CN104560000B - Friction-reducing agent of fracturing fluid composition - Google Patents

Friction-reducing agent of fracturing fluid composition Download PDF

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CN104560000B
CN104560000B CN201310512338.0A CN201310512338A CN104560000B CN 104560000 B CN104560000 B CN 104560000B CN 201310512338 A CN201310512338 A CN 201310512338A CN 104560000 B CN104560000 B CN 104560000B
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friction
fracturing fluid
reducing agent
fluid composition
alkyl
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CN104560000A (en
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鲍新宁
沙鸥
李应成
张卫东
许晓菁
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
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    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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    • C09K8/60Compositions for stimulating production by acting on the underground formation
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    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK 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
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    • E21B43/26Methods for stimulating production by forming crevices or fractures

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Abstract

The present invention relates to a kind of friction-reducing agent of fracturing fluid composition and its application, the problem of resistance-reducing yield is low in the prior art is mainly solved.The present invention is by using friction-reducing agent of fracturing fluid composition, including following components in terms of parts by weight:(1)1 part of Bis-quaternary Ammonium Surfactants;(2)0.01~100 part of alkyl ammonium polyethenoxy ether carboxylate;(3)0.01~100 part of polymer;(4)The technical scheme of 10~10000 parts of water, preferably solves the problem, during shale gas exploitation.

Description

Friction-reducing agent of fracturing fluid composition
Technical field
The present invention relates to friction-reducing agent of fracturing fluid composition and its application.
Background technology
Shale gas refers to that main body is located in dark-coloured mud shale or high-carbon mud shale, to adsorb or free state is is primarily present The gas accumulation of mode.According to the shale gas mining resources truth of a matter and Exploitation Potential, shale gas turned into after compact sandstone gas and The third important resource after coal bed gas.Shale gas reservoir has the characteristics of permeability is extremely low, more than 90% shale gas Well needs to take the well stimulations such as pressure break to link up intrinsic fracture, and it is exactly the development in crack to realize one of key factor of the economic exploitation Degree.The U.S. is the country of earliest exploitation shale gas, and China has many similarities with the U.S. on shale gas geological conditions, Shale gas enrichment geological conditions it is superior, with considerable shale gas development of resources potentiality.Shale gas exploitation technology is main Including staged fracturing of horizontal well technology, multiple fracturing technique, synchronous fracturing technique and riverfrac treatment technology etc., these technologies are continuous Improve shale gas well yield.Riverfrac treatment refers to apply adds friction reducer, activating agent, expansion-resisting agent or linear glue in clear water Deng the fracturing work carried out as working solution.Riverfrac treatment has the advantages that cost is low, it is low to injure and being capable of depth de-plugging.Clearly Hydraulic pressure, which splits, seldom needs cleaning, is substantially absent from residue injury problem, and can provide longer crack, and by fracturing propping agents Transport to as far as fracture network.The technology first successfully since use, had had evolved into shale gas exploitation from 1997 in the U.S. One important means.
The process of oil formation hydraulic fracturing is to use the pump of high-pressure large-displacement on ground, using the principle of liquid pressure transmission, will be had There is the fracturing fluid of certain viscosity, injected with the pressure of the absorbability more than oil reservoir to oil reservoir, and well cylinder pressure is gradually risen Height, so as to suppress high pressure in shaft bottom, when tensile strength of this pressure more than the crustal stress near the borehole wall and formation rock, just exists Nearby stratum produces crack in shaft bottom:Continue to inject the load fluid with proppant, crack extends forward and filled out with proppant, closing well Crack closure is on proppant afterwards, so as to form filling out with certain physical dimension and high flow conductivity near shaft bottom in stratum Sand crack, reaches the purpose of increasing yield and injection.The consumption of fracturing fluid is big, and needs the transmission by underground long range, therefore needs Expend huge energy.In shale gas fracturing process, with the raising of discharge capacity, frictional resistance of the working solution in pipeline will Exponentially increase, the pump pressure of construction is largely consumed and overcoming on pipeline frictional resistance, practical function is used to press off payzone in payzone Pressure it is little;Again because frictional resistance increase, discharge capacity are difficult to improve, crack is difficult to extend forward, does not reach the purpose to form seam net.Institute It is to improve discharge capacity, the effective way of raising fluid efficiency to reduce frictional resistance of the fracturing fluid on pipeline and stratum.The addition of friction reducer The frictional resistance of fracturing fluid system can be substantially reduced, so under same pump pressure, fracturing fluid can just transmit faster, it is farther, Energy consumption can be reduced, so as to produce economic benefit.
