CN111647106B - Viscoelastic polymer emulsion and preparation method thereof, low-viscosity slippery water and high-viscosity sand-carrying fluid - Google Patents
Viscoelastic polymer emulsion and preparation method thereof, low-viscosity slippery water and high-viscosity sand-carrying fluid Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 62
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000012530 fluid Substances 0.000 title claims description 32
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000004945 emulsification Methods 0.000 title abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000003999 initiator Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 10
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 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 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004147 Sorbitan trioleate Substances 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 5
- 229950004959 sorbitan oleate Drugs 0.000 claims description 5
- 235000019337 sorbitan trioleate Nutrition 0.000 claims description 5
- 229960000391 sorbitan trioleate Drugs 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910006069 SO3H Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000012688 inverse emulsion polymerization Methods 0.000 abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- -1 octadecyl dimethyl allyl ammonium bromide Chemical compound 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- 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
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Abstract
The viscoelastic polymer emulsion is prepared into the nanoscale viscoelastic polymer emulsion capable of being pumped and injected in real time by adopting inverse emulsion polymerization, overcomes the defect of low copolymerization rate of the conventional association monomer in the inverse emulsion polymerization process, ensures that the association monomer has weaker hydrophilicity by introducing N-allyl and N-alkyl amino acid type functional association monomer and controlling the pH within the isoelectric point range, reduces the surfactant, minimizes the influence on the HLB of an emulsification system, and can be mostly dissolved in a water phase, thereby effectively improving the copolymerization rate and finally enhancing the association effect.
Description
Technical Field
The invention relates to the technical field of recyclable fracturing fluids in oil and gas fields, in particular to a viscoelastic polymer emulsion, a preparation method thereof and a fracturing fluid.
Background
With the increase of the viscosity of the fracturing fluid, the length of the fracture generated by fracturing is gradually reduced, the width of the fracture is gradually increased, and the low-viscosity fracturing fluid is favorable for controlling the width of the fracturing fracture, prolonging the length of the fracture and obtaining a better seepage channel of a reservoir and a shaft. But the lower the viscosity of the conventional fracturing fluid, the faster the sand-carrying performance of the conventional fracturing fluid is reduced. In order to obtain a good joint forming effect, the contradiction between the viscosity and the sand carrying performance must be overcome, and the structural viscosity of the fracturing fluid is increased by improving the elasticity of the fracturing fluid to realize low-viscosity sand carrying.
The conventional thickening agent undergoes an obvious swelling-dissolving process in the preparation process, the viscosity of the solution is fully extended by polymer molecular chains to reach the maximum value, and a certain time (0.5-2h) is required. If the dissolution rate is to be increased, this can be achieved by reducing the molecular weight of the polymer or by reducing the particle size of the polymer particles. The emulsion polymer system belongs to liquid high molecular polymer, has no swelling process in a solvent, and has uniformly distributed nano-scale particle size distribution, so that the emulsion polymer system has extremely high dissolution efficiency, thereby realizing real-time pump injection without preparing liquid in advance.
The vegetable gum fracturing fluid has high recovery and treatment cost and is easy to decay, and the synthetic polymer fracturing fluid well overcomes the defects and is a main object for researching the currently recoverable fracturing fluid. The polymer aqueous solution can generate association effect by introducing the long carbon chain group, the viscosity in clear water and mineralized water can be improved, and good effect is obtained in aqueous solution polymerization. However, the probability of the nonionic hydrophobic monomer (for example, octadecyl acrylate) which is commercially available at present participating in copolymerization in the inverse emulsion polymerization process is small, the effect is not obvious, the cationic hydrophobic monomer (octadecyl dimethyl allyl ammonium bromide) has strong interfacial activity, and the cationic hydrophobic monomer and the water-phase monomer are copolymerized at the interface in the inverse emulsion polymerization process, so that the copolymerization efficiency is low, and the association effect is not ideal.
