CN104974308B - A kind of pressure break friction reducer and preparation method thereof - Google Patents
A kind of pressure break friction reducer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of pressure break friction reducer, including：Acrylamide monomer, double bond containing cationic monomer, anionic polymer template, chelating agent, molecular weight regulator and water are mixed and pH value is adjusted, the aqueous solution that pH value is 35 is obtained；Organic solvent is contacted with emulsifying agent, oil solution is obtained；The aqueous solution is contacted with the oil solution, water-in-oil emulsion is obtained；Under an inert atmosphere, the water-in-oil emulsion is contacted in batches with initiator, and carries out polymerisation, the mixture for then obtaining polymerisation is contacted with phase inversion agent；Wherein, the hydrophilic lipophilic balance of the emulsifying agent is 46, and the molecular weight of the anionic polymer template is less than 800,000, the structural formula such as formula of the anionic polymer template（I）It is shown, further relate to pressure break friction reducer prepared by a kind of above method.The resistance-reducing yield of pressure break friction reducer prepared by the present invention is high, clay swell inhibition is high, good water solubility and formation damage are low.
Description
Technical field
The present invention relates to a kind of pressure break friction reducer, and a kind of preparation method of pressure break friction reducer.
Background technology
The characteristics of reservoir of shale gas has low porosity and low-permeability, exploitation difficulty is big, at present mainly using smooth
Water fracturing technology is exploited, and fracturing fluid is pumped into stratum, high-voltage high-speed condition at a high speed after the supercharging of high-pressure pump injection device by tubing string
Lower fluid turbulent flow phenomenon during Bottomhole pressure is serious, there is larger frictional resistance between fracturing fluid and tube wall, and fluid rubs
Wipe resistance and limit the flowing of fluid in the duct, cause the reduction of pipeline throughput rate and energy loss increase.Accordingly, it would be desirable to using
The method of friction reducer is added in fluid to reduce the influence of frictional resistance, improves efficiency of construction.
Friction reducer is to add a small amount of high molecular polymer or surfactant in a liquid, makes liquid in turbulent flow
By influenceing turbulence structure significantly to reduce resistance, also referred to as Toms effects.High molecular polymer resistance-reducing yield is high, cheap,
The macromolecule friction reducer commonly used in slippery water fracturing fluid is mainly guanidine glue and polyacrylamide polymer, the insoluble matter one of guanidine glue
As 8% or so, while residue is more after breaking gel, the injury to stratum and crack is larger.Polyacrylamide polymer water is insoluble
Thing is relatively fewer, with certain resistance-reducing performance and resistant to shearing ability.
Patent application CN103045226A discloses a kind of friction reducer and preparation method thereof and using the smooth of the friction reducer
Water fracturing fluid and preparation method thereof, this friction reducer is using polyethylene glycol oxide as main drop resistance composition, with preferably dropping resistive
Can, but organic solvent account for the 40%~85% of friction reducer product quality, nonionic surfactant and account for friction reducer product quality
0~10%, with serious environmental problem, polyethylene glycol oxide resistant to shearing ability is poor in addition, in the slippery water pressure break of high shear
It can rapidly be degraded in construction, cause resistance-reducing performance to decline.
Patent application CN102977877A discloses a kind of shale gas pressure break drag reducer and preparation method thereof, and it is in salt
In the aqueous solution under the protection of dispersant by free radical trigger acrylamide, 2- acrylamide-2-methylpro panesulfonic acids sodium and
Three kinds of monomers progress random copolymerizations of PAA obtain emulsus, dispersed friction reducer, with preferable endurance of cutting energy, but
Product prepared by the method according to the patent application lumps after standing overnight, and viscosity is very high, flow difficulties, it is impossible to apply at satisfaction scene
Work requirement, and under the conditions of flow is relatively low, the resistance-reducing efficiency of the friction reducer of invention synthesis is only 20%.
Be badly in need of that a kind of dissolution velocity is fast, resistance-reducing yield is high, bin stability is high now, clay swell inhibition and shear resistant
Can be high, friction reducer of the low advantage of formation damage and preparation method thereof.
The content of the invention
The purpose of the present invention is to overcome that the dissolution velocity of above-mentioned friction reducer in the prior art is slow, resistance-reducing yield is low, storage is stable
Low, the clay swell inhibition of property is low, anti-shear performance is poor and the defect such as formation damage height there is provided a kind of pressure break friction reducer
Preparation method, and pressure break friction reducer prepared by a kind of this method.
