CN108315005A - It is a kind of with high flow conductivity without sand fracturing fluid, preparation method and fracturing technology and application - Google Patents
It is a kind of with high flow conductivity without sand fracturing fluid, preparation method and fracturing technology and application Download PDFInfo
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- CN108315005A CN108315005A CN201710040397.0A CN201710040397A CN108315005A CN 108315005 A CN108315005 A CN 108315005A CN 201710040397 A CN201710040397 A CN 201710040397A CN 108315005 A CN108315005 A CN 108315005A
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- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/08—Fiber-containing well treatment fluids
Abstract
The present invention relates to a kind of with high flow conductivity without sand fracturing fluid, preparation method and fracturing technology and application.This includes the A groups fracturing fluid containing curable resin performed polymer and the B group fracturing fluids containing curing agent and fiber without sand fracturing fluid, and the A groups fracturing fluid and B group fracturing fluids are used cooperatively.Fracturing fluid prepared by the present invention, which can enter in cracks at different levels, forms fiber reinforcement porous resin, it can be ensured that the complicated seam net system pressed off has higher flow conductivity and supporting crack, the raising rate of oil and gas recovery.And fracturing technology of the present invention is simple, and pressure break risk is relatively low.
Description
Technical field
The present invention relates to a kind of with high flow conductivity without sand fracturing fluid, preparation method and fracturing technology and application,
Belong to the hydraulic fracturing technology field in oil, gas exploitation course.
Background technology
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, does not use fracturing technique, and the oil gas of underground is difficult to mined.Hydraulic fracturing is exactly to utilize high pressure pump group, will
Fracturing fluid is pumped into stratum, forms one or more crack with certain geometric dimension in the earth formation, fracture length is generally from several
Ten meters to hundreds of meters, highly meter height from several meters to tens, the several mm wides of width, then by the load fluid (pressure with proppant
Split 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 then stays in
In crack, play the role of supporting crack, crack is kept to be in open configuration.Hole between proppant particles is hydrocarbon stratum
Water provides circulation passage, to play the effect of fracturing yield increasing.Proppant is the most critical factor of effect of increasing production quality, proppant
Performance determines the flow conductivity (width in crack is multiplied by the permeability in crack) in crack.
Chinese patent literature CN103821491A provides a kind of SAND FRACTURING TECHNOLOGY, the technique be by fibre-bearing load fluid and
Pure frozen glue interval liquid is pumped into a manner of alternate cycles in oil/gas well crack, into the fibre-bearing load fluid quilt in oil/gas well crack
Perforation holes on tubing string are dispersed into different lumps, pile up form sand column in crack from inside to outside, in the sand column
Gap is filled by pure frozen glue interval liquid between adjacent crumby fibre-bearing load fluid, and the section of entire sand column is in the stone walling piled up
Shape；The sand column is supported the crack in closing course and the crack after closure, the pure frozen glue interval liquid position in sand column
In lower resistance, the high flow rate seepage channel for forming oil gas after breaking gel, so that the well yield of oil/gas well increases.Chinese patent
Document CN104727799A discloses a kind of pulse sand fracturing method for realizing crack high flow conductivity, and this method includes step
Suddenly：1, the more cluster pressure breaks of super-low permeability reservoir horizontal well in segments are directed to, and by the super-low permeability reservoir properties study, judging
Higher fracture condudtiviy can be formed by pulsed sand fracturing, if so, executing step 2；2, in fracturing process
By pulsed plus sand technique, fiber fracturing liquid consolidates sand, " cylinder " support is formed in man-made fracture, to manually be split described
The channel network that high speed flow conductivity is formed in seam, makes the man-made fracture have higher flow conductivity, improves well yield.
