic fracturing is exactly to utilize high pressure pump group, will be pressed
It splits liquid pump and enters stratum, form one or more crack with certain geometric dimension in the earth formation, fracture length is generally from tens
Rice arrives several hundred rice, highly meter height from several meters to tens, the several mm wides of width.Then load fluid (the pressure break of proppant will be had
The mixture of liquid and proppant) it is injected into crack.After pressure break, fracturing liquid rubber-breaking, which returns, is discharged to ground, and proppant is split staying in
In seam, play the role of supporting crack, crack is kept to be in open configuration, the hole between proppant particles is formation oil air water
Circulation passage is provided, to play the effect of fracturing yield increasing.Proppant is one of the key factor of effect of increasing production quality, good
The proppant flow conductivity with higher permeability of crack (width in crack multiplied by), can provide smooth circulation for oil gas water
Channel.
Proppant surface is chemically modified, response type or sensitive intelligent proppant are prepared, is Future Technologies hair
One important trend of exhibition.The basic reason of the appearance of response type intelligent proppant is, it is desirable to be existed by controlling proppant surface
Different response characteristics under different fracturing fluid environment improve the flow conductivity of proppant, increase the migration length of proppant.In reality
In the work of border, extend pressure break timeliness, and further control effectively to pressure break spot effect.Further, it is also possible to oil well
Play the role of increasing oil control water, there is positive effect to oil well output is improved.
Chinese patent document CN 101665686A (it is modified 200810146577.8) application number: to disclose a kind of surface
The preparation method of proppant includes the following steps: that the matrix of proppant is heated to 100-240 DEG C by (A)；(B) to after heating
Resin is added in described matrix and stirs and forms mixture, so that the resin adds high score in described matrix surface coating
Sub- surfactant, curing agent simultaneously stir, so that overlay film starts to solidify in the resin in described matrix；(C) resin-
The mixture of matrix starts that lubricant and hydrophobic polymer are added before agglomerating and stirs；(D) it is walked through cooling, broken, screening
Be supported agent after mixture obtained in rapid C.
Chinese patent document CN 103849117A (application number: 201210504777.2) discloses a kind of fracturing propping agents
Preparation method and the fracturing propping agents that are prepared by this method.The preparation method of the fracturing propping agents includes that will contain
There is the solidification of the mixture of particles of aggregates and overlay film binder, wherein the overlay film binder is hydrophilic resin oil/fat composition, and institute
The preparation method for stating hydrophilic resin oil/fat composition includes: that epoxy resin is carried out first at least one modifying agent to contact, described
The condition of first contact makes the base for being capable of providing proton in PART EPOXY base and the modifying agent in the epoxy resin
Group's reaction；And under conditions of being enough to make sour forming salt, mixture and at least one alkaline matter that the first contact is obtained
Carry out the second contact.
But two problems that current response type proppant is generally existing: 1, preparation method is still using traditional overlay film
Method is not broken through and is innovated in method.2, response sensitivity and low precision, response performance are coarse.Therefore, response type or responsive type
The research and development of intelligent proppant, the exploitation to routine and unconventional oil and gas future, all have important meaning.
Summary of the invention
In view of the deficiencies of the prior art, modified fining present in especially current proppant surface functional response modification
The defects of effect is poor, the present invention provide a kind of preparation method of response type intelligent proppant, especially prop up the intelligence of pH response
Support the preparation method of agent.The present invention chemically start with by molecular modification, real by connecting functionalized macromolecular chain in proppant surface
The intelligent response of existing proppant.The modified proppant of obtained intelligence has apparent pH response characteristic, at the low ph, oil
The contact angle dripped under the conditions of the contact angle of modified proppant surface is than high ph-values is smaller, therefore under the conditions of high ph-values, oil droplet exists
The circulation of modified proppant surface is more preferable.Used preparation method is versatile, is suitable for different sizes, variety classes branch
Agent is supportted, and the surface for being suitable for a variety of proppants such as traditional roughing sand, haydite and glass microsphere is modified, has application well latent
Power.