Disclosure of Invention
The invention provides a viscoelastic macromolecule emulsion and a preparation method thereof, which adopts inverse emulsion polymerization to prepare the nanoscale viscoelastic macromolecule emulsion capable of being pumped and injected in real time and overcomes the defect of low copolymerization rate of the existing association monomer in the inverse emulsion polymerization process.
The invention also provides a fracturing fluid which comprises the prepared viscoelastic polymer emulsion, realizes the online conversion of the low-viscosity slippery water and the high-viscosity sand-carrying fluid by timely adjusting the dosage of the viscoelastic polymer emulsion, meets the technical requirement of continuous blending and fracturing in the whole process, and can realize the reutilization of fracturing flowback fluid.
The invention is realized by the following technical scheme:
a viscoelastic polymer emulsion has the following structural formula:
R＝-CH2CH2COOH or CH2CH2SO3H。
The preparation method of the viscoelastic polymer emulsion comprises the following steps
push buttonPreparing 27-30 parts of water phase reaction monomer into an aqueous solution, adjusting the pH to 5.5-6.8, and adding 0.025-0.05 part of oxidizing initiator and 0.04-0.06 part of auxiliary initiator to obtain a water phase;
step 2, emulsifying 52-66 parts of a monomer aqueous solution and 30-47 parts of an oil phase according to parts by weight, then adding 1.0-1.6 parts of a reducing initiator solution into the emulsion for polymerization, and adding 0.2-0.4 part of a reducing initiator into the polymer again to complete the polymerization reaction to obtain an oil-water phase mixture;
and 3, stirring 99-99.5 parts of the oil-water phase mixture and 0.3-0.4 part of the turning phase surfactant by mass to obtain the viscoelastic polymer emulsion.
Preferably, the emulsifier is at least one of sorbitan oleate Span80, sorbitan trioleate Span85, polyoxyethylene sorbitan monooleate Tween80 and polyethylene glycol (400) dioleate polyDOPEG 400.
Preferably, the water-phase reaction monomer is a mixture of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-allyl and N-alkyl amino acid, and the mass part ratio of the water-phase reaction monomer to the N-alkyl amino acid is 100 (10-50) to (10-30) to (5-10).
Preferably, the oxidative initiator is potassium persulfate.
Preferably, the reducing initiator solution is a mixed solution of 0.5% by weight of ascorbic acid and 0.1% by weight of ferrous sulfate.
Preferably, the phase-inversion surfactant is at least one of fatty alcohol-polyoxyethylene ether, isomeric thirteen-position polyoxyethylene ether (E1309) and sodium dodecyl sulfate.
A low-viscosity slickwater, which comprises 0.1-0.2% of viscoelastic polymer emulsion prepared according to any one of claims 2-7, 0.2-0.4% of clay stabilizer, 0.2-0.4% of cleanup additive and the balance of water by mass percentage.
A high-viscosity sand-carrying liquid, which comprises 1.0-1.8% of the viscoelastic polymer emulsion prepared according to any one of claims 2-7, 0.2-0.4% of a clay stabilizer, 0.2-0.4% of a cleanup additive and the balance of water by mass percentage.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a viscoelastic polymer emulsion, which is prepared by adopting inverse emulsion polymerization to prepare a nanoscale viscoelastic polymer emulsion capable of being pumped and injected in real time, overcomes the defect of low copolymerization rate of the conventional association monomer in the inverse emulsion polymerization process, and ensures that the association monomer has weaker hydrophilicity by introducing N-allyl and N-alkyl amino acid functional association monomer and controlling the pH within the isoelectric point range of the association monomer, simultaneously reduces the surfactant of the association monomer, minimizes the influence on the HLB of an emulsification system, and can be mostly dissolved in a water phase, thereby effectively improving the copolymerization rate and finally enhancing the association effect.
The low-viscosity slippery water and the high-viscosity sand-carrying liquid prepared from the viscoelastic high-molecular emulsion can realize the online conversion of the low-viscosity slippery water and the high-viscosity sand-carrying liquid by timely adjusting the dosage of the viscoelastic high-molecular emulsion, have the characteristics of high drag reduction rate under the condition of low concentration and good sand-carrying performance under the condition of high concentration, and meet the technical requirements of continuous mixing and fracturing construction in the whole process.