It is above-mentioned to be required to add sand in the prior art, height is required to fracturing fluid viscosity etc., fracturing fluid viscosity is too low, can carry
Proppant is difficult, proppant cannot be made fully to suspend in fracturing fluid, pressure break cost is higher, and is difficult to be deep into fracture pore
Depths.And in traditional fracturing technique, it is required for using a large amount of proppant, increases the difficulty of pressing crack construction；High concentration
Proppant is easy sand plug, easily leads to pressure break failure；And the use of proppant and high-performance fracturing fluid, has increased considerably pressure break
Cost；After completing pressing crack construction, fracturing fluid needs brokenly glue to return to be discharged to ground, if the row of returning is not thorough, fracturing fluid can be to reservoir
It damages, reduces in-place permeability, cause fracturing effect undesirable.For this purpose, proposing the present invention.
Invention content
In view of the deficiencies of the prior art, the present invention provide it is a kind of with high flow conductivity without sand fracturing fluid.This is without sand pressure
Fracture pore depths can be goed deep by splitting liquid, improve the rate of oil and gas recovery, simple and practicable, can substantially reduce pressure break cost and construction risk.
The present invention also provides a kind of preparation method with high flow conductivity without sand fracturing fluid and fracturing technology and applications.
Technical scheme is as follows：
A kind of no sand fracturing fluid, include the A groups fracturing fluid containing curable resin performed polymer and contain curing agent and fiber
B group fracturing fluids, the A groups fracturing fluid and B group fracturing fluids are used cooperatively.
The A groups fracturing fluid is to add curable resin performed polymer in existing fracturing fluid 1 to be made；The B groups pressure break
Liquid is that addition curing agent and fiber are made in existing fracturing fluid 2.
The existing fracturing fluid 1 or fracturing fluid 2 are commercial products or the pressure break liquid product that is obtained by prior art preparation；
The existing fracturing fluid 1 or fracturing fluid 2 are identical or different.
According to currently preferred, the existing fracturing fluid 1 or fracturing fluid 2 are guanidine gum fracturing fluid.Guanidine gum fracturing fluid can
Market is bought, also can be by prior art preparation；The preparation method of the preferably following guanidine gum fracturing fluid of the present invention：
Guar gum is soluble in water, the glue that mass concentration is 0.2-0.6% is made, then presses and guar gum 1: 4-6
Mass ratio be added mass concentration be 50% crosslinking agent sodium tetraborate solution, be stirred at room temperature to get guanidine gum fracturing fluid.
According to currently preferred, curable resin performed polymer is melamine resin performed polymer, phenolic aldehyde in the A groups fracturing fluid
Resin prepolymer or epoxy resin prepolymer；Most preferably, the curable resin performed polymer is epoxy resin prepolymer.It can city
Purchase is obtained or is made according to the prior art.
The preparation method of the preferably following epoxy resin prepolymer of the present invention：Under atmosphere of inert gases, by acrylic acid rosin
It is mixed with triethylamine, heating makes acrylic acid rosin melt, and butanediol diglycidyl ether is added, and in 130 DEG C of reactions, works as reaction solution
Acid value (KOH) stops reaction when being less than 1mg/g, through being filtered, washed to get epoxy resin prepolymer；The butanediol two shrinks
The mass ratio of glycerin ether and acrylic acid rosin is 1-3: 1；The quality of the triethylamine is the 0.01- of acrylic acid rosin quality
0.04%.
According to currently preferred, the mass content of curable resin performed polymer is 50- in the A groups fracturing fluid
80wt%.
According to currently preferred, the mass content of curing agent is 50-80wt% in the B groups fracturing fluid.
According to currently preferred, the fiber in the B groups fracturing fluid is organic fiber or inorfil；Preferably, institute
State the glass fibre that inorfil is glass fibre or surface is modified.It is commercially available or obtained according to the prior art.
Preferably, the glass fibre that the surface is modified is to mix to come at 50-150 DEG C with nano particle by glass fibre
Carry out surface modification；The mass ratio of the nano particle and glass fibre is 10:1~1:1；The nano particle is nano-silica
SiClx or nano-titanium dioxide.The prior art is pressed with the method for modified by nano particles fiberglass surfacing.
According to currently preferred, the fibre length is 8-12mm；It is preferred that fibre length is 10mm.
According to currently preferred, the mass content of fiber is 0.2%-0.6% in the B groups fracturing fluid.