Water base friction reducer can be divided into according to the action principle of friction reducer by high flexibility macromolecule and viscoelastic surface lives Two kinds of agent of property.HMW high flexibility linear polymeric mainly includes the plants such as polyacrylamide polymer, hydroxypropyl guar Glue macromolecule and cellulose family macromolecule.High molecular polymer can freely stretch among fluid, suppress fluid molecule and exist Molecular collision that turbulent area occurs and the energy loss that produces, reach the purpose of drop resistance.The advantage of high molecular polymer friction reducer It is that concentration is low, low concentration can just realize drop resistance purpose.Patent US 4637418A are reported using acryloyl containing 2- The high molecular polymer of amido -2- methyl propane sulfonic acids (AMPS) structure is compounded with alcohols, can form a kind of friction-reducing agent of fracturing fluid. Viscoelastic surfactant friction reducer mainly includes quaternary cationic surfactant, beet alkali ampholytic ion surface active Agent etc..Its mechanism of action is, when surfactant concentration reaches certain value, to be formd under pipeline shear action, in solution viscous Elastic net structure, can get up a part of kinetic energy storage in turbulent flow whirlpool, reduce whirlpool kinetic energy loss, reach drop resistance mesh , with the raising of shear rate, this viscoplasticity network structure can also strengthen, and improve resistance reducing effect.Viscoelastic surface lives Property agent and high molecular polymer are compounded according to suitable ratio, with good resistance-reducing performance, are used into while can also reduce This.
US 4615825 is disclosed using cetyltrimethylammonium hydroxide, salicylic acid, sodium hydroxide according to appropriate ratio Example compounding can form viscoelastic surfactant;Patent WO 116117A1, which are reported, utilizes anion surfactant(For example it is oily Sour sodium)With cationic surfactant(Such as OTAC)Compound according to a certain percentage, can be formed has Viscoelastic system;Patent CN 1177974 describes alkyl betaine and lived with sulfate type or sulfonate type anionic surface Property agent compounding, form a kind of viscoelastic surfactant;US 2010167967A1 are reported to be lived using double type anionic surface Property agent and double-type cationic surfactant compound the viscoelastic surfactant to be formed.Above-mentioned system all has certain drop Resistive, resistance reducing effect can also be improved further.
The content of the invention
One of technical problems to be solved by the invention are the fracturing fluid compositions resistance-reducing yields containing friction reducer in the prior art Low the problem of, there is provided a kind of friction-reducing agent of fracturing fluid composition suitable for shale gas reservoir.The friction reducer is used for shale gas exploitation mistake Cheng Zhong, with resistance-reducing efficiency it is high the characteristics of.
The two of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem corresponding pressure break Application of the liquid friction reducer composition during shale gas exploitation.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows:A kind of friction-reducing agent of fracturing fluid combination Thing, by weight percentage including following components:
(1)1 part of Bis-quaternary Ammonium Surfactants;
(2)0.01~100 part of alkyl ammonium polyethenoxy ether carboxylate;
(3)0.01~100 polymer;
Wherein component(1)General molecular formula be:
Wherein component(2)General molecular formula be
Wherein, R1, R3, R6For C1~C30Alkyl, R2For C2~C6Alkylene, R4、R14、R5And R15Independently it is derived from C1 ~C4Alkyl;Xh-For anion, wherein h is the negative charge number of the anion;N >=1, j >=1, and n+j=2~20;Wherein M is selected From alkali metal, alkaline-earth metal, NH4, any one in H, i is M positive changes.