The fracturing flow-back fluid treatment process is simple, the flow-back performance is good, the repeated utilization rate is high, the fracturing flow-back fluid can be recycled, the environmental protection pressure is relieved, and the requirement of factory fracturing operation can be met.
Drawings
FIG. 1 is a temperature rise graph of a viscoelastic polymer emulsion prepared in example 6 of the present invention;
FIG. 2 is a temperature rise graph of a viscoelastic polymer emulsion prepared in example 8 of the present invention;
FIG. 3 is a viscoelasticity curve of a dispersion prepared from distilled water for a viscoelastic polymer emulsion according to the present invention;
FIG. 4 is a graph showing the temperature resistance and shear resistance of a sand-carrying fluid prepared from the viscoelastic polymer emulsion prepared in example 9 according to the present invention;
FIG. 5 is a temperature-resistant and shear-resistant graph of a fracturing fluid prepared from the viscoelastic polymer emulsion prepared in example 10 of the present invention.
FIG. 6 is a graph showing the fracturing operation of a fracturing fluid prepared from the viscoelastic polymer emulsion prepared in example 10 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to the attached drawings, which are illustrative, but not limiting, of the present invention.
A viscoelastic macromolecule emulsion adopts inverse emulsion polymerization, and the structural formula is as follows:
R＝-CH2CH2COOH or CH2CH2SO3H。
A preparation method of a viscoelastic polymer emulsion comprises the following steps:
the emulsifier is at least one of sorbitan oleate Span80, sorbitan trioleate Span85, polyoxyethylene sorbitan monooleate Tween80 and polyethylene glycol (400) dioleate polyDOPEG 400, and the addition amount of the emulsifier is 10-20% of the total mass of the emulsion.
Step 2, adding 27-30 parts of water-phase reaction monomer into a jacket reaction kettle by mass, adjusting the pH value to 5.5-6.8 by adopting 0.3-0.4 part of 30% sodium hydroxide solution, controlling the temperature to be less than or equal to 20 ℃, and adding 0.025-0.05 part of oxidizing initiator and 0.04-0.06 part of auxiliary initiator to obtain a water phase;
the water-phase reaction monomer is a mixture of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-allyl and N-alkyl amino acid, the mass ratio of the monomers is 100 (10-50) to (10-30) to (5-10), after an aqueous solution is prepared, sodium hydroxide solution is used for neutralization, the pH value is adjusted to 5.5-6.8, and the neutralization temperature is controlled to be less than or equal to 20 ℃.
The oxidative initiator is potassium persulfate, the addition amount of the oxidative initiator is 0.0001-0.05% of that of the reaction monomer by mass percent, and the auxiliary initiator is azodiisobutyronitrile, and the addition amount of the auxiliary initiator is 0.0001-0.05% of that of the reaction monomer by mass percent.
Step 3, adding 52-66 parts of water phase and 30-47 parts of oil phase into a reaction kettle by mass, starting stirring, introducing nitrogen, emulsifying for 30min, and keeping the temperature at 10-20 ℃;
step 4, dropwise adding 1.0-1.6 parts of reducing initiator solution by using a metering pump for polymerization, wherein the temperature of a reaction system is 40-60 ℃, then adding 0.2-0.4 part of reducing initiator, and continuously keeping the temperature at 40-60 ℃ to ensure that the polymerization reaction is complete to obtain an oil-water phase mixture;
according to the mass percentage, the reducing initiator solution is a mixed solution containing 0.5 percent of ascorbic acid and 0.1 percent of ferrous sulfate, and the addition amount is 0.5-1.5 percent of the mass of the reaction monomer.
And 5, stirring 99-99.5 parts of the oil-water phase mixture and 0.3-0.4 part of the turn phase surfactant for 20min by mass to obtain the viscoelastic polymer emulsion.
