CN103627380B - A kind of water solublity drag reducer and preparation thereof and application - Google Patents

A kind of water solublity drag reducer and preparation thereof and application Download PDF

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CN103627380B
CN103627380B CN201310552770.2A CN201310552770A CN103627380B CN 103627380 B CN103627380 B CN 103627380B CN 201310552770 A CN201310552770 A CN 201310552770A CN 103627380 B CN103627380 B CN 103627380B
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water
drag reducer
sodium
water solublity
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CN103627380A (en
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范华波
李安琪
慕立俊
赵振峰
李宪文
张矿生
薛小佳
吴江
刘锦
吕海燕
周晓群
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Petrochina Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/66Compositions based on water or polar solvents
    • C09K8/68Compositions based on water or polar solvents containing organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular 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
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/062Polyethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/602Compositions for stimulating production by acting on the underground formation containing surfactants
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/602Compositions for stimulating production by acting on the underground formation containing surfactants
    • C09K8/604Polymeric surfactants
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/84Compositions based on water or polar solvents
    • C09K8/86Compositions based on water or polar solvents containing organic compounds
    • C09K8/88Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25Methods for stimulating production
    • E21B43/26Methods for stimulating production by forming crevices or fractures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/28Friction or drag reducing additives

Abstract

The present invention relates to a kind of water solublity drag reducer and preparation thereof and application, by emulsifying agent, solvent naphtha joins formation oil phase in reactor, oil phase adds lipophile acrylmonomers, hydrophilic acrylmonomers is dissolved in the water, pH value is adjusted to 8-9 and forms aqueous phase, aqueous phase is slowly instilled in oil phase, under agitation emulsifying, pass into nitrogen gradation and add initiator, 30 DEG C, reaction 48h, cool, add polymerization inhibitor, namely Reverse Microemulsion System is obtained, by the Reverse Microemulsion System of preparation and surfactant mixing, namely water solublity drag reducer is obtained, for slippery water fracturing fluid reduces pipeline frictional resistance, reduce pump merit and improve the prop-carrying capacity of construction liquid, oil-gas mining suitable in unconventional low permeability reservoir, the solubility property of this drag reducer is good, easy to use, drag-reduction effect obvious, and compared with clear water, drag-reduction effect can reach 50%-70%.

Description

A kind of water solublity drag reducer and preparation thereof and application
Technical field
The invention belongs to oilfield stimulation field, be specifically related to a kind of fracturing drag reducer and preparation thereof and application.
Background technology
Fine and close unconventional reservoir has low hole, hypotonic feature, and exploration and development difficulty is relatively big, and most of fine and close Oil/gas Wells need reservoir reconstruction could obtain more satisfactory yield. At present, sending out well stimulation topmost for fine and close unconventional reservoir happy both at home and abroad is drag reduction pressure break, namely utilizes low frictional resistance slippery water fracturing fluid to carry out volume transformation. Slippery water fracturing fluid system is a kind of new fracturing fluid system grown up for fine and close unconventional reservoir transformation. In the state such as the U.S., Canada, the of the fracturing fluid use of slippery water obtains significant economic benefit and instead of traditional gelatinous fracturing fluid and become most popular fracturing fluid.
Slippery water fracturing fluid refers to a kind of fracturing fluid system adding the additive such as a certain amount of proppant and minimal amount of drag reducer, demulsification cleanup agent, clay stabilizer, antibacterial in clear water. Compare traditional gel fracture liquid system, slippery water fracturing fluid has great advantage in the fine and close unconventional reservoir of exploitation, as slippery water fracturing fluid considerably reduces the gel injury to stratum and crack: traditional gel fracture liquid system uses the gel of higher concentration, the residue of these gels and the filter cake produced in fracturing process can block stratum and reduce fracture condudtiviy, and containing only there being the additives such as a small amount of drag reducer in slippery water fracturing fluid, and it is prone to the row of returning, greatly reduce stratum and Damage to Fractures, thus being conducive to improving yield;And slippery water fracturing fluid is less costly: chemical addition agent and the consumption of proppant in drag reduction water are less, can save construction cost 40%��60%, make many reservoirs originally not having business extraction value just can be developed; In addition use slippery water fracturing fluid can produce the fracture network that the higher volume of complexity is bigger: when this is to have relatively low viscosity and construction due to drag reduction glassware for drinking water to pump into speed higher, what the raising of crack complexity and volume added reservoir effectively increases production volume so that yield increases; What is more important due in drag reduction water additive level few, comparatively clean, be therefore easier to recycle, it is possible to save a large amount of valuable freshwater resources.
