CN103849373B - A kind of fracturing propping agents and preparation method thereof - Google Patents
A kind of fracturing propping agents and preparation method thereof Download PDFInfo
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- CN103849373B CN103849373B CN201210504494.8A CN201210504494A CN103849373B CN 103849373 B CN103849373 B CN 103849373B CN 201210504494 A CN201210504494 A CN 201210504494A CN 103849373 B CN103849373 B CN 103849373B
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- epoxy resin
- fluorochemical
- coupling agent
- propping agents
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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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/14—Polyepoxides
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Abstract
The invention provides a kind of fracturing propping agents and preparation method thereof.Described fracturing propping agents are by cured for the mixture containing particles of aggregates and the overlay film binding agent product formed, wherein, described overlay film binding agent is the hydrophobic resin compositions containing epoxy resin and fluorochemical, described fluorochemical is linked together with at least part of epoxy resin by coupling agent, one end of described coupling agent is covalently joined together with described at least part of epoxy resin by the first coupling group, and the other end of described coupling agent is covalently joined together with fluorochemical by the second coupling group.The fracturing propping agents that the present invention provides have high water blockoff ability and crushing strength.
Description
Technical field
The present invention relates to a kind of fracturing propping agents and the preparation method of a kind of fracturing propping agents.
Background technology
In the recovery process of petroleum gas, high clossing pressure deposits of low permeability after frac treatment,
Making Oil gas-containing rock layer split, oil gas collects from the passage of cracking initiation, and fracturing propping agents are in company with high
Pressure solution liquid entrance Filling, in rock crack, plays the work supporting crack not stress release and close
With, thus keep high flow conductivity, make oil gas unimpeded, increase the yield of petroleum gas.
Existing fracturing propping agents are mainly haydite (typically with bauxite as primary raw material, and through 800
High temperature sintering more than DEG C forms) and quartz sand, its water blockoff ability needs to improve further.
Summary of the invention
It is an object of the invention to provide a kind of new fracturing propping agents and the system of a kind of fracturing propping agents
Preparation Method.The fracturing propping agents that the present invention provides have higher water blockoff ability.
The invention provides a kind of fracturing propping agents, described fracturing propping agents for will containing particles of aggregates with cover
The product that the mixture of film adhesive is cured and is formed, wherein, described overlay film binding agent is containing epoxy
The hydrophobic resin compositions of resin and fluorochemical, described fluorochemical by coupling agent with at least
Part epoxy links together, and described coupling agent has an at least two NCO, described at least
Part epoxy has hydroxyl, and described fluorochemical has can carry protogenic group, described idol
One end of connection agent is covalently joined together with described at least part of epoxy resin by the first coupling group, institute
The other end stating coupling agent is covalently joined together with fluorochemical by the second coupling group, and described
One coupling group is by the NCO in described coupling agent and the hydroxyl in described at least part of epoxy resin
Base is formed, and described second coupling group is by the NCO in described coupling agent and fluorochemical
Protogenic group can be carried formed.
Present invention also offers the preparation method of a kind of fracturing propping agents, the method includes containing aggregate
The mixture solidification of grain and overlay film binding agent, wherein, described overlay film binding agent is containing epoxy resin and to contain
The hydrophobic resin compositions of fluorine compounds, described fluorochemical is by coupling agent and at least part of epoxy
Resin links together, and described coupling agent has at least two NCO, described at least part of epoxy
Resin has hydroxyl, and described fluorochemical has can carry protogenic group, the one of described coupling agent
End is covalently joined together with described at least part of epoxy resin by the first coupling group, described coupling agent
The other end be covalently joined together with fluorochemical by the second coupling group, described first coupling portion
Divide and formed with the hydroxyl in described at least part of epoxy resin by the NCO in described coupling agent, institute
State the second coupling group by the NCO in described coupling agent and can provide in fluorochemical
The group of proton is formed.
The pressure break of the cured preparation of mixture of described particles of aggregates Yu hydrophobic resin compositions is supported
Agent not only has high water blockoff ability, but also has higher crush strength, it is possible to effectively support
Crack, prevents it from closing.