The mass of the oil phase accounts for 30-60% of the total mass of the emulsion, and the mass of the water phase accounts for 40-70% of the total mass of the emulsion.
The diversion phase surfactant is at least one of fatty alcohol-polyoxyethylene ether (AEO9), isomeric thirteen-position polyoxyethylene ether (E1309) and sodium dodecyl sulfate, and the addition amount of the diversion phase surfactant is 3.0-10% of the total mass of the emulsion.
The particle size of the viscoelastic polymer emulsion prepared by the invention is 30-120 nm, the viscoelastic polymer emulsion can be rapidly demulsified and dispersed when meeting water, and the complete dissolution time is less than or equal to 90 s. The 1.0% solution is prepared by distilled water, the apparent viscosity is more than or equal to 90mPa.s, the temperature resistance is more than 100 ℃, the shearing resistance is good, the 1.0% solution is prepared by fracturing flow-back fluid, the apparent viscosity retention rate is more than or equal to 80%, and the salt resistance and the recoverability are good.
The low-viscosity slickwater comprises, by mass, 0.1-0.2% of viscoelastic polymer emulsion, 0.2-0.4% of clay stabilizer, 0.2-0.4% of cleanup additive and the balance water.
The high-viscosity sand-carrying liquid comprises, by mass, 1.0-1.8% of a viscoelastic polymer emulsion, 0.2-0.4% of a clay stabilizer, 0.2-0.4% of a cleanup additive, and the balance of water.
Example 1
A preparation method of a viscoelastic polymer emulsion comprises the following steps:
step 2, adding 27-30 parts of aqueous phase reaction monomer into a jacket reaction kettle by mass, adjusting the pH to 5.5-6.8 by adopting 0.3 part of 30% sodium hydroxide solution, controlling the temperature to be less than or equal to 20 ℃, and adding 0.025 part of potassium sulfate and 0.04 part of azodiisobutyronitrile to obtain an aqueous phase;
the water-phase reaction monomer is a mixture of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-allyl and N-alkyl amino acid, and the mass ratio of the monomers is 100:10:10: 5.
Step 3, pressing 52 parts of water phase and 30 parts of oil phase into a reaction kettle according to the parts by mass, starting stirring, introducing nitrogen, emulsifying for 30min, and keeping the temperature at 10-20 ℃;
step 4, dropwise adding 1.0 part of reducing initiator solution by using a metering pump for polymerization, wherein the temperature of a reaction system is 40 +/-2 ℃, then adding 0.2 part of reducing initiator, and continuously keeping the temperature at 40 +/-2 ℃ to ensure that the polymerization reaction is complete to obtain an oil-water phase mixture;
the reducing initiator solution is a mixed solution containing 0.5 percent of ascorbic acid and 0.1 percent of ferrous sulfate by mass percentage.
And 5, stirring 99 parts of the oil-water phase mixture and 0.3 part of fatty alcohol-polyoxyethylene ether for 20min according to the parts by mass to obtain the viscoelastic polymer emulsion.
Example 2
A preparation method of a viscoelastic polymer emulsion comprises the following steps:
step 2, adding 28 parts of aqueous phase reaction monomer into a jacket reaction kettle, adjusting the pH value to 5.5-6.8 by adopting 0.35 part of 30% sodium hydroxide solution, controlling the temperature to be less than or equal to 20 ℃, and adding 0.35 part of potassium sulfate and 0.5 part of azodiisobutyronitrile to obtain an aqueous phase;
the water-phase reaction monomer is a mixture of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-allyl and N-alkyl amino acid in a mass ratio of 100:25:15: 8.
