CN117143584A - Slick water system based on amphiphilic polymer and preparation method thereof - Google Patents
Slick water system based on amphiphilic polymer and preparation method thereof Download PDFInfo
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- CN117143584A CN117143584A CN202310028378.1A CN202310028378A CN117143584A CN 117143584 A CN117143584 A CN 117143584A CN 202310028378 A CN202310028378 A CN 202310028378A CN 117143584 A CN117143584 A CN 117143584A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002077 nanosphere Substances 0.000 claims abstract description 62
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 125000002091 cationic group Chemical group 0.000 claims abstract description 42
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 34
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 27
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000004927 clay Substances 0.000 claims abstract description 11
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract 3
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- 230000000694 effects Effects 0.000 claims description 15
- IAGIRAMRPKZOQT-UHFFFAOYSA-N prop-2-enylazanium;bromide Chemical compound [Br-].[NH3+]CC=C IAGIRAMRPKZOQT-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 230000001502 supplementing effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N Amide-Hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000008363 phosphate buffer Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000693 micelle Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- MVYQJCPZZBFMLF-UHFFFAOYSA-N hydron;propan-1-amine;bromide Chemical compound [Br-].CCC[NH3+] MVYQJCPZZBFMLF-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- -1 erucic acid amide propyl ammonium bromide Chemical compound 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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
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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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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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
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
- C09K8/608—Polymer compositions
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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
- C09K8/665—Compositions based on water or polar solvents containing inorganic compounds
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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
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a slick water system based on an amphiphilic polymer, which is prepared from the following raw materials in parts by mass: 0.05 to 0.5 weight percent of suspension drag reducer, 0.1 to 1.0 weight percent of clay stabilizer, 0.3 to 1.5 weight percent of cleanup additive and the balance of water; the suspension drag reducer is prepared from the following raw materials in parts by mass: 40% of amphiphilic polymer, 3% of organic montmorillonite and the balance of white oil; the amphiphilic polymer is prepared from acrylamide, acrylonitrile, cationic hydrophobic monomer and aggregate; the aggregate is mesoporous carbon nanospheres loaded with 2-acrylamide-2-methylpropanesulfonic acid. Also disclosed is a method for preparing a slickwater system based on amphiphilic polymers. The beneficial effects achieved by the invention are as follows: the hydrophobic association enables the drag reducer to have lower dosage compared with the traditional suspension drag reducer, and the addition of aggregate enables the network structure formed by the amphiphilic polymer in the aqueous solution to be firmer, so that the drag reducer has better vortex resistance reduction capability, and meanwhile, the cationic amphiphilic polymer also enables the prepared slickwater to have high salt resistance.
Description
Technical Field
The invention relates to the technical field of oilfield exploitation auxiliary agents, in particular to temperature-resistant and salt-resistant slick water based on amphiphilic polymers and a preparation method thereof.
Background
Slickwater fracturing fluids are a common fracturing fluid system for hydraulic fracturing shale oil and gas reservoirs, and in order to avoid energy loss in pipelines, slickwater is required to have a low friction characteristic. The drag reducer is a key component in slick water, and can reduce friction of fluid flowing in a pipeline.
Currently, the most widely used water-based drag reducer is a polyacrylamide drag reducer formed by copolymerizing a plurality of different monomers, and then the drag reducer is formulated with water to form slick water.
When the preparation is finished, the slickwater is mainly used for carrying materials with rigid characteristics such as quartz sand and ceramsite into a stratum, so that on the premise of reducing construction friction resistance, the slickwater is expected to have better supporting performance on the materials such as quartz sand and ceramsite, so that the slickwater slowly settles to enter the deep stratum, and sand blockage is prevented.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides temperature-resistant and salt-resistant slick water based on amphiphilic polymers and a preparation method thereof, which solve the problem that the existing slick water prepared by taking common polymers as resistance reducing agents is not high in salt resistance, and simultaneously solve the problem that propping agents such as quartz sand, ceramsite and the like are quickly settled in the slick water.
