CN103627380A - Water-soluble drag reducer as well as preparation method and application thereof - Google Patents
Water-soluble drag reducer as well as preparation method and application thereof Download PDFInfo
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- CN103627380A CN103627380A CN201310552770.2A CN201310552770A CN103627380A CN 103627380 A CN103627380 A CN 103627380A CN 201310552770 A CN201310552770 A CN 201310552770A CN 103627380 A CN103627380 A CN 103627380A
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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
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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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
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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
- C09K8/84—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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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
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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
- C09K2208/28—Friction or drag reducing additives
Abstract
The invention relates to a water-soluble drag reducer as well as a preparation method and application thereof. The preparation method is characterized by adding an emulsifier and solvent oil to a reactor to form an oil phase, adding a lipophilic propenyl monomer to the oil phase, dissolving a hydrophilic propenyl monomer in water, regulating the pH value to 8-9 to form an aqueous phase, slowly dropping the aqueous phase into the oil phase, carrying out emulsification while stirring, adding an initiator by times under the condition of introducing nitrogen, reacting at 30 DEG C for 48 hours, cooling, adding a polymerization inhibitor so as to obtain an inverse microemulsion system, and mixing the prepared inverse microemulsion system with a surfactant so as to obtain the water-soluble drag reducer. The water-soluble drag reducer is used in quick water fracturing fluid to reduce the friction drag of pipelines, reduces the pump power, improves the sand-carrying capacity of the construction fluid, is suitable for oil and gas exploitation of unconventional low permeability reservoirs, has good dissolving property and obvious drag reduction effect which can reach 50-70% compared with that of the clear water, and is convenient to use.
Description
Technical field
The invention belongs to oilfield stimulation field, be specifically related to flow improver and preparation and application for a kind of waterfrac treatment.
Background technology
Fine and close unconventional reservoir has low hole, hypotonic feature, and exploratory development difficulty is larger, and most of fine and close Oil/gas Wells need reservoir reconstruction could obtain more satisfactory output.At present, for the unconventional reservoir happy of densification, sending out well stimulation topmost is both at home and abroad drag reduction pressure break, utilizes low frictional resistance slippery water fracturing liquid to carry out volume transformation.Slippery water fracturing fluid system is a kind of new fracturing fluid system growing up for the unconventional reservoir reconstruction of densification.In states such as the U.S., Canada, the of the fracturing fluid use of slippery water has obtained significant economic benefit and has been substituted traditional gelatinous fracturing fluid and has become most popular fracturing liquid.
Slippery water fracturing liquid refers to a kind of fracturing fluid system of the additive such as flow improver, breakdown of emulsion cleanup additive, clay stabilizer, sterilant that adds a certain amount of propping agent and minute quantity in clear water.Compare traditional gelatinous fracturing fluid system, slippery water fracturing liquid has great advantage aspect the fine and close unconventional reservoir of exploitation, as slippery water fracturing liquid has greatly reduced the injury of gel to stratum and crack: traditional gelatinous fracturing fluid system is used the gel of higher concentration, the residue of these gels and the filter cake producing in fracturing process can stop up stratum and reduce fracture flow capacity, and in slippery water fracturing liquid, only contain a small amount of additives such as flow improver, and be easy to the row of returning, greatly reduce stratum and crack injury, thereby be conducive to improve output; And slippery water fracturing liquid cost is lower: the chemical additive in drag reduction water and the consumption of propping agent are less, can save construction cost 40%~60%, and many reservoirs of not having business extraction value originally just can be developed; In addition use slippery water fracturing liquid can produce the larger network of fracture of the higher volume of complexity: this be due to drag reduction glassware for drinking water have lower viscosity and when construction to pump into speed higher, the raising of crack complexity and volume has increased effective volume increase volume of reservoir, and output is increased; What is more important is because additive level in drag reduction water is few, comparatively clean, is therefore easier to recycle, can save the Freshwater resources of a large amount of preciousnesses.