Step 3, pressing 60 parts of water phase and 40 parts of oil phase into a reaction kettle according to the parts by weight, starting stirring, introducing nitrogen, emulsifying for 30min, and keeping the temperature at 15 ℃;
step 4, dropwise adding 1.3 parts of reducing initiator solution by using a metering pump for polymerization, wherein the temperature of a reaction system is 50 +/-2 ℃, then adding 0.3 part of reducing initiator, and continuously keeping the temperature at 50 +/-2 ℃ to ensure that the polymerization reaction is complete to obtain an oil-water phase mixture;
and 5, stirring 99.2 parts of the oil-water phase mixture and 0.35 part of isotridecyl polyoxyethylene ether for 20min according to the mass parts to obtain the viscoelastic polymer emulsion.
Example 3
A preparation method of a viscoelastic polymer emulsion comprises the following steps:
step 2, adding 30 parts of aqueous phase reaction monomer aqueous solution into a jacket reaction kettle, adjusting the pH value to 5.5-6.8 by adopting 0.4 part of 30% sodium hydroxide solution, controlling the temperature to be less than or equal to 20 ℃, and adding 0.05 part of potassium sulfate and 0.06 part of azodiisobutyronitrile to obtain an aqueous phase;
the aqueous phase reaction monomer aqueous solution is a mixture of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-allyl and N-alkyl amino acid, and the mass ratio of the acrylamide to the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid to the N-allyl and the N-alkyl amino acid is 100:50:30: 10.
Step 3, pressing 66 parts of water phase and 47 parts of oil phase into a reaction kettle according to parts by mass, starting stirring, introducing nitrogen, emulsifying for 30min, and keeping the temperature at 10-20 ℃;
step 4, dropwise adding 1.6 parts of reducing initiator solution by using a metering pump for polymerization, wherein the temperature of a reaction system is 60 +/-2 ℃, then adding 0.4 part of reducing initiator, and continuously keeping the temperature at 60 +/-2 ℃ to ensure that the polymerization reaction is complete to obtain an oil-water phase mixture;
the reducing initiator solution is a mixed solution containing 0.5 percent of ascorbic acid and 0.1 percent of ferrous sulfate by mass percentage.
And 5, stirring 99.5 parts of the oil-water phase mixture and 0.4 part of sodium dodecyl sulfate for 20min according to the parts by mass to obtain the viscoelastic polymer emulsion.
Example 4
A preparation method of a viscoelastic polymer emulsion comprises the following steps:
the emulsifier comprises 0.2 part of sorbitan oleate Span80, 0.2 part of sorbitan trioleate Span85, 0.3 part of polyoxyethylene sorbitan monooleate Tween80 and 0.2 part of polyethylene glycol 400 dioleate poly.
Step 2, adding 27 parts of aqueous phase reaction monomer aqueous solution into a jacket reaction kettle according to parts by weight, adjusting the pH value to 6.8 by adopting 0.4 part of 30% sodium hydroxide solution, controlling the temperature to be less than or equal to 20 ℃, and adding 0.025 part of oxidizing initiator and 0.06 part of auxiliary initiator to obtain an aqueous phase;
the aqueous phase reaction monomer aqueous solution is a mixture of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-allyl and N-alkyl amino acid, and the mass ratio of the acrylamide to the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid to the N-allyl and the N-alkyl amino acid is 100:40:30: 8.
Step 3, pressing 52 parts of water phase and 47 parts of oil phase into a reaction kettle according to the parts by mass, starting stirring, introducing nitrogen, emulsifying for 30min, and controlling the temperature to be 20 ℃;
step 4, dropwise adding 1.3 parts of reducing initiator solution by using a metering pump for polymerization, wherein the temperature of a reaction system is 55 +/-2 ℃, then adding 0.3 part of reducing initiator, and continuously keeping the temperature at 55 +/-2 ℃ to ensure that the polymerization reaction is complete to obtain an oil-water phase mixture;
and 5, stirring 99 parts of the oil-water phase mixture and 0.3 part of the turn phase surfactant for 20min according to the parts by mass to obtain the viscoelastic polymer emulsion.
The diversion phase surfactant comprises 0.2 part of fatty alcohol-polyoxyethylene ether (AEO9) and 0.1 part of isotridecanoic polyoxyethylene ether (E1309).