The aim of the invention is achieved by the following technical scheme:
(first aspect)
The slick water system based on the amphiphilic polymer is prepared from the following raw materials in parts by mass: 0.05-0.5wt% of suspension drag reducer, 0.1-1.0wt% of clay stabilizer, 0.3-1.5wt% of cleanup additive and the balance of water;
the suspension drag reducer is prepared from the following raw materials in parts by mass: 40% of amphiphilic polymer, 3% of organic montmorillonite and the balance of white oil;
the amphiphilic polymer is prepared from acrylamide, acrylonitrile, cationic hydrophobic monomer and aggregate;
the aggregate is mesoporous carbon nanospheres loaded with 2-acrylamide-2-methylpropanesulfonic acid.
In the scheme, in the drag reducer, the weight parts are as follows: the amphiphilic polymer comprises the following components in parts by weight: 50-70 parts of acrylamide, 20-40 parts of acrylonitrile, 3-5 parts of cationic hydrophobic monomer and 5-7 parts of aggregate; 2-acrylamide-2-methylpropanesulfonic acid in aggregate: the mesoporous carbon nanospheres are 1:3-6.
Based on the above scheme, preferably, in the drag reducer, the weight parts are as follows: 64 parts of acrylamide, 26 parts of acrylonitrile, 4 parts of cationic hydrophobic monomer and 6 parts of aggregate; 2-acrylamide-2-methylpropanesulfonic acid in aggregate: the mesoporous carbon nanospheres are 1:3.
in an advantageous embodiment, the cationic hydrophobic monomer is dodecylamidopropyl allylammonium bromide, tetradecylamide allylammonium bromide, hexadecylamide allylammonium bromide, octadecylamidopropyl allylammonium bromide.
Preferably, erucamide allylammonium bromide is employed as the cationic monomer. When the preparation of erucamide propyl allylammonium bromide was completed, mass spectrometry was used to determine mass spectrometry characterization, as shown in fig. 1. As seen in FIG. 1, the peak at 463.8 for m/z is the proton peak of [ EDAA-Br ] +, indicating that the synthesized product structure is consistent with the target product.
In an advantageous embodiment, the mesoporous carbon nanospheres bearing 2-acrylamide-2-methylpropanesulfonic acid are prepared by: dissolving 2-acrylamide-2-methylpropanesulfonic acid into a solution, and then placing mesoporous carbon nanospheres in the solution and stirring for 24 hours; the precipitate was separated by centrifugation, washed with phosphate buffer and dried at 30℃under vacuum.
(second aspect)
The preparation method of the slick water system based on the amphiphilic polymer is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s1, firstly preparing an amphiphilic polymer;
s11, taking a proper amount of deionized water, adding acrylamide and mesoporous carbon nanospheres bearing 2-acrylamide-2-methylpropanesulfonic acid into water, and introducing nitrogen;
s12, adopting azo diisobutylamidine hydrochloride as an initiator to initiate a polymerization reaction, wherein the temperature is maintained to be 40-45 ℃ in the polymerization reaction; the duration of polymerization is 0.5-1 h;
s13, further adding acrylonitrile and cationic hydrophobic monomer, supplementing azo diisobutylamidine hydrochloride as an initiator, and continuing the polymerization reaction for 2 hours;
s2, taking white oil, adding organic montmorillonite, mechanically stirring for 30min at 1000r/min, then adding the amphiphilic polymer prepared in the step S1, and continuously stirring for 20min at 800r/min to obtain a suspension resistance reducing agent;
s3, adding the suspension resistance reducing agent prepared in the step S2 into a proper amount of water, stirring, gradually adding the clay stabilizer and the cleanup additive, and fully stirring and dissolving uniformly.
In the step S11, the acrylamide is polymerized with the 2-acrylamide-2-methylpropanesulfonic acid; the acrylamide enters the mesoporous carbon nanospheres through the small holes and is subjected to polymerization reaction with part of 2-acrylamide-2-methylpropanesulfonic acid in the mesoporous carbon nanospheres, so that a structure that the polymer passes through the holes of the mesoporous carbon nanospheres is formed, and the polymer is converted into an integral space network structure with fulcrums from a pure linear structure.