Therefore, in slippery water fracturing fluid, the application of the use of additive, particularly drag reducer and demand also get more and more. But the domestic drag reducer having an independent intellectual property right is few at present, mainly based on linear glue and external drag reducer on each elephant, thus virtually improve construction cost.
Summary of the invention
It is an object of the invention to provide a kind of for the of the fracturing fluid water solublity drag reducer of slippery water and preparation thereof and application, by adopting conversed phase micro emulsion copolymerization, control molecular structure simultaneously, high molecular polymer structure is simultaneously introduced hydrophilic and hydrophobic group, and by long-time low-temp reaction, obtain the polymer of larger molecular weight, the polymer making synthesis has good resistance reducing performance and thickening capabilities, pressing crack construction can effectively reduce pipeline frictional resistance, reduce the prop-carrying capacity of pump merit and raising construction liquid. And by adding the scattered surfactant system of hydrotropy, make final product obtain fabulous water dispersible and dissolubility, can effectively meet the site operation requirement of slippery water pressure break.
In the present invention, the preparation of water solublity drag reducer the technical scheme is that and joins in reactor by the 3-5wt% emulsifying agent and 40-42wt% solvent naphtha that account for total system mass fraction, it is sufficiently stirred for, and in oil phase, add 0-5wt% lipophile acrylmonomers, dissolve and after being uniformly dispersed, form oil phase. 10-20wt% hydrophilic acrylmonomers is completely dissolved in water simultaneously, and the sodium hydroxide adding concentration 40% is water-soluble, system pH is adjusted to 8-9 and forms aqueous phase. When starting to react, aqueous phase is slowly instilled in oil phase and stir; low whipping speed is fully emulsified 30min when being 1000 turns/min; being kept stirring for speed subsequently is 300 turns/min; when passing into nitrogen protection, gradation adds 0.25-0.45wt% initiator; keep 30 DEG C, react 48h, cool; the rear polymerization inhibitor adding 0.05wt%, namely obtains translucent, stable Reverse Microemulsion System.
Hydrophilic monomer of the present invention has one or more mixture in acrylamide, Methacrylamide, DMAA, N-[2-(2-methyl-4-oxopentyl), n-methylolacrylamide, acrylic acid, methylpropene sodium sulfonate, methacrylic acid or 2-acrylamide-2-methyl propane sulfonic. Oleophylic monomer has one or more mixture in acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, Hexyl 2-propenoate, N-Hexyl methacrylate, octadecyl acrylate, octadecyl methacrylate or methoxy polyethylene glycol methacrylate-styrene polymer. Emulsifying agent is the mixture of sorbitan fatty acid ester and Polysorbate or alkylphenol polyoxyethylene.Solvent naphtha has one or more mixture in benzene,toluene,xylene, hexamethylene, Pentamethylene., Petroleum, gasoline, kerosene, diesel oil or white oil. Initiator has Ammonium persulfate., potassium peroxydisulfate, Ammonium persulfate .-sulfurous acid (hydrogen) sodium, potassium peroxydisulfate-sulfurous acid (hydrogen) sodium, Ammonium persulfate .-sodium thiosulfate, potassium peroxydisulfate-sodium thiosulfate or water-soluble azo initiator. Polymerization inhibitor has one or more mixture in hydroquinone, Pyrogentisinic Acid's monobutyl ether, tert-butyl catechol or copper naphthenate.