R in above-mentioned technical proposal1, R3Preferably C8~C24Alkyl, alkenyl, any one in aryl.R6Preferably C12 ~C24Alkyl, alkenyl, any one in aryl.It is preferred that n+j=4~12.Xh-H be not particularly limited, can for 1,2, 3rd, 4, until 10000, it can reach the object of the invention;It is preferred that h is 1, now Xh-More preferably F-、Cl-、Br-、I-、NO3 -、 HSO4 -、SO4 2-、CH3COO-、HO-C6H4-COO-、CH3-C6H4-SO3 -、CH3SO3 -、HO-CH2COO-、CH3CH(OH)COO-In Any one;X when h is 2h-It is preferred that SO4 2-, dicarboxylic acids root, the example of wherein dicarboxylic acids root has oxalate, malonate, fourth Two acid groups, glutarate, adipic acid root, tartrate anion etc.;When h is 3, such as citrate;When h is 4, such as equal four benzoic acid Root.Except X h-Outside for simple anion, it can also be polyanion form such as polyphosphate radical, polypropylene acid group.
Preferred R in above-mentioned technical proposal1=R3, and preferably C8~C24Alkyl, still more preferably C16~C18Alkyl. Component(2)It is preferred that R6For C12~C24Alkyl and one kind in the alkyl ammonium polyethenoxy ether carboxylate of n+j=4~12 or any It is several;R6 is more preferably C16~C18Alkyl;More preferably n+j=4~12.
Component in above-mentioned technical proposal(3)Described polymer can use polymer commonly used in the art, preferably guanidine glue, hydroxyl Modified guanidine glue, xanthan acid gel, polyacrylamide, one kind in hydrophobic modification polyacrylamide or any several.Institute State modified guanidine glue preferably hydroxypropyl modified guanidine glue.
It is R as most preferred technical scheme in above-mentioned technical proposal1=R3And be C16~C18Alkyl, R6For C16~C18, n + j is 4 ~ 8.
Friction-reducing agent of fracturing fluid composition described in above-mentioned technical proposal, formula preferably includes 1 part of quaternary ammonium salt Shuangzi table Face activating agent, 0.1~10 part of alkyl ammonium polyethenoxy ether carboxylate, 10~1000 parts of water.
For reduction cost of transportation, friction-reducing agent of fracturing fluid composition described in above-mentioned technical proposal, which can be used, contains component (1)、(2)With(3)Solid form, dissolved again with water when using;It can also include component in order to which onsite application is convenient(4)10~ 10000 parts of water.The component(4)Water can be deionized water, river, underground water, seawater etc., for easy construction, save water Consideration in terms of resource, can directly use job site retaining.The water used in the embodiment of the present invention and comparative example is west The rainwater that the block job site cisterns of southern oil gas branch company western sichuan region palpus five are collected.
Above-mentioned friction-reducing agent of fracturing fluid preparation method of composition is not particularly limited, as long as will be according to above-mentioned aequum each component It is well mixed.For example:By the desired amount of Bis-quaternary Ammonium Surfactants, alkyl ammonium polyethenoxy ether carboxylate and polymerization Thing, is dissolved into required water and stirs.
Component described in above-mentioned technical proposal(1)It can be commercially available, it would however also be possible to employ following methods synthesis is made:
For example:Hexadecyldimethyl benzyl ammonium tertiary amine and Isosorbide-5-Nitrae-dibromobutane are dissolved in 200ml ethanol solutions, concentration, which is added dropwise, is The pH of 5wt% sodium hydrate aqueous solution control system reacts 6 hours between 9~9.5 under the conditions of 65 DEG C.Reaction terminates Afterwards, solvent is evaporated off and obtains white solid powder C16-4-C16
Component described in above-mentioned technical proposal(2)It can be commercially available, it would however also be possible to employ following methods synthesis is made:
For example:Beef tallow amine APEO is dissolved in benzene solvent, and sodium hydroxide is added at 65 DEG C and is alkalized 2 hours, so After add sodium chloroacetate, at 75 DEG C reaction obtain within 5 hours butter ammonium APEO carboxylic acid sodium.
Component described in above-mentioned technical proposal(3)In polymer can be commercially available, can also be by synthesizing Arrive.For example hydroxypropyl guar can be obtained by melon Lovell glue under base catalyst effect with expoxy propane reaction, and structure is as follows:
In order to solve the two of our technical problem, technical scheme is as follows:Any one of one of above-mentioned technical problem The friction-reducing agent of fracturing fluid composition during shale gas exploitation as friction-reducing agent of fracturing fluid composition application.