In the step S13, the acrylamide is polymerized with the acrylonitrile and the hydrophobic monomer, and the hydrophobic monomer has high salt resistance effect; the hydrophobic association between the hydrophobic monomers themselves causes the different molecular chains to attract each other, forming a more complex network structure.
When the fluid flows in the pipeline, the fluid gradually excites the vortex state from the laminar flow along with the increase of the flow speed, a large number of intense vortices are generated in the fluid, the vortices collide with the pipe wall and between the vortices, energy is lost, and the macroscopic friction is high. If slick water with a certain viscosity flows at a high speed, the amount of vortex formed is small due to the interference of polymer molecules, the probability of energy loss caused by mutual collision is reduced, and the friction is reduced macroscopically.
However, in order to avoid the vortex and thus increase the amount of polymer, the presence of a large amount of polymer in the case of a low flow rate affects the speed of laminar flow.
The principle of the scheme is as follows:
a. taking acrylamide as a basic polymer, and grafting a hydrophobic monomer, 2-acrylamide-2-methylpropanesulfonic acid and a cationic hydrophobic monomer on the basic polymer;
b. 2-acrylamide-2-methylpropanesulfonic acid is extremely easy to polymerize with acrylamide, and 2-acrylamide-2-methylpropanesulfonic acid exists in the mesoporous carbon nanospheres; therefore, when the polymerization reaction occurs, a plurality of polymer molecular chains penetrate into the mesoporous carbon nanospheres; because the mesoporous carbon nanospheres have good dispersibility, the mesoporous carbon nanospheres play a role in suspending, dispersing and supporting on the whole polymeric micelle;
c. because the cationic hydrophobic monomer has the characteristics of high temperature resistance and salt resistance, the cationic hydrophobic monomer is grafted to acrylamide, and the final polymerization product also has the characteristics of high temperature resistance and salt resistance;
when the cationic hydrophobic monomer is grafted, vortex is reduced (the prior art), but the cationic hydrophobic monomer is easy to intertwine, and when the branched chain formed after grafting is adsorbed on the aggregate to a certain extent, the branched chain is fixed to a certain extent, so that the excessive entanglement is avoided; the specific principle is that the 2-acrylamide-2-methylpropanesulfonic acid is actually an anionic surfactant, when the mesoporous carbon nanospheres are suspended after the 2-acrylamide-2-methylpropanesulfonic acid is polymerized with acrylamide, the mesoporous carbon nanospheres still release some 2-acrylamide-2-methylpropanesulfonic acid, and when the cationic hydrophobic monomer is polymerized with acrylamide, the 2-acrylamide-2-methylpropanesulfonic acid on the surfaces of the cationic hydrophobic monomer and the mesoporous carbon nanospheres generates certain adsorption, which is equivalent to adsorbing branched chains of the cationic hydrophobic monomer on the surfaces of the mesoporous carbon nanospheres, so that the mesoporous carbon nanospheres are fixed and entanglement is avoided;
d. compared with the traditional polymer, the mesoporous carbon nanospheres are used as the dispersion support materials in a matched mode, the mesoporous carbon nanospheres are firmly fixed with polymer molecules through a mode of polymerization reaction of acrylamide and 2-acrylamide-2-methylpropanesulfonic acid in the mesoporous carbon nanospheres, and compared with the traditional polymer and the nanomaterial through charge adsorption and other modes, the combination mode has higher combination strength and higher combination stability.
The invention has the following advantages:
(1) Through arranging mesoporous carbon nanospheres loaded with 2-acrylamide-2-methylpropanesulfonic acid, acrylamide stretches into the mesoporous carbon nanospheres to form polymer molecular chains, and the bonding strength of the mesoporous carbon nanospheres is enhanced; under the excellent suspension dispersion effect of the mesoporous carbon nanospheres, the whole polymer product has excellent suspension dispersion effect in aqueous solution, a more compact network structure and viscosity can be formed, and the performance of the solution is not affected even if the solution is placed for a long time;
(2) By introducing a cationic hydrophobic monomer, particularly erucamide propyl ammonium bromide, the vortex can be reduced very effectively due to the existence of hydrophobic and chain; because the cationic hydrophobic monomer is adsorbed on the mesoporous carbon nanospheres with negative ions to a certain extent, the cationic hydrophobic monomer is not easy to tangle after grafting, and gel breaking is facilitated;
(3) Because the long-chain cationic surfactant is positive, the negative soil particles during exploitation are easy to adsorb, and the anti-swelling capacity is good;
(4) The cationic hydrophobic monomer, especially the grafted erucic acid amide propyl ammonium bromide, ensures that the whole polymerization product shows excellent salt resistance and high temperature resistance.