In the present invention, the use of water solublity drag reducer the technical scheme is that and Reverse Microemulsion System and a certain amount of surfactant of preparation is sufficiently mixed, dosage of surfactant is the 5-10% of reverse micro emulsion quality, namely water solublity drag reducer is obtained, during extemporaneous preparation by water per ton add mass fraction be 0.06-0.25% water solublity drag reducer, 0.2-0.5% demulsification cleanup agent and 0.5% clay stabilizer, obtain slippery water fracturing fluid after mix homogeneously.
Surfactant of the present invention has one or more mixture in SAS, laurilsulfate sodium, secondary alkyl sulphate sodium, �� mono-sodium olefin sulfonate, succinic acid alkyl ester sulfonate sodium, sulfamic acid sodium, dodecylbenzene sodium sulfonate, coconut oil diethanol amide, fatty alcohol-polyoxyethylene ether.
The drag reducer solubility property of the present invention is good, easy to use, drag-reduction effect obvious, and compared with clear water, drag-reduction effect can reach 50%-70%. And at the scene in hydraulic fracturing job, it is shown that good drag-reduction effect, is discharge capacity 3.5m in construction operating mode3When/min, the drag reducing efficiency of water solublity drag reducer moral is higher by 42.5% than traditional guanidine glue slippery water.
Detailed description of the invention
Embodiment 1:
The solvent naphtha that the emulsifying agent form the mixture that 3g is made up of with Polysorbate sorbitan fatty acid ester and 40g are made up of with Petroleum dimethylbenzene, hexamethylene mixes, wherein Span is 54 with the mass ratio of Polysorbate, and the mass ratio of dimethylbenzene, hexamethylene and Petroleum is 211. Adding 5g methoxy polyethylene glycol methacrylate-styrene polymer after being uniformly dissolved, mix homogeneously forms oil phase.
Being dissolved in 36.7g water by the mixture that 15g is made up of acrylamide, acrylic acid and methylpropene sodium sulfonate, wherein acrylamide, acrylic acid and methylpropene sodium sulfonate mass ratio are 521. Dissolving after fully, the pH value regulating solution with sodium hydrate aqueous solution is 8-9, obtains aqueous phase.
Aqueous phase is slowly dropped in oil phase and stirs; low whipping speed is fully emulsified 30min when being 1000 turns/min; being kept stirring for speed subsequently is 300 turns/min; when passing into nitrogen protection, gradation adds 0.25g potassium peroxydisulfate-sodium thiosulfate initiator system; keep 30 DEG C, react 48h, cool; rear addition 0.05g Pyrogentisinic Acid's monobutyl ether, namely obtains translucent, stable Reverse Microemulsion System.
The mixture that the 100g Reverse Microemulsion System of preparation and 10g are made up of �� mono-sodium olefin sulfonate, dodecylbenzene sodium sulfonate and coconut oil diethanol amide is sufficiently mixed, wherein �� mono-sodium olefin sulfonate, dodecylbenzene sodium sulfonate and coconut oil diethanol amide mass ratio are 221, namely obtain water solublity drag reducer.
It is 0.25% water solublity drag reducer by water per ton adds mass fraction, 0.5% demulsification cleanup agent and 0.5% clay stabilizer preparation slippery water fracturing fluid, at maximum drag reducing efficiency up to 56% under this slippery water different in flow rate of test shown in indoor use pipeline friction test system, as shown in table 1.
Table 1 drag reducer Lab-evaluation result
Embodiment 2:
The solvent naphtha that the 3g mixture being made up of with Polysorbate sorbitan fatty acid ester and 40g are made up of with white oil toluene, hexamethylene is mixed, wherein Span is 54 with the mass ratio of Polysorbate, and the mass ratio of toluene, hexamethylene and white oil is 141. Adding 5g octadecyl acrylate and the mixture of methoxy polyethylene glycol methacrylate-styrene polymer composition after being uniformly dissolved, wherein the mass ratio of octadecyl acrylate and methoxy polyethylene glycol methacrylate-styrene polymer is 11, and mix homogeneously forms oil phase.