The present inventor has found under study for action, as long as by acrylamide monomer, double bond containing cationic monomer, the moon
Ionomer template, chelating agent, molecular weight regulator and water are mixed to prepare the aqueous solution that pH value is 3-5；Then it is this is water-soluble
Water-in-oil emulsion is made in liquid, under an inert atmosphere, and water-in-oil emulsion is carried out into polymerisation, then by mixing that polymerisation is obtained
Compound is contacted with phase inversion agent；Wherein, the hydrophilic lipophilic balance of the emulsifying agent is 4-6, the cationic polymer template
Molecular weight is less than 800,000, the structural formula of the cationic polymer template such as following formula（I）It is shown, you can dissolution velocity is made
It hurry up, resistance-reducing yield is high, clay swell inhibition is high, the friction reducer that anti-shear performance is good and formation damage is low.
R is hydrogen or methyl；
A is O or NH；
Z be OM orWherein, M is Na, K, NH4.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of preparation method of pressure break friction reducer,
This method includes：
（1）By acrylamide monomer, double bond containing cationic monomer, anionic polymer template, chelating agent, molecular weight
Conditioning agent and water mix and adjust pH value, obtain the aqueous solution that pH value is 3-5；
（2）Organic solvent is contacted with emulsifying agent, oil solution is obtained；
（3）By step（1）The obtained aqueous solution and step（2）Obtained oil solution contact, obtains water-in-oil emulsion；
（4）Under an inert atmosphere, by step（3）Obtained water-in-oil emulsion is contacted in batches with initiator, and is polymerize
Reaction, the mixture for then obtaining polymerisation is contacted with phase inversion agent；
Wherein, the hydrophilic lipophilic balance of the emulsifying agent is 4-6, and the molecular weight of the anionic polymer template is less than
800000, the structural formula such as formula of the anionic polymer template（I）It is shown：
R is hydrogen or methyl；
A is O or NH；
Z be OM orWherein, M is Na, K, NH4.
On the other hand, present invention also offers the pressure break friction reducer prepared according to the above method.
Compared with the polymerization of conventional inverter emulsion, preparation method of the invention is used to be added in polymerization reaction system
The method of macromolecule polyalcohol template, by the hydrogen bond between polymer template molecule and polymerized monomer, Van der Waals interaction, quiet
Electric attraction or covalent bond interaction, change polymerization rate, molecular weight product and molecular weight distribution, product copolymerization units
Sequence is arranged evenly, the steric configuration of product；By adjusting the distribution of acrylamide unit and cation unit block, change
Molecular configuration, the space structure of friction reducer polymer, so that the resistance-reducing performance and anti-shear performance of product are improved, due to not
With the distribution of polymerized unit block, friction reducer product hydrolysis product occurs without insoluble matter, and relative due to cation unit
Concentrate, hydrolysate has obvious inhibitory action to the hydration swelling of clay.
Friction reducer produced by the present invention quickly dissolves in water, will not form flake, meets the online mixture of slippery water pressure break
Requirement；The maximum resistance-reducing yield of the aqueous solution of the friction reducer of mass concentration 1% is 74.5-78%；And friction reducer hydrolysate without
Insoluble matter occurs, very low to stratum nocuity, and the core damage rate of the aqueous solution of the friction reducer of mass concentration 1% is 4.3-8.1%；
The clay swell inhibiting rate of the aqueous solution of the friction reducer of mass concentration 1% is 81.5-89%, has significant suppression to make to clay swell
With, thus new expansion-resisting agent need not be added again in actual use, significantly reduce the cost of slippery water.Therefore, use
Resistance-reducing yield height, clay swell inhibition height, good water solubility, the anti-shear performance of pressure break friction reducer prepared by the method for the present invention
Good and formation damage is low.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is the resistance-reducing yield of pressure break friction reducer and the relation curve of flow.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of preparation method of pressure break friction reducer, this method includes：
（1）By acrylamide monomer, double bond containing cationic monomer, anionic polymer template, chelating agent, molecular weight
Conditioning agent and water mix and adjust pH value, obtain the aqueous solution that pH value is 3-5；
（2）Organic solvent is contacted with emulsifying agent, oil solution is obtained；
（3）By step（1）The obtained aqueous solution and step（2）Obtained oil solution contact, obtains water-in-oil emulsion；
（4）Under an inert atmosphere, by step（3）Obtained water-in-oil emulsion is contacted in batches with initiator, and is polymerize
Reaction, the mixture for then obtaining polymerisation is contacted with phase inversion agent；
Wherein, the hydrophilic lipophilic balance of the emulsifying agent is 4-6, and the molecular weight of the anionic polymer template is less than
800000, the structural formula such as formula of the anionic polymer template（I）It is shown：
R is hydrogen or methyl；
A is O or NH；
Z be OM orWherein, M is Na, K, NH4.