Technical scheme is as follows:
A kind of preparation method of response type intelligent proppant is comprised the following steps that using molecule Graft Method
(1) proppant surface initiator is modified: being dispersed proppant in organic solvent and is made into mixed with proppants liquid, to branch
Initiator is added in support agent mixed liquor, under protective gas protection, heating stirring reaction makes the upper functionality of proppant surface modification
Initiator obtains the proppant of initiator modification；
(2) molecule Graft Method is grafted response type functional polymer: the support modified under protective gas protection to initiator
Catalyst, solvent, the monomer containing functional group, ligand are sequentially added in agent, under protective gas protection, heating condition, stirring
Reaction, obtains intermediate product；
(3) obtained intermediate product is filtered, washed, is handled under high temperature or acidulated condition to get response type intelligence
It can proppant.
, according to the invention it is preferred to, the mass ratio of proppant and initiator is (5-100) in step (1): 2；
Preferably, the proppant partial size is 20-140 mesh, and the proppant is the conventional branch such as quartz sand or haydite
Support the unconventional proppant such as agent or glass microsphere；
Preferably, the initiator be halogenated silanes, alpha-brominated ester, α-halogenatedketone, alpha-halogenate nitrile, aryl sulfonyl chloride,
Azodiisobutyronitrile contains bromo-silicane, chlorodimethylsilane bromide propyl isobutyrate, double bromine isobutyryl oxidative ethanes or bromo isobutyryl
Bromine；
Preferably, the organic solvent be acetone, butanone, toluene, dimethylbenzene, methyl phenyl ethers anisole, n,N-Dimethylformamide,
Dimethyl sulfoxide, methanol, acetonitrile or chloroform；The quality of proppant and the volume ratio of organic solvent are 0.1-50g/mL；
Preferably, the protective gas is nitrogen or argon gas；
Preferably, the temperature of heating stirring reaction is 50-150 DEG C, and the reaction time is 0.5-5 hours.
, according to the invention it is preferred to, the monomer containing functional group described in step (2) is epoxy monomer, amine list
Body or the monomer of base class containing carboxylic acid；It is further preferred that the epoxy monomer is bisphenol-type epoxy resin, vinylcyclohexene
Dicyclic oxide, o-phthalic acid diglycidyl ester, the amine monomers are melamine, urea, ethylamine etc., described
The monomer of base class containing carboxylic acid be acrylic acid, acrylic acid methyl ether, ethyl acrylate；
Preferably, the catalyst is cuprous salt, further preferred cuprous bromide or stannous chloride；
Preferably, the ligand is pyridines or amine substance, it is further preferred that the ligand is bipyridyl or five
Methyl diethylene triamine；
Preferably, the solvent is acetone, methylethylacetone, dimethyl sulfoxide, dimethylformamide；
Preferably, the protective gas is nitrogen or argon gas.
, according to the invention it is preferred to, the mass ratio of initiator is modified in step (2) proppant and catalyst are as follows: (10-
100): (2-5)；
Preferably, the mass ratio of the additional amount of ligand and catalyst are as follows: (40-60): (20-40)；
Preferably, the mass ratio of the proppant and the monomer containing functional group of initiator modification are as follows: (500-1000)-
(0.1-50)；
Preferably, the quality of the proppant of initiator modification and the volume ratio of solvent are 0.1-50g/mL.
, according to the invention it is preferred to, mixing time is 1-40 hours in step (2)；In proppant surface under stirring condition
Molecule graft polymerization reaction occurs；
Preferably, the temperature of heating condition is 40-160 DEG C, and the reaction time is 0.5-12 hours.
, according to the invention it is preferred to, the detergent of washing is methanol, water in step (3)；
Preferably, high-temperature process temperature is 50-150 DEG C；
Preferably, the pH value of acidulated condition is 1-5, and further preferred acid is acetic acid, hydrochloric acid, trifluoroacetic acid.
The present invention also provides a kind of preparation methods of response type intelligent proppant, and using resin cladding process, including step is such as
Under:
It is dissolved in resin prepolymer in organic solvent, proppant is added and soaks proppant surface, curing agent is added, in
It is heated 2-6 hours at 80-120 DEG C, alternatively, being solidified at ultraviolet light 5-15 minutes；Up to response type intelligent support
Agent.
, according to the invention it is preferred to, the resin prepolymer be acrylic resin prepolymer, epoxy prepolymer,
Amine resins prepolymer or polyurethane.