Therefore, in slippery water fracturing liquid, the application of the use of additive, particularly flow improver and demand are also more and more.But at present the domestic flow improver that has an independent intellectual property right is few, on each elephant, is mainly to take linear glue and external flow improver as main, thereby has virtually improved construction cost.
Summary of the invention
The object of this invention is to provide a kind of for the of the fracturing fluid water-soluble flow improver of slippery water and preparation and application, by adopting conversed phase micro emulsion copolymerization, control molecular structure simultaneously, in high molecular polymer structure, introduce hydrophilic and hydrophobic grouping simultaneously, and by long-time low-temp reaction, obtain the polymkeric substance of larger molecular weight, make synthetic polymkeric substance there is good resistance reducing performance and thickening capabilities, in pressing crack construction, can effectively reduce pipeline frictional resistance, reduce pump merit and improve the prop-carrying capacity of construction liquid.And the surfactant system by adding hydrotropy to disperse, makes final product obtain fabulous water dispersible and solvability, can effectively meet the site operation requirement of slippery water pressure break.
The technical scheme that in the present invention, the preparation of water-soluble flow improver adopts is: the 3-5wt% emulsifying agent and the 40-42wt% solvent oil that account for total system massfraction are joined in reactor, fully stir, and in oil phase, add 0-5wt% lipophilicity propenyl monomer, after being uniformly dispersed, dissolving forms oil phase.10-20wt% wetting ability propenyl monomer is fully dissolved in the water simultaneously, and adds the sodium hydroxide of concentration 40% water-soluble, system pH is adjusted to 8-9 and forms water.While starting to react, water is slowly splashed in oil phase and stirred; low whipping speed is fully emulsified 30min under the condition of 1000 turn/min; keeping subsequently stirring velocity is 300 turn/min; add 0.25-0.45wt% initiator passing into gradation under the condition of nitrogen protection; keep 30 ℃, reaction 48h, cools; after add the stopper of 0.05wt%, obtain translucent, stable Reverse Microemulsion System.
Hydrophilic monomer of the present invention has one or more mixtures in acrylamide, Methacrylamide, DMAA, diacetone-acryloamide(DAA), n-methylolacrylamide, vinylformic acid, methylpropene sodium sulfonate, methacrylic acid or 2-acrylamide-2-methyl propane sulfonic.Oleophylic monomer has one or more mixtures in methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, octadecyl acrylate, stearyl methacrylate or methoxy polyethylene glycol methacrylate-styrene polymer.Emulsifying agent is the mixture of sorbitan fatty acid ester and polysorbate or alkylphenol polyoxyethylene.Solvent oil has one or more mixtures in benzene,toluene,xylene, hexanaphthene, pentamethylene, petroleum naphtha, gasoline, kerosene, diesel oil or white oil.Initiator has ammonium persulphate, Potassium Persulphate, ammonium persulphate-sulfurous acid (hydrogen) sodium, Potassium Persulphate-sulfurous acid (hydrogen) sodium, ammonium persulphate-Sulfothiorine, Potassium Persulphate-Sulfothiorine or water-soluble azo initiator.Stopper has one or more mixtures in Resorcinol, Pyrogentisinic Acid's monobutyl ether, tert-butyl catechol or copper naphthenate.
The technical scheme that in the present invention, the use of water-soluble flow improver adopts is: the Reverse Microemulsion System of preparation and a certain amount of tensio-active agent are fully mixed, dosage of surfactant is the 5-10% of reverse micro emulsion quality, obtain water-soluble flow improver, during on-the-spot preparation, by adding massfraction in water per ton, be the water-soluble flow improver of 0.06-0.25%, 0.2-0.5% breakdown of emulsion cleanup additive and 0.5% clay stabilizer, obtain slippery water fracturing liquid after mixing.
Tensio-active agent of the present invention has one or more mixtures in Seconary Alkane Sulphonate Sodium, laurilsulfate sodium, secondary alkyl sulphate sodium, α mono-sodium olefin sulfonate, succsinic acid alkyl ester sodium sulfonate, thionamic acid sodium, Sodium dodecylbenzene sulfonate, coconut oil diethanol amide, fatty alcohol-polyoxyethylene ether.