According to method of the present invention, as long as by structural formula such as formula（I）Shown and molecular weight is the institute less than 800,000
State anionic polymer template, with acrylamide monomer, double bond containing cationic monomer, chelating agent, molecular weight regulator and
Water is mixed, and the aqueous solution that pH value is 3-5 is made, then by the aqueous solution and by emulsifying agent system of the hydrophilic lipophilic balance for 4-6
The oil solution contact obtained, is made water-in-oil emulsion, then carries out polymerisation, then contact with phase inversion agent, you can dissolving speed is made
Degree is fast, resistance-reducing yield is high, clay swell inhibition is high, anti-shear performance is high and the low friction reducer of formation damage.But in order that
The dissolution velocity of friction reducer is faster made from obtaining, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher and stratum
Nocuity is lower, the anionic polymer template be preferably selected from Sodium Polyacrylate, polyacrylic acid potassium, sodium polymethacrylate,
At least one of polymethylacrylic acid potassium and poly- 2- acrylamide-2-methylpro panesulfonic acids sodium；More preferably poly- 2- acryloyls
Amido -2- methyl propane sulfonic acid sodium.
Preferably, the cationic polymer template molecule amount is 5-80 ten thousand.
In the present invention, molecular weight refers to viscosity average molecular weigh.
According to method of the present invention, acrylamide monomer, double bond containing cationic monomer, anionic polymer mould
Plate, chelating agent, molecular weight regulator, the consumption of water can be the conventional amount used of this area, but in order that obtain obtained drop resistance
The dissolution velocity of agent is faster, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher and formation damage is lower,
Relative to the acrylamide monomer of 100 parts by weight, the consumption of the double bond containing cationic monomer is preferably 10-100
Parts by weight, more preferably 20-50 parts by weight；The consumption of the anionic polymer template is preferably 1-10 parts by weight, more preferably
For 1-5 parts by weight；The consumption of the chelating agent is preferably 0.001-5 parts by weight, more preferably 0.02-0.2 parts by weight；Molecular weight
The consumption of conditioning agent is preferably 0.001-1 parts by weight, more preferably 0.01-0.1 parts by weight；The consumption of water is preferably 50-200 weights
Measure part, more preferably 100-150 parts by weight.
According to method of the present invention, the acrylamide monomer can be used to prepare polyacrylamide for this area
The conventional acrylamide monomer of emulsion, but in order that obtained friction reducer dissolution velocity faster, resistance-reducing yield it is higher,
Clay swell inhibition is higher, shear resistant is higher and formation damage is lower, and the acrylamide monomer is preferably selected from third
Acrylamide, Methacrylamide, N, N- DMAAs, N, N- acrylamides, NIPA, N-
At least one of NMA and N- hydroxyethyl acrylamides, more preferably acrylamide.
According to method of the present invention, what the double bond containing cationic monomer can be known in the art can be used in
The double bond containing cationic monomer of polyacrylamide emulsion is prepared, but in order that obtains the dissolution velocity of obtained friction reducer more
It hurry up, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher and formation damage is lower, the double bond containing sun
Ion monomer is preferably selected from acrylamidopropyl-benzyl ammonium chloride, dimethyl diallyl ammonium chloride, methacryloxypropyl second
In base trimethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac and methacryiamidopropyl dimethyl benzyl ammonium chloride
At least one, more preferably MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and/or acrylyl oxy-ethyl-trimethyl salmiac,
More preferably MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
According to method of the present invention, any one chelating agent that the chelating agent can be known in the art, still
In order that the dissolution velocity of friction reducer is faster made from obtaining, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher
Lower with formation damage, the chelating agent is preferably selected from disodium ethylene diamine tetraacetate, triethylenediamine pentaacetic acid, citric acid, lemon
At least one of lemon hydrochlorate and poly- hydroxy acrylic acid；More preferably disodium ethylene diamine tetraacetate and/or citrate, the lemon
Lemon hydrochlorate is preferably selected from least one of potassium citrate, sodium citrate, calcium citrate and ammonium citrate.