Detailed description of the invention
The fracturing propping agents that the present invention provides are by the mixture warp containing particles of aggregates and overlay film binding agent
The product being solidified to form, wherein, described overlay film binding agent is containing epoxy resin and fluorochemical
Hydrophobic resin compositions, described fluorochemical is connected to at least part of epoxy resin by coupling agent
Together, described coupling agent has at least two NCO, and described at least part of epoxy resin has hydroxyl
Base, described fluorochemical has can carry protogenic group, and one end of described coupling agent passes through first
Coupling group is covalently joined together with described at least part of epoxy resin, and the other end of described coupling agent leads to
Crossing the second coupling group to be covalently joined together with fluorochemical, described first coupling group is by described idol
NCO in connection agent is formed with the hydroxyl in described at least part of epoxy resin, described second coupling
Part is by carrying protogenic group in the NCO in described coupling agent and fluorochemical
Formed.
According to the present invention, the hydroxyl in described epoxy resin is used for reacting with coupling agent, and then by asphalt mixtures modified by epoxy resin
Fat is linked together by chemical bond with fluorochemical, and the content of described hydroxyl can contain according to intended
The amount of fluorine compounds carries out suitable selection.Prepare by described hydrophobic resin compositions from improving further
The angle of water plugging property of fracturing propping agents set out, the hydroxyl value of described epoxy resin is preferably
0.02-0.4mol/100g, more preferably 0.04-0.2mol/100g.Hydroxyl value meets the asphalt mixtures modified by epoxy resin of above-mentioned requirements
Fat is commercially available, it would however also be possible to employ various methods synthesis commonly used in the art, the most no longer describes in detail.
Described hydroxyl value can save at the 3.1-3.3 of " epoxy resin hydroxyl value assay method " according to Huang Biwu etc.
Method disclosed in (thermosetting resin, 4:42-45, nineteen ninety-five) measures, it is also possible to be available commercially
Epoxy resin the description of product in know.In the embodiment of the present invention, the hydroxyl value of epoxy resin comes from business
The description of product of the epoxy resin buied.
According to the present invention, the epoxy radicals in described epoxy resin is mainly used in and firming agent haptoreaction, with
Form cross-linked structure.The content of described epoxy resin epoxy group is so that described hydrophobic resin compositions energy
Enough formation on the surface of particles of aggregates has the clad of some strength and is as the criterion.From improving by described further
The angle of the crushing strength of fracturing propping agents prepared by hydrophobic resin compositions is set out, described asphalt mixtures modified by epoxy resin
The epoxide number of fat is preferably 0.05-0.6mol/100g, more preferably 0.12-0.55mol/100g, further
It is preferably 0.25-0.51mol/100g.
According to the present invention, described fluorochemical can be former containing fluorine in common various molecular structures
Son, and there is at least one compound that can carry protogenic group.Described can carry protogenic base
Group namely has the group of active hydrogen, and its instantiation can include but not limited to hydroxyl and amido.Institute
Stating fluorochemical can be such as selected from C1-C12Containing fluoroalkyl alcohol and C1-C12Fluorine-containing alkylamine in
One or more compounds.The instantiation of described fluorochemical can include but not limited to: tetrafluoro
Butyl ethyl alcohol, perfluoro hexyl ethyl alcohol and hexafluoroisopropanol.
According to the present invention, fluorochemical is used for improving the hydrophobicity of the epoxy resin as matrix resin,
So that the fracturing propping agents prepared by described hydrophobic resin compositions have good water plugging property.
In described hydrophobic resin compositions, the content of fluorochemical has order with final fracturing propping agents
The hydrophobicity that people is satisfied is as the criterion.Preferably, relative to 100 parts by weight epoxy resin, described fluorine-containing chemical combination
The content of thing is 1-50 weight portion.From improving the pressure prepared by described hydrophobic resin compositions further
Split the water plugging property of proppant, the most also make epoxy resin and fluorochemical have the good compatibility
Angle set out, relative to 100 parts by weight epoxy resin, the content of described fluorochemical is more preferably
5-45 weight portion.In described hydrophobic resin compositions, the content of fluorochemical can be hydrophobic by preparing this
Rate of charge during property resin combination is calculated.
According to the present invention, described coupling agent has at least two NCO such that it is able to will contain fluorination
Compound is linked together with at least part of epoxy resin by chemical bond.Described coupling agent can be common
Various molecular structures have the compound of at least two NCO.Its instantiation can include but
It is not limited to: alkylene diisocyanate, toluene di-isocyanate(TDI), isophorone diisocyanate, hexichol
One or more in dicyclohexylmethane diisocyanate and cyclohexyl diisocyanate.From improving by institute further
State water blockoff ability and the angle of crushing strength of fracturing propping agents prepared by hydrophobic resin compositions
Setting out, described coupling agent is preferably toluene di-isocyanate(TDI), isophorone diisocyanate and cyclohexyl two
One or more in isocyanates.