Flow improver solubility property of the present invention is good, easy to use, drag-reduction effect is obvious, compares with clear water, and drag-reduction effect can reach 50%-70%.And at the scene in waterfrac treatment operation, shown good drag-reduction effect, in construction operating mode, be discharge capacity 3.5m
3in the situation of/min, the drag reducing efficiency of water-soluble flow improver moral is higher by 42.5% than traditional guanidine glue slippery water.
Embodiment
Embodiment 1:
The solvent oil that the emulsifying agent of the compositions of mixtures that 3g is comprised of with polysorbate sorbitan fatty acid ester and 40g are comprised of with petroleum naphtha dimethylbenzene, hexanaphthene mixes, wherein the mass ratio of Span and polysorbate is 5 ︰ 4, and the mass ratio of dimethylbenzene, hexanaphthene and petroleum naphtha is 2 ︰ 1 ︰ 1.After being uniformly dissolved, add 5g methoxy polyethylene glycol methacrylate-styrene polymer, mix formation oil phase.
The mixture that 15g is comprised of acrylamide, vinylformic acid and methylpropene sodium sulfonate is dissolved in 36.7g water, and wherein acrylamide, vinylformic acid and methylpropene sodium sulfonate mass ratio are 5 ︰ 2 ︰ 1.After dissolving fully, by the pH value of aqueous sodium hydroxide solution regulator solution, be 8-9, obtain water.
Water is slowly splashed in oil phase and stirred; low whipping speed is fully emulsified 30min under the condition of 1000 turn/min; keeping subsequently stirring velocity is 300 turn/min; add 0.25g Potassium Persulphate-Sulfothiorine initiator system passing into gradation under the condition of nitrogen protection; keep 30 ℃, reaction 48h, cools; after add 0.05g Pyrogentisinic Acid monobutyl ether, obtain translucent, stable Reverse Microemulsion System.
The mixture that the 100g Reverse Microemulsion System of preparation and 10g are comprised of with coconut oil diethanol amide α mono-sodium olefin sulfonate, Sodium dodecylbenzene sulfonate fully mixes, wherein α mono-sodium olefin sulfonate, Sodium dodecylbenzene sulfonate and coconut oil diethanol amide mass ratio are 2 ︰ 2 ︰ 1, obtain water-soluble flow improver.
By adding massfraction in water per ton, it is 0.25% water-soluble flow improver, 0.5% breakdown of emulsion cleanup additive and 0.5% clay stabilizer preparation slippery water fracturing liquid, shown in indoor use pipeline friction test system, test under this slippery water different in flow rate and can reach 56% at maximum drag reducing efficiency, as shown in table 1.
Table 1 flow improver Lab-evaluation result
Embodiment 2:
The solvent oil that the mixture that 3g is comprised of with polysorbate sorbitan fatty acid ester and 40g are comprised of with white oil toluene, hexanaphthene mixes, wherein the mass ratio of Span and polysorbate is 5 ︰ 4, and the mass ratio of toluene, hexanaphthene and white oil is 1 ︰ 4 ︰ 1.The mixture that adds 5g octadecyl acrylate and methoxy polyethylene glycol methacrylate-styrene polymer to form after being uniformly dissolved, wherein the mass ratio of octadecyl acrylate and methoxy polyethylene glycol methacrylate-styrene polymer is 1 ︰ 1, mixes formation oil phase.
The mixture that 18g is comprised of DMAA, methacrylic acid and 2-acrylamide-2-methyl propane sulfonic is dissolved in 33.7g water, and wherein DMAA, methacrylic acid and 2-acrylamide-2-methyl propane sulfonic mass ratio are 2 ︰ 1 ︰ 1.After dissolving fully, by the pH value of aqueous sodium hydroxide solution regulator solution, be 8-9, obtain water.