According to currently preferred, the mass ratio of fiber and curing agent in the B groups fracturing fluid is (0.2-0.5):(2-
60)；Preferably (0.2-0.5):(30-40)；Further preferably 0.4:30.
According to currently preferred, the A groups fracturing fluid and B group fracturing fluids are with the use of being according to curable resin pre-polymerization
Body：Curing agent=100:(2-60) mass ratio is used cooperatively；Further preferably press curable resin performed polymer：Curing agent=100:
(30-40) mass ratio is used cooperatively；Most preferably according to curable resin performed polymer：Curing agent=100:The cooperation of 30 mass ratioes makes
With.
According to currently preferred, curing agent is water-based polyurethane curing agent in the B groups fracturing fluid.The aqueous poly- ammonia
The commercially available acquisition of ester curing agent, or be prepared according to 105968304 A of patent document CN.
A kind of preparation method without sand fracturing fluid with high flow conductivity, including steps are as follows：
(1) preparation of A groups fracturing fluid
Curable resin performed polymer is scattered in existing fracturing fluid 1 to get A group fracturing fluids；
(2) preparation of B groups fracturing fluid
Curing agent and fiber are scattered in existing fracturing fluid 2 to get B group fracturing fluids；
The existing fracturing fluid 1 or fracturing fluid 2 are identical or different.
It is a kind of with high flow conductivity without sand fracturing technology, including use the present invention without sand fracturing fluid, steps are as follows：
The A group fracturing fluids that the no sand fracturing fluid is noted to stratum pump, after forming crack, then are pumped into the no sand fracturing fluid
B group fracturing fluids, under formation temperature, hydraulic fracturing effect, resins synthesis and/or coating reaction, formation, which occurs, in underground has
The fiber of the spongelike structure of hole reinforces porous resin.
It is a kind of to be applied to oil-gas mining hydraulic fracturing without sand fracturing fluid with high flow conductivity.
The present invention without sand fracturing technology, first pump note A group fracturing fluids to stratum, high pressure formed in shaft bottom, thus on stratum
In press off man-made fracture, after forming crack, be pumped into B group fracturing fluids, B group fracturing fluids have blended fiber reinforced material, A, B group fracturing fluid
Under formation temperature, pressure break effect, resins synthesis and/or cladding chemical reaction occurs in underground, it is anti-that chemistry occurs for A group fracturing fluids
It should be coated on fiber surface at resin, after resin solidification, accumulation forms with high intensity and has the spongy of many holes
The fiber of structure reinforces porous resin, and to fill crack, after crack closure, fiber reinforcement porous resin, which can be used as support wall, to be had
Imitate supporting crack.On the one hand fiber, which reinforces porous resin, can provide the flow-guiding channel of oil gas water, on the other hand, high intensity it is whole
Body resin can play the role of supporting crack again.
Beneficial effects of the present invention are as follows：
Be not in the feelings of sand plug in fracturing process 1. the fracturing fluid and fracturing technology of the present invention need not use proppant
Condition solves the problems, such as the frequent sand plug of traditional fracturing process；
2. the fracturing fluid and fracturing technology of the present invention need not take sand, therefore not have viscosity requirement, the requirement to chemical agent
Also low, pump-in pressure is greatly reduced, construction risk is reduced；
3. the fracturing fluid of the present invention need not the row of returning while shortening pressing crack construction the problem of being not present to reservoir damage
Duration, and considerably reduce pressure break cost.
4. the fracturing fluid and fracturing technology of the present invention act on bigger to the unconventional reservoirs pressure break such as shale, tight sand, because
Complicated seam net is often formed for unconventional reservoir pressure break, crack is relatively narrow, and proppant is difficult to be filled to inside secondary fracture, affects
Fracturing effect, after technique using the present invention, fracturing fluid, which can enter in cracks at different levels, to be formed fiber and reinforces porous resin, can
There is higher flow conductivity with the complicated seam net system for ensuring pressed off, improve the rate of oil and gas recovery, it is special to can be used for responsive type
The oil-gas mining of reservoir.