According to the present invention, described coupling agent is for connecting fluorochemical and epoxy resin by chemical bond
Together, the amount of described coupling agent can be according to the amount of fluorochemical in described hydrophobic resin compositions
Carry out suitable selection.Specifically, described coupling agent and described fluorochemical can provide proton
The mol ratio of group can be 1-1.2:1.Under preferable case, described coupling agent and described epoxy resin
In the mol ratio of hydroxyl be 1-1.2:1.
According to the present invention, described particles of aggregates can be that existing various can be used in prepares fracturing propping agents
Particulate material, such as, described particles of aggregates can be selected from roughing sand, slag, haydite and glass microballoon
In one or more.Wherein, described roughing sand both can be natural silica Sand, it is also possible to for artificial silica sand.
Described natural silica Sand can be fluvial sand, sea sand and aeolian sand, is preferably the aeolian sand from desert.
According to the present invention, the average diameter of described particles of aggregates can in very large range change, it is possible to
The most reasonably selecting, such as, the average diameter of described particles of aggregates can be 0.04-5
Millimeter, preferably 0.05-2 millimeter, more preferably 0.1-0.85 millimeter.Described particles of aggregates average straight
Footpath is to use sieve method to measure.That is, particles of aggregates is made to measure it by various sizes of sieve aperture average
Diameter.
According to the present invention, the sphericity of described particles of aggregates can select in wider scope and become
Dynamic, as a rule, sphericity is the best, and the flow conductivity after crushing is the strongest, it is therefore preferable that in the case of,
The circularity of described particles of aggregates and sphericity are preferably >=0.6.Wherein, " sphericity " refers to the journey of granule subglobular
Degree；" circularity " refers to the relative sharpness of grain corner or measuring of curvature, sphericity and the assay method of circularity
Known to those skilled in the art, such as, chart method can be used to be measured.
According to the present invention, described particles of aggregates can enter with the content of overlay film binding agent in wider scope
Row selects and variation, such as, relative to particles of aggregates described in 100 weight portions, described overlay film binding agent
Amount can be 1-10 weight portion, preferably 2-8 weight portion.
Additionally, present invention also offers the preparation method of a kind of fracturing propping agents, the method includes containing
The mixture solidification of particles of aggregates and overlay film binding agent, wherein, described overlay film binding agent is containing asphalt mixtures modified by epoxy resin
The hydrophobic resin compositions of fat and fluorochemical, described fluorochemical is by coupling agent and at least portion
Dividing epoxy resin to link together, described coupling agent has at least two NCO, described at least portion
Dividing epoxy resin to have hydroxyl, described fluorochemical has can carry protogenic group, described coupling
One end of agent is covalently joined together with described at least part of epoxy resin by the first coupling group, described
The other end of coupling agent is covalently joined together with fluorochemical by the second coupling group, and described first
Coupling group is by the NCO in described coupling agent and the hydroxyl in described at least part of epoxy resin
Being formed, described second coupling group is by the NCO in described coupling agent and the energy in fluorochemical
Enough carry protogenic group to be formed.
According to the present invention, described hydrophobic resin compositions can use existing various method to be prepared into
Arriving, under preferable case, the method for described hydrophobic resin compositions includes entering epoxy resin with coupling agent
Row first contacts, and with fluorochemical, the mixture obtained is carried out second contacts, at least part of epoxy
Resin has hydroxyl, and described fluorochemical has can carry protogenic group, and described coupling agent has
At least two NCO, the condition of described first contact makes the hydroxyl in epoxy resin and described idol
Part NCO in connection agent is formed covalently bound, and the condition of described second contact makes described fluorine-containing
The protogenic group that can carry in compound is formed altogether with remaining NCO in described coupling agent
Valency connects.
The method according to the invention, the kind of described epoxy resin, fluorochemical and coupling agent and use
Amount has been carried out detailed description above, and here is omitted.