Water is slowly splashed in oil phase and stirred; low whipping speed is fully emulsified 30min under the condition of 1000 turn/min; keeping subsequently stirring velocity is 300 turn/min; add 0.25g ammonium persulfate-sodium bisulfite initiator system passing into gradation under the condition of nitrogen protection; keep 30 ℃, reaction 48h, cools; after add 0.05g Resorcinol, obtain translucent, stable Reverse Microemulsion System.
The mixture that the 100g Reverse Microemulsion System of preparation and 5g are comprised of with fatty alcohol-polyoxyethylene ether Seconary Alkane Sulphonate Sodium, coconut oil diethanol amide fully mixes, wherein Seconary Alkane Sulphonate Sodium, coconut oil diethanol amide and fatty alcohol-polyoxyethylene ether mass ratio are 1 ︰ 1 ︰ 2, obtain water-soluble flow improver.
By adding massfraction in water per ton, it is 0.18% water-soluble flow improver, 0.5% breakdown of emulsion cleanup additive and 0.5% clay stabilizer preparation slippery water fracturing liquid, under this slippery water different in flow rate of indoor use pipeline friction test system testing, at maximum drag reducing efficiency, can reach 62%, as shown in table 2.
Table 2 flow improver Lab-evaluation result
Embodiment 3:
The solvent oil that the mixture that 5g is comprised of with alkylphenol polyoxyethylene sorbitan fatty acid ester and 40g are comprised of with gasoline benzene mixes, wherein the mass ratio of Span and alkylphenol polyoxyethylene is 1 ︰ 2, and benzene is 1 ︰ 2 with quality of gasoline ratio.The mixture that adds 5g methyl acrylate and methoxy polyethylene glycol methacrylate-styrene polymer to form after being uniformly dissolved, wherein the mass ratio of methyl acrylate and methoxy polyethylene glycol methacrylate-styrene polymer is that 4 ︰ 3 mix formation oil phase.
The mixture that 20g is comprised of n-methylolacrylamide, vinylformic acid and 2-acrylamide-2-methyl propane sulfonic is dissolved in 29.5g water, and wherein n-methylolacrylamide, vinylformic acid and 2-acrylamide-2-methyl propane sulfonic mass ratio are 3 ︰ 1 ︰ 1.After dissolving fully, by the pH value of aqueous sodium hydroxide solution regulator solution, be 8-9, obtain water.
Water is slowly splashed in oil phase and stirred; low whipping speed is fully emulsified 30min under the condition of 1000 turn/min; keeping subsequently stirring velocity is 300 turn/min; add 0.45g Potassium Persulphate-sulfurous acid (hydrogen) sodium initiator system passing into gradation under the condition of nitrogen protection; keep 30 ℃, reaction 48h, cools; after add 0.05g tert-butyl catechol, obtain translucent, stable Reverse Microemulsion System.
The mixture that the 100g Reverse Microemulsion System of preparation and 5g are comprised of laurilsulfate sodium, succsinic acid alkyl ester sodium sulfonate, fatty alcohol-polyoxyethylene ether fully mixes, wherein laurilsulfate sodium, succsinic acid alkyl ester sodium sulfonate, fatty alcohol-polyoxyethylene ether mass ratio are 5 ︰ 5 ︰ 1, obtain water-soluble flow improver.
By adding massfraction in water per ton, it is 0.15% water-soluble flow improver, 0.5% breakdown of emulsion cleanup additive and 0.5% clay stabilizer preparation slippery water fracturing liquid, under this slippery water different in flow rate of indoor use pipeline friction test system testing, at maximum drag reducing efficiency, can reach 66%, as shown in table 3.