5. the fracturing fluid and fracturing technology of the present invention can be in nothings such as slippery water pressure break, titanium dioxide carbon/nitrogen gas/liquefied natural gas
It uses in water fracturing technique, can be used for preposition pressure break or is used cooperatively with traditional fracturing technique.
6. the fracturing fluid and fracturing technology of the present invention make pressure break become a simple and practicable technology, construction equipment
Simplify, design scheme also effectively simplifies, and pressure break risk is greatly lowered.
Description of the drawings
Fig. 1 is single resin covered fiber schematic diagram, wherein 1 is resin, 2 be fiber.
Fig. 2 is the design sketch that resin covered fiber is laid in crack, wherein 3 be the resin after solidification, 4 be foaming structure tree
Hole in fat, 5 be fiber.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material
Material, unless otherwise specified, commercially obtains.
In embodiment, existing fracturing fluid used is guanidine gum fracturing fluid, is prepared by the following method：By the cities 10g
It purchases guar gum (Renqiu City E-BANG Chemical Co., Ltd. produces, guar gum GRJ-1) to be dissolved in 2500g water, it is dense that quality is made
The original gelatin that degree is 0.4%；Then the crosslinking agent sodium tetraborate solution that 2g mass concentrations are 50% is added, is stirred at room temperature
2min is to get guanidine gum fracturing fluid.
Epoxy resin prepolymer used is prepared by the following method：By 100g acrylic acid rosins and 0.03g triethylamines
It is added in the four-hole bottle with blender, condenser pipe, dropping funel and nitrogen conduit, leads to nitrogen, make acrylic acid in 130 DEG C of heating
Rosin melts, and 100g butanediol diglycidyl ethers are added, and 5h is reacted in 130 DEG C, through being filtered, washed to get epoxy resin prepolymer
Aggressiveness.
Water-based polyurethane curing agent used is prepared according to the embodiment 1 in patent document CN 105968304A.
Embodiment 1
A kind of no sand fracturing fluid, including A groups fracturing fluid and B group fracturing fluids, the A groups fracturing fluid is in guanidine gum fracturing fluid
It adds epoxy resin prepolymer to be made, the B groups fracturing fluid is to add water-based polyurethane curing agent in guanidine gum fracturing fluid and change
Property glass fibre be made.
The above-mentioned preparation method without sand fracturing fluid with high flow conductivity, including steps are as follows：
(1) preparation of A groups fracturing fluid
80g epoxy resin prepolymers are scattered in 100g guanidine gum fracturing fluids to get A group fracturing fluids；
(2) preparation of B groups fracturing fluid
24g water-based polyurethane curing agents, glass fibre, the 3g nano-titanium dioxides that 0.32g length is 10mm are scattered in
To get B group fracturing fluids in 100g guanidine gum fracturing fluids.
The mass ratio of water-based polyurethane curing agent and A group fracturing fluid epoxy resin performed polymers is in the B groups fracturing fluid
30:100。
The mass ratio of glass fibre and A group fracturing fluid epoxy resin performed polymers is 0.4 in the B groups fracturing fluid:100.
The A groups fracturing fluid and B groups fracturing fluid in mass ratio 1:1 is used cooperatively.
It is carried out without sand fracturing technology using above-mentioned fracturing fluid, including steps are as follows：
The A group fracturing fluids that the no sand fracturing fluid is noted to stratum pump, after forming crack, then are pumped into the no sand fracturing fluid
B group fracturing fluids, under formation temperature, hydraulic fracturing effect, resins synthesis and/or coating reaction, formation, which occurs, in underground has
The fiber of the spongelike structure of hole reinforces porous resin.
Embodiment 2-6
As described in Example 1, as different from Example 1：
The quality score of water-based polyurethane curing agent and A group fracturing fluid epoxy resin performed polymers in the B groups fracturing fluid
It Wei 20:100,35:100,40:100,50:100,60:100.