The present invention is applied to shale gas reservoir reservoir, and western sichuan region five reservoirs of palpus are using friction-reducing agent of fracturing fluid combination of the invention Thing, resistance-reducing yield can reach more than 70%, achieve preferable technique effect, can be applied in shale gas reservoir exploitation production.
Brief description of the drawings
Fig. 1 is the Multifunctional flowing loop instrument schematic diagram for evaluating the resistance reducing effect of friction-reducing agent of fracturing fluid composition.Figure Include kinetic pump 1, crosslinking agent tank 2, crosslinking agent pump 3, pressure sensor 4, heat exchanger 5, base fluid tank 6, solution feed pump 7, waste liquid Pump 8 and vent line 9.
Embodiment
【Embodiment 1】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0mol hexyls dimethyl tertiary amine and 0.5mol glycol dibromides are dissolved in 200ml ethanol solutions In, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C small When.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C6-2-C6
(2)0.5mol octylame APEOs(2)It is dissolved in 200ml benzene, is added to equipped with stirring, reflux, divides In the reactor of water installations, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, return Stream reaction 5 hours, removes solvent, pungent ammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol.
(3)By 1 part of C6-2-C6Bis-quaternary Ammonium Surfactants, 100 parts of pungent ammonium polyoxyethylene(2)Ether carboxylate and 10 parts Hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 10000 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid combination of compositions physical performance is evaluated
Friction-reducing agent of fracturing fluid composition room is carried out according to the method in SY/T 6376-2008 fracturing fluid general technical specifications Interior resistance-reducing performance evaluation, loads Multifunctional flowing loop instrument by clear water(Schematic device is shown in Fig. 1), when determining clear water by pipeline Stable pressure differential deltapp 1;Stable pressure differential deltap when above-mentioned friction-reducing agent of fracturing fluid composition flows through pipeline is determined after the same methodp 2, by formula(1)Calculate resistance-reducing yield η:
(1)
It is 2.5m that discharge capacity is chosen from obtained friction pressure data3When/min fracturing fluid flows through internal diameter for 62mm oil pipes Resistance-reducing yield value, the results are shown in Table 2.
【Embodiment 2】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0mol octyls dimethyl tertiary amine and 0.5mol1,3- dibromopropane are dissolved in 200ml ethanol solutions, The pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5, is reacted 6 hours under the conditions of 65 DEG C. After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C8-3-C8
(2)0.5mol lauryl amine APEOs(2)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, pungent ammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol.
(3)By 1 part of C8-3-C8Bis-quaternary Ammonium Surfactants, 2 part of 12 ammonium polyoxyethylene(2)Ether carboxylate and 0.5 Part hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 3】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0mol octyls dimethyl tertiary amine and 0.5mol1,4- dibromobutane are dissolved in 200ml ethanol solutions, The pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5, is reacted 6 hours under the conditions of 65 DEG C. After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C8-4-C8
(2)0.5mol cetylamine APEOs(2)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, 16 ammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol.
(3)By 1 part of C8-4-C8Bis-quaternary Ammonium Surfactants, 0.5 part of cetyltrimethyl ammonium polyoxyethylene(2)Ether carboxylate With 0.01 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 150 parts of water, stirring 2 is small When, the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent is formed, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 4】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0mol Dodecyl Dimethyl Amines and 0.5mol1,2- Bromofumes are dissolved in 200ml ethanol solutions In, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C small When.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C12-2-C12
(2)0.5mol octadecylamine APEOs(2)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol.
(3)By 1 part of C12-2-C12Bis-quaternary Ammonium Surfactants, 3 parts of octadecylammonium polyoxyethylene(2)Ether carboxylate and 1 Part hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 500 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 5】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol Dodecyl Dimethyl Amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C12-4-C12
(2)0.5mol lauryl amine APEOs(2)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, 12 ammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol.
(3)By 1 part of C12-4-C12Bis-quaternary Ammonium Surfactants, 20 parts of dodecyl ammonium polyoxyethylene(2)Ether carboxylic acid Salt and 5 parts of hydroxypropyl guars(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 2500 parts of water, stirring 2 is small When, the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent is formed, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 6】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,6- dibromo-hexanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-6-C16
(2)0.5mol cetylamine APEOs(2)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, 16 ammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol.