Being dissolved in 33.7g water by the mixture that 18g is made up of DMAA, methacrylic acid and 2-acrylamide-2-methyl propane sulfonic, wherein DMAA, methacrylic acid and 2-acrylamide-2-methyl propane sulfonic mass ratio are 211. Dissolving after fully, the pH value regulating solution with sodium hydrate aqueous solution is 8-9, obtains aqueous phase.
Aqueous phase is slowly dropped in oil phase and stirs; low whipping speed is fully emulsified 30min when being 1000 turns/min; being kept stirring for speed subsequently is 300 turns/min; when passing into nitrogen protection, gradation adds 0.25g ammonium persulfate-sodium bisulfite initiator system; keep 30 DEG C, react 48h, cool; rear addition 0.05g hydroquinone, namely obtains translucent, stable Reverse Microemulsion System.
The mixture that the 100g Reverse Microemulsion System of preparation and 5g are made up of SAS, coconut oil diethanol amide and fatty alcohol-polyoxyethylene ether is sufficiently mixed, wherein SAS, coconut oil diethanol amide and fatty alcohol-polyoxyethylene ether mass ratio are 112, namely obtain water solublity drag reducer.
It is 0.18% water solublity drag reducer by water per ton adds mass fraction, 0.5% demulsification cleanup agent and 0.5% clay stabilizer preparation slippery water fracturing fluid, at maximum drag reducing efficiency up to 62% under indoor use this slippery water different in flow rate of pipeline friction test system test, as shown in table 2.
Table 2 drag reducer Lab-evaluation result
Embodiment 3:
Being mixed by the solvent naphtha that the 5g mixture being made up of with alkylphenol polyoxyethylene sorbitan fatty acid ester and 40g are made up of with gasoline benzene, wherein Span is 12 with the mass ratio of alkylphenol polyoxyethylene, and benzene is 12 with quality of gasoline ratio. Adding 5g acrylic acid methyl ester. and the mixture of methoxy polyethylene glycol methacrylate-styrene polymer composition after being uniformly dissolved, wherein the mass ratio of acrylic acid methyl ester. and methoxy polyethylene glycol methacrylate-styrene polymer is that 43 mix homogeneously form oil phase.
Being dissolved in 29.5g water by the mixture that 20g is made up of n-methylolacrylamide, acrylic acid and 2-acrylamide-2-methyl propane sulfonic, wherein n-methylolacrylamide, acrylic acid and 2-acrylamide-2-methyl propane sulfonic mass ratio are 311. Dissolving after fully, the pH value regulating solution with sodium hydrate aqueous solution is 8-9, obtains aqueous phase.
Aqueous phase is slowly dropped in oil phase and stirs; low whipping speed is fully emulsified 30min when being 1000 turns/min; being kept stirring for speed subsequently is 300 turns/min; when passing into nitrogen protection, gradation adds 0.45g potassium peroxydisulfate-sulfurous acid (hydrogen) sodium initiator system; keep 30 DEG C, react 48h, cool; rear addition 0.05g tert-butyl catechol, namely obtains translucent, stable Reverse Microemulsion System.
The mixture that the 100g Reverse Microemulsion System of preparation and 5g are made up of laurilsulfate sodium, succinic acid alkyl ester sulfonate sodium, fatty alcohol-polyoxyethylene ether is sufficiently mixed, wherein laurilsulfate sodium, succinic acid alkyl ester sulfonate sodium, fatty alcohol-polyoxyethylene ether mass ratio are 551, namely obtain water solublity drag reducer.
It is 0.15% water solublity drag reducer by water per ton adds mass fraction, 0.5% demulsification cleanup agent and 0.5% clay stabilizer preparation slippery water fracturing fluid, at maximum drag reducing efficiency up to 66% under indoor use this slippery water different in flow rate of pipeline friction test system test, as shown in table 3.