Drawings
FIG. 1 is a mass spectral characterization of erucamide propyl ammonium bromide;
FIG. 2 is an electron micrograph of a suspension friction reducer of comparative example 1 in aqueous solution to form a network structure;
FIG. 3 example 2 electron microscopy of a network structure formed by a suspension polymer in aqueous solution;
FIG. 4 shows the reaction process in the preparation of cationic hydrophobic monomers.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Example 1
The preparation method of the temperature-resistant salt-resistant slickwater based on the amphiphilic polymer comprises the following steps:
s1, firstly preparing an amphiphilic polymer;
s11, taking a proper amount of deionized water, adding 50 parts of acrylamide and 5 parts of mesoporous carbon nanospheres (1.25 parts of 2-acrylamide-2-methylpropanesulfonic acid and 4.75 parts of open-cell carbon nanospheres) loaded with 2-acrylamide-2-methylpropanesulfonic acid into water, and introducing nitrogen;
s12, adopting azo diisobutylamidine hydrochloride as an initiator to initiate a polymerization reaction, wherein the temperature is maintained at 40 ℃ in the polymerization reaction; the duration of polymerization was 0.5h;
s13, further adding 20 parts of acrylonitrile and 3 parts of hydrophobic monomer, supplementing azo diisobutylamidine hydrochloride as an initiator, and continuing the polymerization reaction for 2 hours;
s2, taking white oil, adding organic montmorillonite, mechanically stirring for 30min at 1000r/min, then adding the amphiphilic polymer prepared in the step S1, and continuously stirring for 20min at 800r/min to obtain a suspension resistance reducing agent; amphiphilic polymers: white oil: organic montmorillonite=40: 3:57.
s3, adding the suspension resistance reducing agent prepared in the step S2 into a proper amount of water, stirring, gradually adding the clay stabilizer and the cleanup additive, and fully stirring and dissolving uniformly; suspension drag reducer: clay stabilizer: discharge assisting agent: water=0.05:0.1:0.3: 95.55.
example 2
The preparation method of the temperature-resistant salt-resistant slickwater based on the amphiphilic polymer comprises the following steps:
s1, firstly preparing an amphiphilic polymer;
s11, taking a proper amount of deionized water, adding 64 parts of acrylamide and 6 parts of mesoporous carbon nanospheres loaded with 2-acrylamide-2-methylpropanesulfonic acid (1 part of 2-acrylamide-2-methylpropanesulfonic acid and 5 parts of open-cell carbon nanospheres) into water, and introducing nitrogen;
s12, adopting azo diisobutylamidine hydrochloride as an initiator to initiate a polymerization reaction, wherein the temperature is maintained at 42 ℃ in the polymerization reaction; the duration of polymerization was 0.8h;
s13, further adding 30 parts of acrylonitrile and 4 parts of cationic hydrophobic monomer, supplementing azo diisobutylamidine hydrochloride as an initiator, and continuing the polymerization reaction for 2 hours;
s2, taking white oil, adding organic montmorillonite, mechanically stirring for 30min at 1000r/min, then adding the amphiphilic polymer prepared in the step S1, and continuously stirring for 20min at 800r/min to obtain a suspension resistance reducing agent; amphiphilic polymers: white oil: organic montmorillonite=40: 3:57.
s3, adding the suspension resistance reducing agent prepared in the step S2 into a proper amount of water, stirring, gradually adding the clay stabilizer and the cleanup additive, and fully stirring and dissolving uniformly; suspension drag reducer: clay stabilizer: discharge assisting agent: water = 0.2:0.5:0.8:98.5.