Examples 5-10 provide methods for preparing viscoelastic polymeric emulsions in which the amounts of each material added are as shown in table 1.
TABLE 1
Performance test
Referring to fig. 1, a temperature rise graph of the viscoelastic polymer emulsion prepared in example 6 is shown.
Referring to fig. 2, a temperature rise graph of the viscoelastic polymer emulsion prepared in example 8 is shown.
Experimental example 5:
the viscoelastic polymer emulsion of example 10 was dispersed in distilled water at 0.5% and tested for viscoelasticity using a high temperature high pressure rotational viscometer of RS6000, HAAKE, USA, and the results are shown in FIG. 3.
Test example 6
The viscoelastic polymer emulsions prepared in examples 5 to 10 were prepared into 0.5% dispersion with 3# white oil as a dispersion medium, magnetically stirred at 500rpm for 10min, ultrasonically treated for 5min, and the particle size was measured with a malvern particle sizer, and the results are shown in table 2:
TABLE 2
Test example 7
The viscoelastic polymer emulsions prepared in examples 5 to 10 were mixed with distilled water as a dispersion medium to prepare a 1.0% dispersion, the mixture was stirred with a 1000rpm homogenizer in Qingdao Haitongda, the vortex loss time was recorded as a dissolution time, and the apparent viscosity was measured with a six-speed viscometer, and the results are shown in Table 3:
TABLE 3
| Examples | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 |
| Dissolution time(s) | 86 | 71 | 85 | 72 | 61 | 79 |
| Apparent viscosity (mPa.s) | 93 | 114 | 105 | 117 | 129 | 93 |
Test example 8
Using the viscoelastic polymer emulsions prepared in example 9 and example 10, respectively preparing low-viscosity slickwater, wherein the low-viscosity slickwater comprises 0.15% of viscoelastic polymer emulsion, 0.3% of clay stabilizer, 0.3% of cleanup additive and the balance of water by mass percent, and the drag reduction rate of the slickwater is tested, and the calculation formula of the drag reduction rate is as follows:
in the formula: delta P0-the friction pressure drop, MPa, of the pipe section without drag reducer injection;
ΔPDRand the friction pressure drop of the pipe section under the same output after the drag reducer is injected is MPa.
According to the calculation of the drag reduction rate formula, a drag reduction evaluation instrument is assembled in a laboratory. In the experiment, the drag reduction rate is calculated by using a formula (1) mainly by testing the pressure difference between two points before and after adding the viscoelastic polymer emulsion into clear water, and the result is shown in table 4:
TABLE 4
Test example 9
The high-viscosity sand-carrying fluid prepared by the method of the embodiments 9 and 10 comprises 1.0% of viscoelastic macromolecule emulsion, 0.3% of clay stabilizer and 0.3% of cleanup additive by mass percent, and is tested for temperature resistance and shear resistance at a shear rate of 170s-1And the viscosity is more than 50mpa & s at the temperature of 90 ℃, so that the requirement of fracturing sand-carrying performance is met.
Referring to fig. 4 and 5, the temperature resistance and the shear resistance of the high-viscosity sand-carrying fluid are plotted.
Test example 10
The industrial production is carried out in the embodiment 10, the fracturing fluid prepared from the viscoelastic macromolecule emulsion is subjected to a field application test, and the whole process is continuously mixed on line. The construction pressure is 54-60 MPa, and the highest sand ratio is 30%. The requirements of low-viscosity slick water resistance reduction and high-viscosity sand-carrying fluid fracturing in the early stage are met, and the construction process is smooth.
Referring to fig. 6, a graph of a fracturing job is shown.