Described first contact is not particularly limited by the present invention with the second condition contacted, preferable case
Under, under optimum condition, described first contact makes the epoxy radicals in epoxy resin with the second condition contacted
Do not react with the NCO in described coupling agent.Can be by controlling the temperature of the first contact
Degree makes the NCO in described coupling agent react with the hydroxyl in epoxy resin, and the most not
React with the epoxy radicals in epoxy resin, such as: described first contact can be made with second to contact each
Carry out at a temperature of comfortable 50-90 DEG C, preferably make described first contact contact the temperature at 50-70 DEG C with second
Carry out under degree.Described first contact with the second time contacted can according to carry out this contact temperature and
The concrete kind of reactant carrying out reacting carries out suitable selection, it is preferable that described first contact time
Between be 1-3 hour, described second contact time be 1-8 hour.
According to the present invention, described first contact contacts to enter the most in the presence of at least one solvent with second
OK, so on the one hand can more easily the severe degree of reaction be adjusted, on the other hand can also
The contact making each reactant is the most abundant.Described solvent can be various can either dissolved epoxy, again
The liquid of coupling agent and fluorochemical can be dissolved.Specifically, described solvent can be selected from toluene, fourth
Alcohol and isomer (such as 1-n-butyl alcohol and the tert-butyl alcohol) thereof and butanone.
The consumption of described solvent can be conventional selection.Usually, relative to 100 weight parts matrix resins,
The consumption of described solvent can be 50-200 weight portion.
According to the present invention, described first contact contacts with described second and carries out in the presence of at least one solvent
Time, the method for the present invention also includes removing the solvent in the mixture that the second contact obtains.Can be used this
The various methods that field is commonly used remove described solvent, such as: decompression distillation.
According to the present invention, the consumption of described overlay film binding agent can form cladding on the surface of particles of aggregates
Layer is as the criterion.Usually, relative to particles of aggregates described in 100 weight portions, the amount of described overlay film binding agent can
Think 1-10 weight portion, preferably 2-8 weight portion.
According to the present invention, during preparing fracturing propping agents, it is also possible to according to practical situation selectivity
Ground adds epoxy curing agent.Specifically, described epoxy curing agent can be various selected from commonly use
Epoxy resin can be made to crosslink amine curing agent and/or the acid anhydride type curing agent of reaction.Its instantiation
Can include but not limited to: phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, benzophenone
Tetracarboxylic dianhydride, maleic anhydride, tung oil acid anhydride, alkylene succinic anhydride, THPA, hexahydro
Phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, carbic anhydride, glutaric anhydride, terpenic acid
Acid anhydride, methylcyclohexene tetracarboxylic dianhydride, dodecenylsuccinic acid acid anhydride, poly-Azelaic Acid acid anhydride, poly sebacic polyanhydride,
PHT4, tetrachlorophthalic anhydride, trimellitic anhydride glycol ester, trimellitic anhydride glyceride, hexichol
Base sulfone tetracarboxylic dianhydride, ethylenediamine, diethylenetriamine, two amido diphenyl sulphone (DPS)s, two amido diphenyl-methanes,
M-diaminobenzene., dicyandiamide, polyetheramine, diethylenetriamines, hexamethylene diamine, trimethylhexamethylenediamine
And TEPA.Preferably, described epoxy curing agent selected from THPA, HHPA, two
Amido diphenyl-methane, diethylenetriamine and dicyandiamide.
The consumption of described epoxy curing agent can carry out suitable selection according to its kind, so that described
Epoxy resin in hydrophobic resin compositions can solidify, and makes the fracturing propping agents finally given have
Certain intensity is as the criterion.Usually, the consumption of described epoxy curing agent can be the reason of this firming agent
0.9-1.2 times of opinion consumption.Known various methods can be used to determine the theoretical amount of firming agent.
Such as, when described epoxy curing agent is amine curing agent, can be calculated it by below equation theoretical
Consumption:
W=(M/Hn) × E,
Wherein, W is the quality of the firming agent required for every 100g epoxy resin, g；
M is the molecular weight of firming agent；
E is the epoxide number of epoxy resin, mol/100g；
HnFor the number of active hydrogen on amido in each firming agent molecule.
The most such as, when described epoxy curing agent is acid anhydride type curing agent, below equation can be passed through
The theoretical amount of calculating firming agent:
W=AE× E × K,
Wherein, W is the quality of the firming agent required for every 100g epoxy resin, g；
AEMolecular weight for anhydride；
E is the epoxide number of epoxy resin, mol/100g；
K is to be in an empirical value within 0.5-1.1, generally 0.85.