Table 3 flow improver Lab-evaluation result
Claims (10)
1. a preparation method for water-soluble flow improver, is characterized in that:
(1) preparation of oil phase: emulsifying agent, solvent oil are joined in reactor, fully stir, after being uniformly dispersed, dissolving forms oil phase, and in oil phase, add lipophilicity propenyl monomer, wherein emulsifier is the 3-5% of total system massfraction, solvent oil consumption is the 40-42% of total system massfraction, and lipophilicity propenyl monomer accounts for the 0-5% of total system massfraction;
(2) preparation of water: wetting ability propenyl monomer is dissolved in the water, add sodium hydroxide solution, system pH is adjusted to 8-9 and forms water, wetting ability propenyl monomer total amount accounts for the 10-20% of total system massfraction, water consumption is the 32.5-37.5% of total system massfraction, and described sodium hydroxide solution is the aqueous sodium hydroxide solution of concentration 40%;
(3) monomer polymerization technique: water is slowly splashed in oil phase and stirred, low whipping speed is fully emulsified 30min under the condition of 1000 turn/min, keeping subsequently stirring velocity is 300 turn/min, adds initiator passing into gradation under the condition of nitrogen protection, keeps 30 ℃, reaction 48h, cool, after add stopper, obtain Reverse Microemulsion System, wherein initiator amount is the 0.25-0.45% of total system massfraction, and wherein stopper consumption is 0.05% of total system massfraction;
(4) Reverse Microemulsion System of preparation and tensio-active agent are mixed, obtain water-soluble flow improver, dosage of surfactant is the 5-10% of reverse micro emulsion quality.
2. the preparation method of a kind of water-soluble flow improver according to claim 1, is characterized in that: described hydrophilic monomer is one or more mixtures in acrylamide, Methacrylamide, DMAA, diacetone-acryloamide(DAA), n-methylolacrylamide, vinylformic acid, methylpropene sodium sulfonate, methacrylic acid or 2-acrylamide-2-methyl propane sulfonic.
3. the preparation method of a kind of water-soluble flow improver according to claim 1, is characterized in that: described oleophylic monomer is one or more mixtures in methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, octadecyl acrylate, stearyl methacrylate or methoxy polyethylene glycol methacrylate-styrene polymer.
4. the preparation method of a kind of water-soluble flow improver according to claim 1, is characterized in that: described emulsifying agent is the mixture of sorbitan fatty acid ester and polysorbate or alkylphenol polyoxyethylene.
5. the preparation method of a kind of water-soluble flow improver according to claim 1, is characterized in that: described solvent oil is one or more mixtures in benzene,toluene,xylene, hexanaphthene, pentamethylene, petroleum naphtha, gasoline, kerosene, diesel oil or white oil.
6. the preparation method of a kind of water-soluble flow improver according to claim 1, is characterized in that: described initiator is ammonium persulphate, Potassium Persulphate, ammonium persulphate-sulfurous acid (hydrogen) sodium, Potassium Persulphate-sulfurous acid (hydrogen) sodium, ammonium persulphate-Sulfothiorine, Potassium Persulphate-Sulfothiorine or water-soluble azo initiator.
7. the preparation method of a kind of water-soluble flow improver according to claim 1, is characterized in that: described stopper is one or more mixtures in Resorcinol, Pyrogentisinic Acid's monobutyl ether, tert-butyl catechol or copper naphthenate.
A kind of water-soluble flow improver according to claim 1 preparation method, it is characterized in that: described tensio-active agent is one or more mixtures in Seconary Alkane Sulphonate Sodium, laurilsulfate sodium, secondary alkyl sulphate sodium, α mono-sodium olefin sulfonate, succsinic acid alkyl ester sodium sulfonate thionamic acid sodium, Sodium dodecylbenzene sulfonate, coconut oil diethanol amide, fatty alcohol-polyoxyethylene ether.
9. a water-soluble flow improver, is characterized in that: prepared by method according to claim 1.
10. an application for water-soluble flow improver claimed in claim 9, is characterized in that: for slippery water fracturing liquid, reduce pipeline frictional resistance, reduce the prop-carrying capacity of pump merit and raising construction liquid, be applicable to the oil-gas mining of unconventional low permeability reservoir; During on-the-spot preparation, by adding massfraction in water per ton, be the water-soluble flow improver of 0.06-0.25%, 0.2-0.5% breakdown of emulsion cleanup additive and 0.5% clay stabilizer, obtain slippery water fracturing liquid after mixing.
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