Table 3 drag reducer Lab-evaluation result

Claims (9)

1. the preparation method of a water solublity drag reducer, it is characterised in that:
(1) preparation of oil phase: emulsifying agent, solvent naphtha are joined in reactor, it is sufficiently stirred for, dissolving forms oil phase after being uniformly dispersed, and in oil phase, add lipophile acrylmonomers, wherein emulsifier is the 3-5% of total system mass fraction, solvent naphtha consumption is the 40-42% of total system mass fraction, and lipophile acrylmonomers accounts for the 0-5% of total system mass fraction;
(2) preparation of aqueous phase: hydrophilic acrylmonomers is dissolved in the water, add sodium hydroxide solution, system pH is adjusted to 8-9 and forms aqueous phase, hydrophilic acrylmonomers total amount accounts for the 10-20% of total system mass fraction, water consumption is the 32.5-37.5% of total system mass fraction, and described sodium hydroxide solution is the sodium hydrate aqueous solution of concentration 40%;
(3) monomer polymerization technique: aqueous phase is slowly instilled in oil phase and stirs, low whipping speed is fully emulsified 30min when being 1000 turns/min, being kept stirring for speed subsequently is 300 turns/min, when passing into nitrogen protection, gradation adds initiator, keep 30 DEG C, reaction 48h, cool, rear addition polymerization inhibitor, namely Reverse Microemulsion System is obtained, wherein initiator amount is the 0.25-0.45% of total system mass fraction, and wherein polymerization inhibitor consumption is the 0.05% of total system mass fraction;
(4) by the Reverse Microemulsion System of preparation and surfactant mixing, namely obtaining water solublity drag reducer, dosage of surfactant is the 5-10% of reverse micro emulsion quality;
Described surfactant is one or more mixture in SAS, laurilsulfate sodium, secondary alkyl sulphate sodium, �� mono-sodium olefin sulfonate, succinic acid alkyl ester sulfonate sodium, sulfamic acid sodium, dodecylbenzene sodium sulfonate, coconut oil diethanol amide, fatty alcohol-polyoxyethylene ether.
2. the preparation method of a kind of water solublity drag reducer according to claim 1, it is characterised in that: described hydrophilic acrylmonomers is one or more mixture in acrylamide, Methacrylamide, DMAA, N-[2-(2-methyl-4-oxopentyl), n-methylolacrylamide, acrylic acid, methylpropene sodium sulfonate, methacrylic acid or 2-acrylamide-2-methyl propane sulfonic.
3. the preparation method of a kind of water solublity drag reducer according to claim 1, it is characterised in that: described lipophile acrylmonomers is one or more mixture in acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, Hexyl 2-propenoate, N-Hexyl methacrylate, octadecyl acrylate, octadecyl methacrylate or methoxy polyethylene glycol methacrylate-styrene polymer.
4. the preparation method of a kind of water solublity drag reducer according to claim 1, it is characterised 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 solublity drag reducer according to claim 1, it is characterised in that: described solvent naphtha is one or more mixture in benzene,toluene,xylene, hexamethylene, Pentamethylene., Petroleum, gasoline, kerosene, diesel oil or white oil.
6. the preparation method of a kind of water solublity drag reducer according to claim 1, it is characterised in that: described initiator is Ammonium persulfate., potassium peroxydisulfate, ammonium persulfate-sodium bisulfite, potassium peroxydisulfate-sodium sulfite, Ammonium persulfate .-sodium thiosulfate, potassium peroxydisulfate-sodium thiosulfate or water-soluble azo initiator.
7. the preparation method of a kind of water solublity drag reducer according to claim 1, it is characterised in that: described polymerization inhibitor is one or more mixture in hydroquinone, Pyrogentisinic Acid's monobutyl ether, tert-butyl catechol or copper naphthenate.
8. a water solublity drag reducer, it is characterised in that: prepared by method according to claim 1.
9. the application of the water solublity drag reducer described in a claim 8, it is characterised in that: for slippery water fracturing fluid reduces pipeline frictional resistance, reduce pump merit and improve the prop-carrying capacity of construction liquid, it is adaptable to the oil-gas mining of unconventional low permeability reservoir; During extemporaneous preparation by water per ton add mass fraction be 0.06-0.25% water solublity drag reducer, 0.2-0.5% demulsification cleanup agent and 0.5% clay stabilizer, obtain slippery water fracturing fluid after mix homogeneously.
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