Test example 11:
and (3) reconfiguring the fracturing flow-back fluid after gel breaking into fracturing fluid with the concentration of 1.0%, stirring for 2min, testing by using a six-speed viscometer to obtain the fracturing fluid with the apparent viscosity of 78mPa.s and the fracturing fluid with the concentration of 1.0% prepared by using field clear water to obtain the fracturing fluid with the apparent viscosity of 96mPa.s and the viscosity retention rate of 81.2%.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. A viscoelastic polymer emulsion is characterized in that the structural formula is as follows:
R＝-CH2CH2COOH or-CH2CH2SO3H。
2. The preparation method of the viscoelastic polymer emulsion is characterized by comprising the following steps
Step 1, stirring 30-47 parts of 3# white oil and 0.3-1 part of emulsifier uniformly by mass to obtain an oil phase;
push buttonPreparing 27-30 parts of water phase reaction monomer into an aqueous solution, adjusting the pH to 5.5-6.8, and adding 0.025-0.05 part of oxidizing initiator and 0.04-0.06 part of auxiliary initiator to obtain a water phase;
the water-phase reaction monomer is a mixture of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-allyl-N-alkyl amino propionic acid or N-allyl-N-alkyl amino ethanesulfonic acid, and the mass part ratio of the water-phase reaction monomer to the water-phase reaction monomer is 100 (10-50) to (10-30) to (5-10);
step 2, emulsifying 52-66 parts of a monomer aqueous solution and 30-47 parts of an oil phase according to parts by weight, then adding 1.0-1.6 parts of a reducing initiator solution into the emulsion for polymerization, and adding 0.2-0.4 part of a reducing initiator into the polymer again to complete the polymerization reaction to obtain an oil-water phase mixture;
and 3, stirring 99-99.5 parts of the oil-water phase mixture and 0.3-0.4 part of the turning phase surfactant by mass to obtain the viscoelastic polymer emulsion.
3. The method of claim 2, wherein the emulsifier is at least one of sorbitan oleate Span80, sorbitan trioleate Span85, polyoxyethylene sorbitan monooleate Tween80, polyethylene glycol (400) dioleate polyDOPEG 400.
4. The method of claim 2, wherein the oxidative initiator is potassium persulfate and the co-initiator is azobisisobutyronitrile.
5. The method of claim 2, wherein the reducing initiator solution is a mixture of 0.5% ascorbic acid and 0.1% ferrous sulfate.
6. The method for preparing a viscoelastic polymer emulsion according to claim 2, wherein the phase-inversion surfactant is at least one of fatty alcohol-polyoxyethylene ether, isomeric tridecyl polyoxyethylene ether (E1309), and sodium dodecyl sulfate.
7. A low viscosity slickwater, which is characterized by comprising 0.1 to 0.2 percent of viscoelastic polymer emulsion prepared according to any one of claims 2 to 6, 0.2 to 0.4 percent of clay stabilizer, 0.2 to 0.4 percent of cleanup additive and the balance of water by mass percentage.
8. The high-viscosity sand-carrying fluid is characterized by comprising 1.0-1.8% of the viscoelastic high-molecular emulsion prepared according to any one of claims 2-6, 0.2-0.4% of a clay stabilizer, 0.2-0.4% of a cleanup additive and the balance of water in percentage by mass.
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| US20100144560A1 (en) * | 2008-12-08 | 2010-06-10 | Beall Brian B | Methods and compositions for reducing fluid loss during treatment with viscoelastic surfactant gels |
| CN102690390A (en) * | 2012-05-31 | 2012-09-26 | 西南石油大学 | Hydrophobically associating water soluble polymer oil-displacing agent and synthetic method thereof |
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| US20180112119A1 (en) * | 2016-10-25 | 2018-04-26 | Yangtze University | Reverse Emulsion-based Slick Water Concentration System with Drag Reduction, Flow Back Enhancement and Clay Stabilization Functions |
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| US20100144560A1 (en) * | 2008-12-08 | 2010-06-10 | Beall Brian B | Methods and compositions for reducing fluid loss during treatment with viscoelastic surfactant gels |
| CN102690390A (en) * | 2012-05-31 | 2012-09-26 | 西南石油大学 | Hydrophobically associating water soluble polymer oil-displacing agent and synthetic method thereof |
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