Embodiment 7-10
As described in Example 1, as different from Example 1：
Nano-titanium dioxide is added without in the B groups fracturing fluid, i.e. glass fibre is unmodified glass fibre, glass fibre
Length is 8mm；
The mass ratio of the unmodified glass fibre and A group fracturing fluid epoxy resin performed polymers is respectively 0.2:100,
0.3:100,0.4:100,0.5:100。
Embodiment 11-14
As described in Example 1, as different from Example 1：
Nano-titanium dioxide is added without in the B groups fracturing fluid, i.e. glass fibre is unmodified glass fibre, glass fibre
Length is 10mm；
The mass ratio of the unmodified glass fibre and A group fracturing fluid epoxy resin performed polymers is respectively 0.2:100,
0.3:100,0.4:100,0.5:100.
Embodiment 15-18
As described in Example 1, as different from Example 1：
Nano-titanium dioxide is added without in the B groups fracturing fluid, i.e. glass fibre is unmodified glass fibre, glass fibre
Length is 12mm；
The mass ratio of the unmodified glass fibre and A group fracturing fluid epoxy resin performed polymers is respectively 0.2:100,
0.3:100,0.4:100,0.5:100。
Test example 1
By the epoxy in the water-based polyurethane curing agent and embodiment 1-6A group fracturing fluids in embodiment 1-6B group fracturing fluids
Resin prepolymer for 24 hours, for 24 hours then at 70 DEG C of solidifications, is cooled to and is placed at room temperature for for 24 hours, obtain epoxy resin, with to be measured in room temperature curing naturally
Examination.
Using CMT microcomputer controlled electronic universal testers, measures epoxy resin according to GB7124-1986 and stretch shearing by force
Degree measures epoxy resin according to GB 6329-1985 and just draws bonding action；Using LX-D type Shore durometers, according to GB 2411-
1980 measure epoxy resin hardness；Heat analysis:2~4mg of extracting epoxy resin sample is placed in sealing pond, in the U.S.
Thermal weight loss (TG) is measured on PerkinElmerDSC-2C differential scanning calorimeters, heating rate is 20 DEG C/min.
As a result as shown in table 1,2.
Influence of the mass ratio of 1 aqueous epoxy curing agent of table and epoxy resin prepolymer to epoxy resin mechanical property
As shown in Table 1, embodiment 1, embodiment 3 and the water-based polyurethane curing agent in embodiment 4B group fracturing fluids and A groups
For epoxy resin prepolymer mass ratio in fracturing fluid at 30: 100-40: 100, the shear behavior of epoxy resin is more preferable and just draws
Bonding action is preferable, wherein with the waterborne curing agent in B group fracturing fluids in embodiment 1 and the epoxy resin prepolymer in A group fracturing fluids
Aggressiveness mass ratio is best at 30: 100.From Shore durometer number it is found that waterborne curing agent exists with epoxy resin prepolymer mass ratio
The ability of the resistance to mechanical pressure of epoxy resin is most strong when 30: 100.
The mass ratio of 2 waterborne curing agent of table and epoxy resin prepolymer influences epoxy resin heat resistance
By the epoxy in the water-based polyurethane curing agent and embodiment 1-6A group fracturing fluids in embodiment 1-6B group fracturing fluids
The epoxy resin of the cured preparation of resin prepolymer carries out heat analysis on differential scanning calorimeter, and the results are shown in Table 2.From table
Known to 2:The mass ratio of water-based polyurethane curing agent in B group fracturing fluids and the epoxy resin prepolymer in A group fracturing fluids is 30:
It is little in 400 DEG C of decomposition percentage difference below in 100~40: 100 ranges, it is 55% or so, and extreme value thermal decomposition temperature
Degree is higher, but decomposes percentage when mass ratio increases to 50: 100 and be significantly improved, and reaches 65% or more.