(3)By 1 part of C16-6-C16Bis-quaternary Ammonium Surfactants, 1 part of cetyltrimethyl ammonium polyoxyethylene(2)Ether carboxylate With 1 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, shape Into the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 7】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(4)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(4)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 1 part of octadecylammonium polyoxyethylene(4)Ether carboxylate and 0.5 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, shape Into the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 8】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(6)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(6)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 1 part of octadecylammonium polyoxyethylene(6)Ether carboxylate and 1 Part hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 9】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(8)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(8)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 1 part of octadecylammonium polyoxyethylene(8)Ether carboxylate and 1 Part hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 10】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(8)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(8)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 1 part of octadecylammonium polyoxyethylene(8)Ether carboxylate and 1 Part hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 500 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 11】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(10)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(10)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 1 part of octadecylammonium polyoxyethylene(10)Ether carboxylate and 0.5 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 1000 parts of water, stirs 2 hours, The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent is formed, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 12】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(6)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(6)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 0.8 part of octadecylammonium polyoxyethylene(6)Ether carboxylate and 0.2 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 200 parts of water, stirs 2 hours, shape Into the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 13】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(6)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(6)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 1.2 parts of butter ammonium polyoxyethylene(6)Ether carboxylate and 1 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 14】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol hexadecyldimethyl benzyl ammoniums tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C16-4-C16
(2)0.5mol octadecylamine APEOs(8)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(8)Ether carboxylate 0.44mol.
(3)By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 0.8 part of butter ammonium polyoxyethylene(8)Ether carboxylate and 1 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 15】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol octadecyldimethyls tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C18-4-C18
(2)0.5mol octadecylamine APEOs(2)Be dissolved in 200ml benzene, be added to equipped with stirring, reflux, In the reactor of division box, 1.0mol powdered sodium hydroxides are added, 65 DEG C alkalize 2 hours, add 0.6mol sodium chloroacetates, Back flow reaction 5 hours, removes solvent, octadecylammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol.
(3)By 1 part of C18-4-C18Bis-quaternary Ammonium Surfactants, 1 part of octadecylammonium polyoxyethylene(2)Ether carboxylate and 1 Part hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 300 parts of water, stirs 2 hours, is formed The viscoelastic fracturing fluid friction reducer composition of homogeneous transparent, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Embodiment 16】
1. the preparation of friction-reducing agent of fracturing fluid composition
(1)1.0 mol octadecyldimethyls tertiary amines and 0.5mol 1,4- dibromobutanes are dissolved in 200ml ethanol molten In liquid, the pH for the sodium hydrate aqueous solution control system that concentration is 5wt% is added dropwise between 9~9.5,6 are reacted under the conditions of 65 DEG C Hour.After reaction terminates, solvent is evaporated off and obtains 0.8mol white solid powders C18-4-C18
(2)The lauryl amine APEOs of 0.5mol bis-(2)It is dissolved in 200ml benzene, is added to equipped with stirring, backflow dress Put, in the reactor of division box, add 1.0mol powdered sodium hydroxides, 65 DEG C alkalize 2 hours, add 0.6mol monoxones Sodium, back flow reaction 5 hours removes solvent, 22 ammonium polyoxyethylene is recrystallized to give in ethanol(2)Ether carboxylate 0.44mol。
(3)By 1 part of C18-4-C18Bis-quaternary Ammonium Surfactants, 1 part of docosyl ammonium polyoxyethylene(2)Ether carboxylic acid Salt and 100 parts of hydroxypropyl guars(30 DEG C, 170s-1Under, apparent viscosity is 80mPas), it is dissolved into 10000 parts of water, stirring 2 Hour, the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent is formed, composition is shown in Table 1.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, compares the results are shown in Table 2 for convenience.
【Comparative example 1】
1. the preparation of friction-reducing agent of fracturing fluid composition
By 1 part of hydroxypropyl guar(30 DEG C, 170s-1Under, apparent viscosity is 80mPas)It is dissolved into 200 parts of water, stirring 2 Hour, form the viscoelastic fracturing fluid friction reducer of homogeneous transparent.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, resistance-reducing yield data are 71%.