Preferably, the organic solvent is acetone, dimethyl sulfoxide, dimethylformamide, methylethylacetone；
Preferably, the mass ratio of resin prepolymer and organic solvent is 1:(1-100)；
Preferably, the curing agent is double amine curing agents, further preferred m-xylene diamine, hexamethylene dimethylamine, two
Methyl toluene diamines；
Preferably, resin prepolymer is (1-50)-(500-1000) in the mass ratio of proppant, curing agent and proppant
Mass ratio is (0.1-10)-(500-1000)；
Preferably, the wave band of ultraviolet light is 200-400nm.
Resin prepolymer of the invention can be arrived according to prior art preparation.
What the present invention did not elaborated, press state of the art.
The principle of the present invention:
The Precision Method that the present invention carries out the high grafting response polymer of accuracy in preparation method is modified system
Method that is standby, breaching traditional overlay film.Product hydrophilic-hydrophobic-hydrophilicity can be converted.The present invention enters from microcosmic angle
Hand, carries out fining study on the modification, and it is anti-to carry out molecule grafting to proppant surface for the preparation method of macroscopical overlay film of abandoning tradition
It answers, grafting is modified proppant surface by the response performance of molecule with the molecule of response type functional group.
Beneficial effects of the present invention:
1, the present invention can prepare hydrophobically modified proppant, later by the hydrolysis process to hydrophobic polymeric, recapture parent
Water proppant realizes the hydrophilic effect conversion of hydrophilic-hydrophobic-.
2, the modified fining degree of the present invention is high, passes through particle surface contact angle test, it can be seen that intuitive modified branch
Support the variation difference of agent surface contact angle.
3, preparation method of the present invention is versatile, is suitable for different sizes, variety classes proppant, and it is former to be suitable for tradition
The surface of a variety of proppants such as sand, haydite is modified, has good development prospect, there is very big development potentiality.
Detailed description of the invention
Fig. 1 is under difference pH environmental condition of the invention, and the variation at underwater droplets contact angle illustrates.
Fig. 2 is oil droplet under varying environment pH in test example 1 of the present invention in PAA modification of surfaces contact angle variation diagram.
Fig. 3 is response type intelligent proppant surface liquid-drop contact angle variation diagram in test example 2 of the present invention.
Fig. 4 is that capillary of response type intelligent proppant under conditions of pH=3 tests spectrogram in test example 3.
Fig. 5 is that capillary of response type intelligent proppant under conditions of pH=10 tests spectrogram in test example 3.
Specific embodiment
The present invention is described in detail below with reference to embodiment and Figure of description, but not limited to this.
Embodiment 1:
A kind of preparation method of response type intelligent proppant is comprised the following steps that using molecule graft polymerization method
(1) sand grain surface initiator is modified: being weighed 5g 20-140 mesh sand proppant and is dispersed in 100mL acetone and is made into
Mixed liquor is added in the reagent bottle equipped with magneton, is slowly dropped into 2g chlorodimethylsilane with reagent needle tubing under stirring conditions
Bromide propyl isobutyrate, under nitrogen protection, agitating and heating 3h at 90 DEG C of oil bath is condensed back 10-20h, is cooled to room temperature.With
Tetrahydrofuran and acetone are washed respectively, are precipitated；It is dried in vacuo at room temperature, obtains surface chlorodimethylsilane bromide propyl isobutyrate
Sand grains proppant.
(2) grafted hydrophobic molecule: sand that 100mg surface modification is crossed is weighed in 250mL round-bottomed flask with spoon, is put into
Magneton weighs 30mg cuprous bromide catalyst, seals with rubber stopper, and leads to nitrogen.10g N,N-dimethylformamide DMF examination is added
Agent measures the monomer 10mL of hydrophobic polymeric containing double bond and is added in flask, and the monomer of hydrophobic polymeric containing double bond is tert-butyl acrylic acid
Ester monomer, and 45 μ L bipyridyls are added, it shakes up, seals with rubber stopper, lead to nitrogen.After 30min, under nitrogen environment by catalyst with
Monomers reagents mixing, keeps rubber stopper sealing state, moves into warmed-up 50 DEG C of oil bath, reacts 10 hours.
(3) it filters, with acetone soln washed product, 1mL sulfuric acid (concentration 2.0wt%) is added and reacts 2 hours, is rung
Answer type intelligence proppant proppant.