According to the present invention, the condition of described solidification can be the conventional selection of this area, as a rule, institute
The condition stating solidification can include solidification temperature and hardening time.Described solidification temperature can be according to selection
The kind of firming agent carries out suitable selection, as a rule, when the temperature of described solidification is 100-250 DEG C
Time, just enable to described solidification and be smoothed out.As a rule, the prolongation of described hardening time is conducive to
Solidify the most complete, but the long amplitude inconspicuous that state of cure is improved hardening time, therefore,
Consider effect and efficiency, be preferably 0.05-0.5 hour described hardening time.
From the angle avoiding between particles of aggregates mutually bonding, preferably described in be solidificated in stirring
Under the conditions of carry out.
The present invention is described in detail below in conjunction with embodiment.
In following example and comparative example, according to the method for regulation in SY/T5108-2006, pressure break is supported
The performance of agent detects.
In following example and comparative example, following methods is used to measure the water shut-off of the fracturing propping agents prepared
Can: the fracturing propping agents of preparation are filled in sidewall there is scale and the bottom punctulate cylindrical, hollow of tool
In container, the upper surface of fracturing propping agents is continuously added into water until beginning with from the bottom of hollow container
Water oozes out, the height of the water layer on the upper surface of fracturing propping agents when having water to ooze out bottom record hollow container
Degree, wherein, the height of described hollow container is 1m, and internal diameter is 5cm；Fracturing propping agents hold in hollow
Packed height in device is 5cm.When having water to ooze out bottom hollow container on the upper surface of fracturing propping agents
The height value of water layer is the biggest, illustrates that the water plugging property of these fracturing propping agents is the best.
Embodiment 1-3 is for hydrophobic resin compositions that the present invention is described and its preparation method and application.
Embodiment 1
(1) by 100g epoxy resin (commercially available from Langfang Nore believe Chemical Co., Ltd., the trade mark is E-44,
Epoxide number is 0.44mol/100g, and hydroxyl value is 0.088mol/100g) it is dissolved in 50g toluene, with stirring
Mixing and temperature is increased to 50 DEG C, be subsequently adding 15.3g toluene di-isocyanate(TDI), stirring is anti-at such a temperature
Answer 2 hours；Be subsequently adding 23g tetrafluoro butyl ethyl alcohol (commercially available from Fuxin Heng Tong fluorine chemistry company limited,
The trade mark is TEOH-4), after continuing reaction 2 hours, by the mixture that obtains at a temperature of 60 DEG C
It is evaporated under reduced pressure in rotary evaporator, to remove toluene, thus obtains the hydrophobic resin group of the present invention
Compound.
(2) the hydrophobic resin compositions that 100g step (1) obtains (is purchased with 2000g roughing sand
From proppant company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 mesh) mix and blend 2 minutes, so
Rear addition 40g THPA and 3g diethylenetriamine, stir 3 minutes at 180 DEG C, then temperature dropped
As little as room temperature (being 25 DEG C), thus obtain fracturing propping agents.The performance of these fracturing propping agents is in Table 1
List.
Comparative example 1
Use the method identical with embodiment 1 step (2) to prepare fracturing propping agents, except for the difference that, make
The epoxy resin used by embodiment 1 step (1) replaces hydrophobic resin compositions, thus is pressed
Split proppant.The performance of these fracturing propping agents is listed in Table 1.
Embodiment 2
(1) by 100g epoxy resin (commercially available from Langfang Nore believe Chemical Co., Ltd., the trade mark is E-31,
Epoxide number is 0.31mol/100g, and hydroxyl value is 0.166mol/100g) it is dissolved in 50g toluene, with stirring
Mix and temperature is increased to 50 DEG C, be subsequently adding 27.6g cyclohexyl diisocyanate, stir at such a temperature
React 2 hours；It is subsequently adding 43.8g tetrafluoro butyl ethyl alcohol (limited commercially available from Fuxin Heng Tong fluorine chemistry
Company, the trade mark is TEOH-4), after continuing reaction 2 hours, by the mixture that obtains the temperature of 60 DEG C
It is evaporated under reduced pressure in a rotary evaporator under degree, to remove toluene, thus obtains the hydrophobicity of the present invention
Resin combination.
(2) the hydrophobic resin compositions that 160g step (1) obtains (is purchased with 2000g roughing sand
From proppant company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 mesh) mix and blend 2 minutes, so
Rear addition 20g bis-amido diphenyl-methane, stirs 3 minutes at 180 DEG C, then temperature is reduced to room temperature
(being 25 DEG C), thus obtain fracturing propping agents.The performance of these fracturing propping agents is listed in Table 1.