In conclusion by the epoxy resin prepolymer in the water-based polyurethane curing agent and A group fracturing fluids in B group fracturing fluids
Influence of the mass ratio to epoxy resin mechanical property and heat resistance it is found that water-based polyurethane curing agent and epoxy resin prepolymer
Mass ratio be in 30: 100~35: 100 ranges, especially when at 30: 100 epoxy resin cure it is more complete, extreme value thermal decomposition
Temperature highest is 387.9 DEG C, and structure is relatively stablized.This is because excessive curing agent cannot participate in being formed admittedly in curing system
Change structure, in the environment of higher temperature, instead because of the heat resistance of its chemical constitution de-stabilising effect cured product.Cause
This, excessive curing agent not can be used to participate in curing reaction.
Test example 2
What is formed after A groups fracturing fluid in embodiment 7-18 and B group fracturing fluids are used cooperatively reinforces porous ring containing fiber
Oxygen resin prepares high 8.0mm, internal diameter 4.0mm cylindrical resin test specimens according to ISO9917 standards.It is poly- to prepare two semi-cylindricals
Teflon mold first reinforces fiber in porous epoxy resin difference slicing and filling to two molds, then by mold pairing,
Both ends add glass plate to flatten.Illumination 40s is distinguished in all directions with light-solidified lamp, is detached mold after resin is fully cured, is taken
Go out resin test specimen.After test specimen is fully cured, crush test is carried out.
According to compressive strength standard as defined in American National Standard, using the compression strength of universal testing machine test sample,
Loading velocity is 1.0mm/min, the destruction value F (N) when record test specimen is broken, according to formula CS=4F/ π d2(CS is pressure resistance
Degree, d are the diameter of cylindrical sample) it calculates.
Experiment uses fracture condudtiviy to evaluate instrument, and instrument can add the fiber of formation with simulation stratum condition
Strong porous epoxy foams structure carries out long-term flow conductivity evaluation.150 DEG C of instrument highest experimental temperature, maximum close pressure
200MPa is entirely capable of meeting the actual needs in China oil field.The instrument is designed according to API standard, and test result is as shown in table 3.
Fiber under the different fiber parameters of table 3 reinforces the performance test of porous epoxy resin
From table 3 it is observed that when glass fibre length is 10mm, larger compression strength and water conservancy diversion energy can be reached
Power, long fiber can influence cladding of the epoxy resin to fiber instead so that entire fiber reinforces porous epoxy foams
The hole of structure is reduced, and reduces the handling capacity of oil gas water.It is 0.4% in the mass ratio of glass fibre and epoxy prepolymer
When, as soon as compression strength and flow conductivity can reach a larger peak value, the hole of formation is also more.In glass fibre and ring
The mass ratio of oxygen resin prepolymer be higher than 0.4% when, fiber can mutually be wrapped over it is more, cause resin to fiber cladding excessively, shape
At hole it is just few, to reduce flow conductivity.Therefore best fiber parameters are preferably, length 10mm, glass fibre and ring
The mass ratio of oxygen resin prepolymer is 0.4%.
Test example 3
After A groups fracturing fluid in embodiment 1 and B group fracturing fluids are used cooperatively, for 24 hours in room temperature curing, cure then at 70 DEG C
For 24 hours, it is cooled to naturally and is placed at room temperature for for 24 hours, the porous epoxy resin sponge structure to being formed by modified glass-fiber reinforcement carries out
Flow conductivity test experiments, test equipment is identical as the equipment in test example 2, and is formed pair with quartz sand, resin sand, walnut shell
Than examining whether it reaches the flow conductivity of normal proppant, as shown in table 4.
4 long-term flow conductivity experimental test result of table
When clossing pressure is relatively low it can be seen from 4 test data of table, 1 gained fiber of embodiment reinforces porous asphalt mixtures modified by epoxy resin
Fat flow conductivity is not as good as the natural supports agent such as quartz sand and walnut shell.But when clossing pressure is higher, flow conductivity has exceeded instead
Other natural support agent, it is broken that this illustrates that natural support agent easily occurs under high pressure, and the flow conductivity between proppant is made to reduce, from
And it is unfavorable to pressure break.And fiber that the present invention obtains reinforces porous epoxy resin under high pressure, due to its special voltage endurance capability,
Keep its percentage of damage less, foaming structure integrality is good, still has good flow conductivity, is suitable for high pressure formation.