According to method of the present invention, to the molecular weight regulator, there is no particular limitation, for example, can be selected from first
At least one of sour sodium, sodium acetate, glycerine and isopropanol, preferably sodium formate.
According to method of the present invention, the water can be the conventional experimental water in this area, for example, can be distillation
Water and/or deionized water.
According to method of the present invention, in step（1）In, acrylamide monomer, double bond containing cationic monomer, the moon
Ionomer template, chelating agent, molecular weight regulator and the order of water mixing are not particularly limited, as long as enabling to propylene
Acid amides system monomer, double bond containing cationic monomer, anionic polymer template, chelating agent, molecular weight regulator and water are deposited simultaneously
It is in reaction system.
According to method of the present invention, in step（1）In, acrylamide monomer, double bond containing cationic monomer, the moon
Ionomer template, chelating agent, molecular weight regulator and the condition of water mixing can be to be stirred, preferably at room temperature
Ground, the condition of mixing includes：15-25 DEG C of temperature, stirring is to being completely dissolved.
According to method of the present invention, in step（1）In, to the method for adjusting pH value, there is no particular limitation,
The method that regulation pH value commonly used in the art can be used, for example, can be by into reactant mixture plus alkali or sour
Method adjusts the pH value of the aqueous solution, and to the alkali, there is no particular limitation with sour species, as long as enabling to the aqueous solution
PH value in the range of 3-5.
According to method of the present invention, in step（2）In, to the consumption of the organic solvent, there is no particular limitation,
In order that the dissolution velocity of friction reducer is faster made from obtaining, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher
Lower with formation damage, relative to the acrylamide monomer of 100 parts by weight, the consumption of the organic solvent is preferably
50-200 parts by weight, more preferably 90-150 parts by weight.
According to method of the present invention, the organic solvent can for it is well known by persons skilled in the art any one have
Machine solvent, the organic solvent can be selected from toluene, dimethylbenzene, hexane, hexamethylene, normal heptane, isoparaffin, gasoline, kerosene
At least one of with white oil；In order that obtained friction reducer dissolution velocity faster, resistance-reducing yield is higher, clay swell suppresses
The higher, shear resistant of property is higher and formation damage is lower, be preferably selected from toluene, dimethylbenzene, normal heptane, isoparaffin, gasoline,
At least one of kerosene and white oil；More preferably isoparaffin and/or white oil；More preferably boiling point higher than 150 DEG C, flash-point it is big
In 60 DEG C of isoparaffin and/or white oil.
According to method of the present invention, in step（2）In, to the consumption of the emulsifying agent, there is no particular limitation, but
Be in order that obtained friction reducer dissolution velocity faster, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant more
High and formation damage is lower, and relative to the acrylamide monomer of 100 parts by weight, the consumption of the emulsifying agent is preferably
5-20 parts by weight, more preferably 8-15 parts by weight.
According to method of the present invention, in order in step（3）In the emulsion of Water-In-Oil is made, as long as by the breast
The hydrophilic lipophilic balance of agent is defined to 4-6, still, in order that obtained friction reducer dissolution velocity faster, drop
Resistance rate is higher, clay swell inhibition is higher, shear resistant is higher and formation damage is lower, the emulsifying agent be preferably it is non-from
Sub- emulsifying agent, is more preferably selected from sorbitan oleate, sorbitan monooleate APEO, alkylphenol-polyethenoxy
At least one of ether, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether and aliphatic amine polyoxyethylene ether.
According to method of the present invention, in step（3）In, the aqueous solution order of addition of the contact with the oil solution
Do not limit, the oil solution can be added in the aqueous solution, the aqueous solution can also be added to the oil molten
In liquid, the present invention is not particularly limited.But in order to be more beneficial for improving the stability of obtained water-in-oil emulsion, so that
The dissolution velocity of obtained friction reducer is faster, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher and stratum wound
Evil property is lower, it is preferable that the aqueous solution is added into progress contact mixing in the oil solution.The oil solution and the water
The contact hybrid mode present invention of solution is also not particularly limited, as long as the two contact mixing can form stable water in oil emulsion
Liquid, it is preferable that oil solution contact with the aqueous solution is blended in the lower progress of high speed shearing emulsification effect, so as to shape
Into stable water-in-oil emulsion.In the present invention, the water-in-oil emulsion of described stabilization refers to single in the presence of emulsifying agent
The body aqueous solution（Drop）It is equably scattered in organic solvent in short grained form.