example 3
The preparation method of the temperature-resistant salt-resistant slickwater based on the amphiphilic polymer comprises the following steps:
s1, firstly preparing an amphiphilic polymer;
s11, taking a proper amount of deionized water, adding 70 parts of acrylamide and 7 parts of mesoporous carbon nanospheres loaded with 2-acrylamide-2-methylpropanesulfonic acid (1 part of 2-acrylamide-2-methylpropanesulfonic acid and 6 parts of open-cell carbon nanospheres) into water, and introducing nitrogen;
s12, adopting azo diisobutylamidine hydrochloride as an initiator to initiate a polymerization reaction, wherein the temperature is maintained at 45 ℃; the duration of polymerization was 1h;
s13, further adding 40 parts of acrylonitrile and 5 parts of cationic hydrophobic monomer, supplementing azo diisobutylamidine hydrochloride as an initiator, and continuing the polymerization reaction for 2 hours;
s2, taking white oil, adding organic montmorillonite, mechanically stirring for 30min at 1000r/min, then adding the amphiphilic polymer prepared in the step S1, and continuously stirring for 20min at 800r/min to obtain a suspension resistance reducing agent; amphiphilic polymers: white oil: organic montmorillonite=40: 3:57.
s3, adding the suspension resistance reducing agent prepared in the step S2 into a proper amount of water, stirring, gradually adding the clay stabilizer and the cleanup additive, and fully stirring and dissolving uniformly; suspension drag reducer: clay stabilizer: discharge assisting agent: water=0.5:1.0:1.5:97.
The cationic hydrophobic monomers used in examples 1 to 3 were erucamide allylammonium bromide.
Comparative example 1
Compared with example 2, the difference is that 40 parts of montmorillonite is used instead of mesoporous nanospheres. (60)
Comparative example 2
The difference compared to example 2 is that no mesoporous carbon nanospheres were added. (30)
Comparative example 3
The difference compared with example 2 is that the cationic hydrophobic monomer of the present scheme is replaced with a general cationic monomer having no hydrophobic chain (produced by Henan provincial pure chemical Co., ltd.). (90)
Comparative example 4
The difference compared to example 2 is that no cationic hydrophobic monomer is added. (75)
Test example 1
The water for skating prepared in example 2, comparative example 1, comparative example 2, comparative example 3, comparative example 4 was evaluated, and 3 groups of samples were selected, respectively. The results of the performance test are shown in Table 1.
Table 1 results of performance experiments
As can be seen from table 1:
from the apparent viscosity data, the comparative examples 1, 2, 3 and 4 are all reduced compared with the experimental example 2, which shows that the addition of mesoporous carbon nanoporous spheres or cationic hydrophobic monomers helps to improve the tackifying performance of the polymer, mainly because the mesoporous carbon nanoporous spheres can be used as physical support points of polymer molecular chains in aqueous solution, and the cationic hydrophobic monomers can increase the bonding degree between molecules through hydrophobic association, thereby helping to increase the crosslinking performance of the polymer molecules and further improving the solution viscosity.
From the aspect of the sedimentation rate of propping agent, comparative examples 1 and 2 have poorer sand suspending effect compared with experimental examples 2, 3 and 4, and comparative examples 3 and 4 also have poorer sand suspending effect compared with example 2, which indicates that the addition of mesoporous carbon nano-pore spheres and cationic hydrophobic monomers is beneficial to improving the viscoelasticity of polymer solution, and the mesoporous carbon nano-pore spheres have more obvious effect, mainly because the mesoporous carbon nano-pore spheres form a stable structure with the whole molecule through covalent bonds, and the cationic hydrophobic monomers can only improve the structural stability through weaker non-covalent effect and are more easily damaged.
From the aspect of resistivity reduction, the comparative examples 1, 2, 3 and 4 have no large difference compared with the experimental example 2, mainly because the polymer molecules can form a network structure in water so as to effectively reduce the turbulence phenomenon of the water, and the resistivity reduction of different polymers is relatively small because the turbulence phenomenon of the water can not change due to the strength of the network structure.
Test example 2
Comparative example 1 the suspension drag reducer corresponding to example 2 was placed in water to form a water solution, and the resulting network structure electron microscopy images were as shown in fig. 2 and 3. FIG. 2 is an electron microscope image of a network structure formed by the suspension friction reducer of comparative example 1 in an aqueous solution; FIG. 3 is an electron microscope image of the network structure formed in the aqueous solution of the suspension friction reducer according to example 2.