Embodiment 2:
A kind of preparation method of response type intelligent proppant is comprised the following steps that using molecule graft polymerization method
(1) haydite external dopant is modified: being weighed 100g 20-140 mesh ceramsite propping agent and is dispersed in 100mL toluene and matches
At mixed liquor, it is added in the reagent bottle equipped with magneton, is slowly dropped into the bis- bromine isobutyryls of 2g with reagent needle tubing under stirring conditions
Oxidative ethane, under nitrogen protection, agitating and heating 3h at 50 DEG C of oil bath is condensed back 20h, is cooled to room temperature.With tetrahydrofuran and
Acetone is washed respectively, is precipitated；It is dried in vacuo at room temperature, obtains the ceramsite propping agent of the double bromine isobutyryl oxidative ethane modifications in surface.
(2) molecule Graft Method connects hydrophobic brush: weighing haydite that 1000mg surface modification is crossed in 250mL round bottom with spoon
In flask, it is put into magneton, 50mg cuprous bromide catalyst is weighed, seals with rubber stopper, leads to nitrogen.10g N, N- dimethyl is added
Formamide DMF reagent measures the monomer 20mL of hydrophobic polymeric containing double bond and is added in flask, and the monomer of hydrophobic polymeric containing double bond is double
Phenol A epoxy monomer, and 60 μ L pentamethyldivinyltriamine are added, it shakes up, seals with rubber stopper, lead to nitrogen.30min
Afterwards, catalyst is mixed under nitrogen environment with resin monomer and reagent, keeps rubber stopper sealing state, move into warmed-up 50 DEG C
In oil bath, react 20 hours.
(3) it filters, with acetone soln washed product, is heated to 200 degrees Celsius 2 hours, obtains response type intelligent proppant
Proppant.
Embodiment 3:
A kind of preparation method of response type intelligent proppant is comprised the following steps that using molecule graft polymerization method
(1) sand grain surface initiator is modified: being weighed 50g 20-140 mesh sand proppant and is dispersed in 150mL acetone and is made into
Mixed liquor is added in the reagent bottle equipped with magneton, is slowly dropped into 2g bromo isobutyl acylbromide with reagent needle tubing under stirring conditions,
Under nitrogen protection, agitating and heating 3h at 150 DEG C of oil bath is condensed back 15h, is cooled to room temperature.With tetrahydrofuran and acetone point
It Xi Di, not precipitate；It is dried in vacuo at room temperature, obtains the sand grains proppant of surface bromo isobutyl acylbromide modification.
(2) molecule Graft Method connects hydrophobic brush: weighing sand that 500mg surface modification is crossed in 250mL round bottom with spoon
In flask, it is put into magneton, 40mg cuprous chloride catalyst is weighed, seals with rubber stopper, leads to nitrogen.10g N, N- dimethyl is added
Formamide DMF reagent measures the monomer 15mL of hydrophobic polymeric containing double bond and is added in flask, and the monomer of hydrophobic polymeric containing double bond is first
Base ethylamine, and 50 μ L bipyridyls are added, it shakes up, seals with rubber stopper, lead to nitrogen.After 30min, by catalyst under nitrogen environment
It is mixed with resin monomer and reagent, keeps rubber stopper sealing state, moved into warmed-up 50 DEG C of oil bath, react 15 hours.
(3) it filters, with acetone soln washed product, 1mL sulfuric acid (concentration 2.0wt%) is added and reacts 2 hours, is rung
Answer type intelligence proppant proppant.
Embodiment 4:
A kind of preparation method of response type intelligent proppant is comprised the following steps that using resin cladding process
It is (pre- with reference to resin in Chinese patent document CN1401686A embodiment 1 that resin prepolymer is made using the prior art
The preparation method of polymers is made).
Pre-cure urethane resin liquid is uniformly mixed with dimethylbenzene according to the mass ratio of 8:15, liquid hydrophobic propylene is obtained
Acid resin glue.The quartz sand of 20-140 mesh water or acid solution or lye are cleaned, scavenging period 2 hours, after must cleaning
Quartz sand；5 mass parts of liquid pre-polymerization resin are taken, 100 mass parts of quartz sand after cleaning are added pre- to the proppant after cleaning
Poly resin glue, agitation or rolling are blended proppant with hydrophobic acrylic glue in 30 minutes, reach proppant surface quilt
The degree of resin glue wetting.1 mass parts cyclo-hexylamine is added, is blended uniformly, discharges after being heated to 90 DEG C, 6 hours, is cooling
2 hours, obtain response type intelligent proppant.