In embodiment 1, glass fibre is the glass fibre being modified by titanium dioxide nanoparticle, tight with resin-bonded
It is close, since titanium dioxide nanoparticle has higher reactivity, the solidification process of epoxy resin can be participated in, therefore significantly
Improve the interface interaction between two-phase.Therefore the porous epoxy resin that the modified glass-fiber that prepared by embodiment 1 is reinforced so that
Bond strength between fiber and resin can reach more preferably use condition.
Claims (10)
1. a kind of no sand fracturing fluid, which is characterized in that include the A groups fracturing fluid containing curable resin performed polymer and containing solidification
The B group fracturing fluids of agent and fiber, the A groups fracturing fluid and B group fracturing fluids are used cooperatively.
2. no sand fracturing fluid according to claim 1, which is characterized in that curable resin pre-polymerization in the A groups fracturing fluid
Body is melamine resin performed polymer, phenolic resin performed polymer or epoxy resin prepolymer；Most preferably, the curable resin pre-polymerization
Body is epoxy resin prepolymer.
3. no sand fracturing fluid according to claim 1, which is characterized in that curable resin pre-polymerization in the A groups fracturing fluid
The mass content of body is 50-80wt%；The mass content of curing agent is 50-80wt% in the B groups fracturing fluid；The B groups pressure
The mass content for splitting fiber in liquid is 0.2-0.6wt%.
4. no sand fracturing fluid according to claim 1, which is characterized in that the fiber in the B groups fracturing fluid is organic fibre
Dimension or inorfil；Preferably, the inorfil is glass fibre or the glass fibre that surface is modified；It is further preferred that
The glass fibre that the surface is modified is to mix glass fibre to carry out surface modification, institute at 50-150 DEG C with nano particle
The mass ratio for stating nano particle and glass fibre is 10:1-1:1, the nano particle is nano silicon dioxide or nanometer titanium dioxide
Titanium；
Preferably, curing agent is water-based polyurethane curing agent in the B groups fracturing fluid.
5. no sand fracturing fluid according to claim 1, which is characterized in that the fibre length is 8-12mm；It is preferred that fiber
Length is 10mm.
6. no sand fracturing fluid according to claim 1, which is characterized in that fiber and curing agent in the B groups fracturing fluid
Mass ratio be (0.2-0.5):(2-60)；Preferably (0.2-0.5):(30-40)；Further preferably 0.4:30.
7. no sand fracturing fluid according to claim 1, which is characterized in that the A groups fracturing fluid and the cooperation of B group fracturing fluids make
With being according to curable resin performed polymer：Curing agent=100:(2-60) mass ratio is used cooperatively；
It is preferred that pressing curable resin performed polymer：Curing agent=100:(30-40) mass ratio is used cooperatively；Most preferably according to curable
Resin prepolymer：Curing agent=100:30 mass ratioes are used cooperatively.
8. a kind of preparation method without sand fracturing fluid such as claim 1-7 any one of them with high flow conductivity, including
Steps are as follows：
(1) preparation of A groups fracturing fluid
Curable resin performed polymer is scattered in existing fracturing fluid 1 to get A group fracturing fluids；
(2) preparation of B groups fracturing fluid
Curing agent and fiber are scattered in existing fracturing fluid 2 to get B group fracturing fluids；
The existing fracturing fluid 1 or fracturing fluid 2 are identical or different.
9. it is a kind of with high flow conductivity without sand fracturing technology, including use the present invention without sand fracturing fluid, steps are as follows：
The A group fracturing fluids that the no sand fracturing fluid is noted to stratum pump, after forming crack, then are pumped into the B groups of the no sand fracturing fluid
Under formation temperature, hydraulic fracturing effect in underground resins synthesis and/or coating reaction occur for fracturing fluid, being formed has hole
Spongelike structure fiber reinforce porous resin.
10. a kind of being applied to oil-gas mining with high flow conductivity such as claim 1-7 any one of them without sand fracturing fluid
Hydraulic fracturing.
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