As can be seen from the figures: 1. the network structure formed by the suspension drag reducer with the mesoporous carbon nanospheres is more compact (fig. 3 is more compact than fig. 2); 2. the micelle formed by the suspension drag reducer with the mesoporous carbon nanospheres is finer.
The reason for this phenomenon is: 1. in the polymerization process, if acrylamide is polymerized with 2-acrylamide-2-methylpropanesulfonic acid at mesoporous carbon nanospheres (at the inner part and the orifice), a plurality of micelles can pass through the mesoporous carbon nanospheres (the micelle does not need to pass through the mesoporous carbon nanospheres in the figure 2 of the mesoporous carbon nanospheres, and only needs to adsorb montmorillonite); 2. after the cationic hydrophobic monomer is on the whole polymer, the cationic hydrophobic branched chain which is originally in a free state can be adsorbed at the mesoporous carbon nanospheres (positive for the cationic hydrophobic monomer and negative for the 2-acrylamide-2-methylpropanesulfonic acid at the mesoporous carbon nanospheres, so that the cationic hydrophobic branched chain is adsorbed); 3. since some acrylamide is polymerized with 2-acrylamide-2-methylpropanesulfonic acid at the mesoporous carbon nanospheres (at the inner part and the orifice), but the amount of 2-acrylamide-2-methylpropanesulfonic acid at the single orifice of the mesoporous carbon nanospheres is smaller, the polymerization is that the formed adhesive tape is finer.
The benefits of the phenomenon are:
1. because the pore size distribution of the mesoporous carbon nanospheres is adjustable, and the volume of the internal cavity is adjustable, if a plurality of closed cavities exist in the internal cavity, the mesoporous carbon nanospheres with good suspension effect can be formed (the scheme is selected so as to improve the suspension performance); when a plurality of micelles pass through the mesoporous carbon nanospheres during polymerization, the mesoporous carbon nanospheres are equivalent to nodes with good suspension effect on the micelles, and the whole micelles are suspended through the nodes with good suspension effect, so that the whole polymer shows good suspension performance;
2. in the common drag reducer, hydrophobic cationic monomers are also adopted to reduce vortex (vortex is reduced, so that the flowing effect of slickwater can be improved), but after grafting, the hydrophobic cationic branches are easy to entangle, so that the flowing effect is reduced to a certain extent (the flowing effect can be improved as a whole, but the performance is not developed to the limit); therefore, the mesoporous carbon nanospheres are introduced in the scheme, and the 2-acrylamide-2-methylpropanesulfonic acid stored in the mesoporous carbon nanospheres is negative, and the hydrophobic cation branched chains are positive, so that the hydrophobic cation branched chains can be adsorbed on the mesoporous carbon nanospheres to a certain extent, entanglement is avoided, and the vortex-blocking effect of the hydrophobic cation branched chains is extremely achieved.
3. Although the polymer network structure contained in slick water can reduce vortex flow, thereby improving fluidity during exploitation; however, it does not mean that the denser the polymer network structure is, when the polymer network structure is very dense, the polymer network structure can block not only vortex but also the normal flow of liquid, namely, when the polymer network structure is very dense, the mobility is reduced; in this scheme, as can be seen from fig. 3, the micelle is very thin, so when the flow velocity of the liquid reaches a certain degree, the network structures can be damaged to a certain extent (fig. 2 is not easy to damage due to the thick micelle), that is, the densification of this scheme can not cause obstruction to the flow of the liquid (i.e. the eddy current is reduced, and the normal transportation of the liquid can not be hindered).
The foregoing examples represent only preferred embodiments, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.
Claims (8)
1. Slick water system based on amphiphilic polymers, characterized in that: the material is prepared from the following raw materials in parts by mass: 0.05-0.5wt% of suspension drag reducer, 0.1-1.0wt% of clay stabilizer, 0.3-1.5wt% of cleanup additive and the balance of water;
the suspension drag reducer is prepared from the following raw materials in parts by mass: 40% of amphiphilic polymer, 3% of organic montmorillonite and the balance of white oil;
the amphiphilic polymer is prepared from acrylamide, acrylonitrile, cationic hydrophobic monomer and aggregate;
the aggregate is mesoporous carbon nanospheres loaded with 2-acrylamide-2-methylpropanesulfonic acid.