【Comparative example 2】
1. the preparation of friction-reducing agent of fracturing fluid composition
By 1 part of C16-4-C16Bis-quaternary Ammonium Surfactants, 1 part of docosyl polyoxyethylene(2)Ether carboxylate and 1 Part hydroxypropyl guar, is dissolved into 300 parts of water, stirs 2 hours, forms the viscoelastic fracturing fluid friction reducer combination of homogeneous transparent Thing.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, resistance-reducing yield data are 48%.
【Comparative example 3】
1. the preparation of friction-reducing agent of fracturing fluid composition
By the C of 1.8 parts of embodiments 1216-4-C16Bis-quaternary Ammonium Surfactants and 1 part of hydroxypropyl guar are dissolved into 220 In part water, stir 2 hours, form the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, resistance-reducing yield data are 50%.
【Comparative example 4】
1. the preparation of friction-reducing agent of fracturing fluid composition
Octadecylammonium polyoxyethylene prepared by 1.8 parts of embodiments 12(6)Ether carboxylate and 1 part of hydroxypropyl guar are dissolved into In 220 parts of water, stir 2 hours, form the viscoelastic fracturing fluid friction reducer composition of homogeneous transparent.
2. friction-reducing agent of fracturing fluid composition properties are evaluated
Method of evaluating performance be the same as Example 1, resistance-reducing yield data are 61%.
Component in the friction-reducing agent of fracturing fluid composition of the present invention(1)And component(2)Have in terms of resistance-reducing yield is improved bright Aobvious synergy.This can from embodiment 12 and comparative example 3 and comparative example 4 it is year-on-year in can intuitively find out.
Table 1(It is continued)Embodiment 1-16 fracturing fluids are constituted
Table 1(It is continuous)Embodiment 1-16 fracturing fluids are constituted
The embodiment 1-16 fracturing fluid resistance-reducing yields of table 2

Claims (10)

1. a kind of friction-reducing agent of fracturing fluid composition, including following components in terms of parts by weight:
(1)1 part of Bis-quaternary Ammonium Surfactants;
(2)0.01~100 part of alkyl ammonium polyethenoxy ether carboxylate;
(3)0.01~100 part of polymer;
Wherein component(1)General molecular formula be:
Wherein component(2)General molecular formula be
Wherein, R1, R3, R6For C1~C30Alkyl, R2For C2~C6Alkylene, R4、R14、R5And R15Independently it is derived from C1~C4 Alkyl;Xh-For anion, wherein h is the negative charge number of the anion;N >=1, j >=1, and n+j=2~20;Wherein M is selected from alkali Metal, alkaline-earth metal, NH4, any one in H, i is M positive changes.
2. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that R1, R3For C8~C24Alkyl, alkenyl, Any one in aryl.
3. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that R6For C12~C24Alkyl, alkenyl, virtue Any one in base.
4. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that n+j=4~12.
5. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that wherein component(1)X in general molecular formulah-For F-、Cl-、Br-、I-、NO3 -、SO3H-、CH3COO-、HO-C6H4-COO-、CH3-C6H4-SO3 -、CH3SO3 -、HO-CH2COO-、CH3CH (OH)COO-In any one.
6. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that R1=R3, it is C8~C24Alkyl.
7. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that component(2)Selected from R6For C12~C24's Alkyl and one kind or any several in the alkyl ammonium polyethenoxy ether carboxylate of n+j=4~12.
8. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that component(3)Described polymer is guanidine Glue, hydroxypropyl modified guanidine glue, xanthan acid gel, polyacrylamide, one kind in hydrophobic modification polyacrylamide or any several Kind.
9. friction-reducing agent of fracturing fluid composition according to claim 1, it is characterised in that the friction-reducing agent of fracturing fluid composition is also Including component(4)10~10000 parts of water;Described wet concentration is from any one in deionized water, river, underground water, seawater.
10. friction-reducing agent of fracturing fluid is used as friction-reducing agent of fracturing fluid during shale gas exploitation any one of claim 1 to 9 Application.
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