Embodiment 3
(1) by 100g epoxy resin (commercially available from Langfang Nore believe Chemical Co., Ltd., the trade mark is E-51,
Epoxide number is 0.51mol/100g, and hydroxyl value is 0.046mol/100g) it is dissolved in 50g toluene, with stirring
Mix and temperature is increased to 50 DEG C, be subsequently adding 10.2g isophorone diisocyanate, stir at such a temperature
Mix reaction 2 hours；Be subsequently adding 16.9g perfluoro hexyl ethyl alcohol (Fuxin Heng Tong fluorine chemistry company limited,
The trade mark is TEOH-6), after continuing reaction 2 hours, the mixture obtained is revolved at a temperature of 60 DEG C
Turn in vaporizer and be evaporated under reduced pressure, to remove toluene, thus obtain the hydrophobic resin combination of the present invention
Thing.
(2) the hydrophobic resin compositions that 100g step (1) obtains (is purchased with 2000g roughing sand
From proppant company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 mesh) mix and blend 2 minutes, so
Rear addition 40g THPA and 3g dicyandiamide, stir 3 minutes at 180 DEG C, then temperature be reduced to
Room temperature (being 25 DEG C), thus obtain fracturing propping agents.The performance of these fracturing propping agents is listed in Table 1.
Comparative example 2
Method same as in Example 3 is used to prepare hydrophobic resin compositions and fracturing propping agents, no
With, in step (1) perfluoro hexyl ethyl alcohol with 9.8g hydroxy-terminated polysiloxane (commercially available from Dongguan
City Aurion spy organosilicon material company limited, hydroxyl value is 8 weight %) replace, the fracturing propping agents obtained
Performance list in Table 1.
Table 1
Wherein, " sphericity " refers to the degree of proppant particles subglobular；" circularity " refers to the relative sharpness of its corner angle or measuring of curvature, by
Chart method measures；" body density " refers to the proppant of unit mass and the ratio of its stacking volume；" apparent density " refer to the proppant of unit mass and its
The ratio of particle volume；" turbidity " refers to add the proppant of certain volume in the distilled water of unit volume, then stirs, the muddy journey of liquid
Degree is referred to as the turbidity of proppant；" acid solubility " refers to, at the acid solution of regulation and in the sour molten time, determine that certain mass proppant is dissolved by acid
The percentage ratio of quality and total proppant quality；" percentage of damage " refers to the proppant to certain volume, carries out pressure-bearing test under rated pressure,
The percentage of damage determined characterizes the ability of proppant resistant to breakage.
As it can be seen from table 1 the fracturing propping agents prepared by described hydrophobic resin compositions not only have
Good water plugging property, but also have higher crushing strength, can effective support fracturing crack.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. fracturing propping agents, described fracturing propping agents are will be containing particles of aggregates and overlay film binding agent
Mixture is cured and the product that formed, it is characterised in that described overlay film binding agent is containing asphalt mixtures modified by epoxy resin
The hydrophobic resin compositions of fat and fluorochemical, described fluorochemical is by coupling agent and at least portion
Dividing epoxy resin to link together, described coupling agent has at least two NCO, described at least portion
Dividing epoxy resin to have hydroxyl, described fluorochemical has can carry protogenic group, described coupling
One end of agent is covalently joined together with described at least part of epoxy resin by the first coupling group, described
The other end of coupling agent is covalently joined together with fluorochemical by the second coupling group, and described first
Coupling group is by the NCO in described coupling agent and the hydroxyl in described at least part of epoxy resin
Being formed, described second coupling group is by the NCO in described coupling agent and the energy in fluorochemical
Enough carry protogenic group to be formed.
Fracturing propping agents the most according to claim 1, wherein, described in 100 weight portions
Epoxy resin, the amount of described fluorochemical is 1-50 weight portion.
Fracturing propping agents the most according to claim 2, wherein, described in 100 weight portions
Epoxy resin, the amount of described fluorochemical is 5-45 weight portion.
Fracturing propping agents the most according to claim 1 and 2, wherein, described can provide proton
Group be hydroxyl and/or amido.
Fracturing propping agents the most according to claim 1 and 2, wherein, described fluorochemical is
Selected from C1-C12Containing fluoroalkyl alcohol and C1-C12Fluorine-containing alkylamine in one or more compounds.