2. The amphiphilic polymer-based slick water system of claim 1, wherein: the amphiphilic polymer comprises the following components in parts by weight: 50-70 parts of acrylamide, 20-40 parts of acrylonitrile, 3-5 parts of cationic hydrophobic monomer and 5-7 parts of aggregate;
2-acrylamide-2-methylpropanesulfonic acid in aggregate: the mesoporous carbon nanospheres are 1:3-6.
3. The amphiphilic polymer-based slick water system of claim 2, wherein: the amphiphilic polymer comprises the following components in parts by weight: 64 parts of acrylamide, 26 parts of acrylonitrile, 4 parts of cationic hydrophobic monomer and 6 parts of aggregate;
2-acrylamide-2-methylpropanesulfonic acid in aggregate: the mesoporous carbon nanospheres are 1:3.
4. the amphiphilic polymer-based slick water system of claim 1, wherein: the cationic hydrophobic monomer is dodecylamidopropyl allylammonium bromide, tetradecylamide allylammonium bromide, hexadecylamide allylammonium bromide and octadecylamidopropyl allylammonium bromide.
5. The amphiphilic polymer-based slick water system of claim 1, wherein: the mesoporous carbon nanospheres bearing 2-acrylamide-2-methylpropanesulfonic acid are prepared by the following steps:
dissolving 2-acrylamide-2-methylpropanesulfonic acid into a solution, and then placing mesoporous carbon nanospheres in the solution and stirring for 24 hours;
the precipitate was separated by centrifugation, washed with phosphate buffer and dried at 30℃under vacuum.
6. The preparation method of the slick water system based on the amphiphilic polymer is characterized by comprising the following steps of: the preparation method comprises the following preparation steps:
s1, firstly preparing an amphiphilic polymer;
s11, taking a proper amount of deionized water, adding acrylamide and mesoporous carbon nanospheres bearing 2-acrylamide-2-methylpropanesulfonic acid into water, and introducing nitrogen;
s12, adopting azo diisobutylamidine hydrochloride as an initiator to initiate a polymerization reaction, wherein the temperature is maintained to be 40-45 ℃ in the polymerization reaction; the duration of polymerization is 0.5-1 h;
s13, further adding acrylonitrile and cationic hydrophobic monomer, supplementing azo diisobutylamidine hydrochloride as an initiator, and continuing the polymerization reaction for 2 hours;
s2, taking white oil, adding organic montmorillonite, mechanically stirring for 30min at 1000r/min, then adding the amphiphilic polymer prepared in the step S1, and continuously stirring for 20min at 800r/min to obtain a suspension resistance reducing agent;
s3, adding the suspension resistance reducing agent prepared in the step S2 into a proper amount of water, stirring, gradually adding the clay stabilizer and the cleanup additive, and fully stirring and dissolving uniformly.
7. The method for preparing the slick water system based on amphiphilic polymers according to claim 6, characterized in that: in the step S11, acrylamide is polymerized with 2-acrylamide-2-methylpropanesulfonic acid;
the acrylamide enters the mesoporous carbon nanospheres through the small holes and is subjected to polymerization reaction with part of 2-acrylamide-2-methylpropanesulfonic acid in the mesoporous carbon nanospheres, so that one or more polymer chains penetrate through the pore canal of the same mesoporous carbon nanospheres, and the polymer is converted from a pure linear structure into an integral space reticular structure taking the constraint of the mesoporous carbon nanospheres as a fulcrum.
8. The method for preparing the slick water system based on amphiphilic polymers according to claim 6, characterized in that: in the step S13, the acrylamide is polymerized with the acrylonitrile and the hydrophobic monomer, and the hydrophobic monomer has high salt resistance effect;
the hydrophobic association between the hydrophobic monomers themselves causes the different molecular chains to attract each other, forming a more complex network structure.
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