Embodiment 5:
As described in Example 4, a kind of preparation method of response type intelligent proppant, using resin cladding process, including step
It is as follows:
Pre-cure urethane resin liquid is uniformly mixed with dimethyl sulfoxide according to the mass ratio of 8:30, liquid hydrophobic is obtained
Acrylic size.The haydite of 20-140 mesh water or acid solution or lye are cleaned, scavenging period 2 hours, after obtaining cleaning
Haydite；5 mass parts of liquid pre-polymerization resin are taken, pre-polymerization is added to the proppant after cleaning in 100 mass parts of haydite after cleaning
Resin glue, agitation or rolling are blended proppant with hydrophobic acrylic glue in 30 minutes, reach proppant surface and are set
The degree of rouge glue wetting.1 mass parts polyetheramine is added, is blended uniformly, discharging, cooling 2 are small after being heated to 110 DEG C, 4 hours
When, obtain response type intelligent proppant.
Test example 1
With molecule Graft Method in the macromolecules such as quartz sand proppant surface grafting PtBA (the polyacrylic acid tert-butyl ester), Zhi Hou
Under acid condition, the PtBA of proppant surface is hydrolyzed to PAA (polyacrylic acid) macromolecular.
It is hydrophilic that hydrophilic-hydrophobic-is presented in response type intelligent proppant made from this test example testing example 1 before and after hydrolysis
Performance change.Shown in the hydrophilic test of Fig. 1, from left to right: hydrophilicity is presented in unmodified quartz sand surface in water droplet；Water droplet exists
Hydrophobic performance is presented in polyacrylic acid tert-butyl ester Modified Quartz Sand surface；Polyacrylic acid modified quartz sand surface is in water droplet after hydrolyzing
Existing hydrophilicity.
Test example 2
With molecule Graft Method in macromolecules such as ceramsite propping agent surface grafting PtBA (the polyacrylic acid tert-butyl ester), later in acid
Under the conditions of property, the PtBA of proppant surface is hydrolyzed to PAA (polyacrylic acid) macromolecular.
It is hydrophilic that hydrophilic-hydrophobic-is presented in response type intelligent proppant made from this test example testing example 2 before and after hydrolysis
Performance change.Shown in the hydrophilic test of Fig. 2, from left to right: hydrophilicity is presented on unmodified haydite surface in water droplet；Water droplet is poly-
Hydrophobic performance is presented in the modified haydite surface of tert-butyl acrylate；Polyacrylic acid modified haydite surface presentation is hydrophilic after hydrolyzing for water droplet
Performance.
Test example 3
The contact angle of response type intelligent proppant made from testing example 4 changes, as a result as shown in Figure 3.It can by Fig. 3
Know, when change environment pH 3 is 12, oil droplet is equally turned into hydrophilic state by hydrophobic state in the contact angle state of proppant surface.For
Further verifying, takes capillary tube method further to detect pH response characteristic below.
Capillary test chart of the response type intelligent proppant made from testing example 1 under the conditions of pH=3 or 10 (passes through
The sand that capillary tube method test surfaces are grafted response polymer rises situation in the capillary of different pH aqueous solutions, to test
Its amphipathic property feature), as a result as shown in Figure 4,5.There is hydrophobic phenomenon in the solution that pH is 3 in test discovery；It is in pH
In 12 solution, there is hydrophilic phenomenon.Thus it further demonstrates, under the conditions of low ph conditions, particle surface PAA macromolecular is in
Existing rolled state, i.e., typical Wenzel model, therefore wetting is slower, contact angle is small；Under high pH environmental condition, particle surface
Extended state is presented in PAA macromolecular, typical Cassie model is presented, therefore contact angle is larger, capillary phenomenon is obvious, and solution exists
Rise in capillary very fast.
Claims (10)
1. a kind of preparation method of response type intelligent proppant is comprised the following steps that using molecule Graft Method
(1) proppant surface initiator is modified: being dispersed proppant in organic solvent and is made into mixed with proppants liquid, to proppant
Initiator is added in mixed liquor, under protective gas protection, heating stirring reaction causes the upper functionality of proppant surface modification
Agent obtains the proppant of initiator modification；
(2) molecule Graft Method is grafted response type functional polymer: in the proppant modified under protective gas protection to initiator
Catalyst, solvent, the monomer containing functional group, ligand are sequentially added, under protective gas protection, heating condition, is stirred to react,
Obtain intermediate product；
(3) obtained intermediate product is filtered, washed, is handled under high temperature or acidulated condition to get response type intelligent branch
Support agent.
2. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that support in step (1)
The mass ratio of agent and initiator is (5-100): 2.
3. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that described in step (1)
Proppant be quartz sand, haydite or glass microsphere.
4. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that described in step (1)
Initiator be halogenated silanes, alpha-brominated ester, α-halogenatedketone, alpha-halogenate nitrile, aryl sulfonyl chloride, azodiisobutyronitrile, brominated silicon
Alkane, chlorodimethylsilane bromide propyl isobutyrate, double bromine isobutyryl oxidative ethanes or bromo isobutyl acylbromide；
Preferably, the organic solvent is acetone, butanone, toluene, dimethylbenzene, methyl phenyl ethers anisole, n,N-Dimethylformamide, diformazan
Base sulfoxide, methanol, acetonitrile or chloroform；
Preferably, the protective gas is nitrogen or argon gas.
5. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that support in step (1)
The quality of agent and the volume ratio of organic solvent are 0.1-50g/mL；
Preferably, the temperature of heating stirring reaction is 50-150 DEG C, and the reaction time is 0.5-5 hours.
6. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that described in step (2)
The monomer containing functional group be epoxy monomer, amine monomers or the monomer of base class containing carboxylic acid；Preferably, the epoxies list
Body is bisphenol-type epoxy resin, vinylcyclohexene dicyclic oxide, o-phthalic acid diglycidyl ester, the amine list
Body is melamine, urea, ethylamine etc., and the monomer of base class containing carboxylic acid is acrylic acid, acrylic acid methyl ether, acrylic acid second
Ester；
Preferably, the catalyst is cuprous salt, further preferred cuprous bromide or stannous chloride；
Preferably, the ligand is pyridines or amine substance, it is further preferred that the ligand is bipyridyl or pentamethyl
Diethylene triamine；
Preferably, the solvent is acetone, methylethylacetone, dimethyl sulfoxide, dimethylformamide；
Preferably, the protective gas is nitrogen or argon gas.
7. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that cause in step (2)
The proppant of agent modification and the mass ratio of catalyst are as follows: (10-100): (2-5)；
Preferably, the mass ratio of the additional amount of ligand and catalyst are as follows: (40-60): (20-40)；
Preferably, the mass ratio of the proppant and the monomer containing functional group of initiator modification are as follows: (500-1000)-(0.1-
50)；
Preferably, the quality of the proppant of initiator modification and the volume ratio of solvent are 0.1-50g/mL.
8. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that stirring in step (2)
Time is 1-40 hours；Molecule graft polymerization reaction occurs in proppant surface under stirring condition；
Preferably, the temperature of heating condition is 40-160 DEG C, and the reaction time is 0.5-12 hours.
9. the preparation method of response type intelligent proppant according to claim 1, which is characterized in that washing in step (3)
Detergent is methanol, water；
Preferably, high-temperature process temperature is 50-150 DEG C；
Preferably, the pH value of acidulated condition is 1-5.
10. a kind of preparation method of response type intelligent proppant is comprised the following steps that using resin cladding process
It is dissolved in resin prepolymer in organic solvent, proppant is added and soaks proppant surface, curing agent is added, in 80-
It is heated 2-6 hours at 120 DEG C, alternatively, being solidified at ultraviolet light 5-15 minutes；Up to response type intelligent proppant.
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| CN112282722A (en) * | 2020-06-05 | 2021-01-29 | 中国海洋石油集团有限公司 | Low-density organic water-control proppant and preparation method thereof |
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| CN111040753A (en) * | 2019-10-28 | 2020-04-21 | 中国石油化工股份有限公司 | Supercritical CO2Hydrophobic modification method of fracturing fluid proppant |
| CN111040753B (en) * | 2019-10-28 | 2022-04-19 | 中国石油化工股份有限公司 | Supercritical CO2Hydrophobic modification method of fracturing fluid proppant |
| CN112282722A (en) * | 2020-06-05 | 2021-01-29 | 中国海洋石油集团有限公司 | Low-density organic water-control proppant and preparation method thereof |
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