Fracturing propping agents the most according to claim 5, wherein, described fluorochemical is for being selected from
One or more compounds in tetrafluoro butyl ethyl alcohol, perfluoro hexyl ethyl alcohol and hexafluoroisopropanol.
Fracturing propping agents the most according to claim 1, wherein, described coupling agent is alkylidene two
Isocyanates, toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate
With one or more in cyclohexyl diisocyanate.
Fracturing propping agents the most according to claim 7, wherein, described coupling agent is that toluene two is different
One or more in cyanate, isophorone diisocyanate and cyclohexyl diisocyanate.
Fracturing propping agents the most according to claim 1 and 2, wherein, the hydroxyl of described epoxy resin
Value is 0.02-0.4mol/100g, and epoxide number is 0.05-0.6mol/100g.
Fracturing propping agents the most according to claim 1 and 2, wherein, with the bone of 100 weight portions
On the basis of material granule, the content of described overlay film binding agent is 1-10 weight portion.
11. fracturing propping agents according to claim 10, wherein, with the aggregate of 100 weight portions
On the basis of granule, the content of described overlay film binding agent is 2-8 weight portion.
The preparation method of 12. 1 kinds of fracturing propping agents, the method includes to glue containing particles of aggregates and overlay film
The mixture solidification of knot agent, it is characterised in that described overlay film binding agent is containing epoxy resin with containing fluorination
The hydrophobic resin compositions of compound, described fluorochemical is by coupling agent and at least part of epoxy resin
Linking together, described coupling agent has at least two NCO, described at least part of epoxy resin
Having hydroxyl, described fluorochemical has can carry protogenic group, and one end of described coupling agent leads to
Cross the first coupling group to be covalently joined together with described at least part of epoxy resin, described coupling agent another
One end is covalently joined together with fluorochemical by the second coupling group, described first coupling group by
Hydroxyl in NCO in described coupling agent and described at least part of epoxy resin is formed, and described the
Two coupling group are by providing proton in the NCO in described coupling agent and fluorochemical
Group formed.
13. preparation methoies according to claim 12, wherein, described hydrophobic resin compositions
Preparation method include that with coupling agent, epoxy resin is carried out first contacts, and by the mixture obtained with contain
Fluorine compounds carry out the second contact, and at least part of epoxy resin has hydroxyl, and described fluorochemical has
Can carry protogenic group, described coupling agent has at least two NCO, described first contact
Condition make hydroxyl in epoxy resin form covalency with the part NCO in described coupling agent
Connect, described second contact condition make in described fluorochemical can carry protogenic group with
In described coupling agent, remaining NCO is formed covalently bound.
14. preparation methoies according to claim 13, wherein, described first contact and second connects
Touch and carry out at a temperature of each comfortable 50-90 DEG C.
15. preparation methoies according to claim 14, wherein, described first contact and second connects
Touch and carry out at a temperature of each comfortable 50-70 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021055202A1 (en) * | 2019-09-17 | 2021-03-25 | Saudi Arabian Oil Company | Coated proppant and methods of making and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1492803A (en) * | 2001-02-01 | 2004-04-28 | ���ǻ�ѧ��˾ | Composite proppant, filtration medium, gravel packing media, and sports field media, and methods for making and using same |
| CN1839034A (en) * | 2003-04-15 | 2006-09-27 | 氦克逊特种化学品公司 | Particulate material containing thermoplastic elastomer and methods for making and using same |
| CN102167969A (en) * | 2009-10-26 | 2011-08-31 | 禾逊专业化学公司 | Low temperature coated particles for use as proppants or in gravel packs, methods for making and using the same. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1492803A (en) * | 2001-02-01 | 2004-04-28 | ���ǻ�ѧ��˾ | Composite proppant, filtration medium, gravel packing media, and sports field media, and methods for making and using same |
| CN1839034A (en) * | 2003-04-15 | 2006-09-27 | 氦克逊特种化学品公司 | Particulate material containing thermoplastic elastomer and methods for making and using same |
| CN102167969A (en) * | 2009-10-26 | 2011-08-31 | 禾逊专业化学公司 | Low temperature coated particles for use as proppants or in gravel packs, methods for making and using the same. |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021055202A1 (en) * | 2019-09-17 | 2021-03-25 | Saudi Arabian Oil Company | Coated proppant and methods of making and use thereof |
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