According to method of the present invention, in step（4）In, the consumption of the initiator can be conventional amount used, still
In order that the dissolution velocity of friction reducer is faster made from obtaining, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher
Lower with formation damage, relative to the acrylamide monomer of 100 parts by weight, the consumption of the initiator is preferably
0.001-2 parts by weight, more preferably 0.01-0.2 parts by weight.
According to method of the present invention, the initiator can be the conventional initiator for polymerisation, can be with
For water-soluble redox system initiator and/or azo-initiator, wherein, the water-soluble redox system is containing aerobic
Agent and reducing agent, it is preferable that the mass ratio of the Oxidizing and Reducing Agents is 5：1-1：1, the oxidant is selected from peroxidating
Hydrogen, persulfate, potassium permanganate, bromate, benzoyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide and two
At least one of cumene peroxide, the reducing agent is selected from bisulfites, sulphite, rongalite, thiosulfuric acid
At least one of sodium, sodium hydrosulfite, triethylamine and tetramethylethylenediamine, azo-initiator are selected from 2,2 '-azo diisobutyl
At least one of amidine hydrochloride and 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride].
According to method of the present invention, in step（4）In, the consumption of the phase inversion agent can be conventional amount used, still
In order that the dissolution velocity of friction reducer is faster made from obtaining, resistance-reducing yield is higher, clay swell inhibition is higher, shear resistant is higher
Lower with formation damage, relative to the acrylamide monomer of 100 parts by weight, the consumption of the phase inversion agent is preferably 1-
20 parts by weight, more preferably 5-10 parts by weight.
According to method of the present invention, as long as the phase inversion agent ensure that friction reducer is keeping the feelings of higher resistance-reducing yield
It is very fast in water-soluble dissolution velocity under condition, in order that obtained friction reducer dissolution velocity faster, resistance-reducing yield it is higher, viscous
Soil expansion inhibition is higher, shear resistant is higher and formation damage is lower, it is preferable that the phase inversion agent is lost selected from polyoxyethylene
Water Span, NPE, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol
APEO, heterogeneous ten alcohol polyoxyethylene ether, isomery undecyl alcohol APEO, isomerous tridecanol polyoxyethylene ether and fat
At least one of amine APEO；It is more preferably selected from polyoxyethylene sorbitan fatty acid ester, Nonyl pheno
It is ether, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyethenoxy ether, heterogeneous ten alcohol polyoxyethylene ether, different
At least one of structure undecyl alcohol APEO and isomerous tridecanol polyoxyethylene ether.
According to method of the present invention, in step（4）In there is provided the mode of inert atmosphere can be conventional for this area
Various methods, for example, the methods such as nitrogen and/or argon gas can be passed through into reaction system.
According to method of the present invention, in step（4）In, the contact addition of the water-in-oil emulsion and the initiator
Order there is no particular limitation, water-in-oil emulsion can be added in initiator, initiator can also be added to oily bag
In aqueous emulsion, it is preferable that the initiator is added portionwise in the water-in-oil emulsion, in the present invention, it is added portionwise and refers to
Divide 3-5 addition, there is no particular limitation for every batch of amount added, as long as the total amount added is within the scope of the invention
Can.When initiator is water-soluble redox system initiator, reducing agent is first added, then divides 3-5 addition oxidant, also may be used
First to add oxidant, then divide 3-5 addition reducing agent, it is preferable that first add oxidant, then divide 3-5 addition reducing agent.
According to method of the present invention, in step（4）In, the mixture that polymerisation is obtained is contacted with phase inversion agent, is added
Plus order there is no particular limitation, phase inversion agent can be added in mixture, can also added mixture in phase inversion agent,
Preferably, the phase inversion agent is added in mixture.
According to method of the present invention, in step（4）In, to the water-in-oil emulsion and the contact of the initiator
There is no particular limitation for temperature, for example, can be 15-25 DEG C.
According to method of the present invention, in step（4）In, for polymerisation condition without particular/special requirement, can adopt
With the conventional condition in this area, for example, the condition of polymerisation can include：Temperature is 20-50 DEG C, and the reaction time is that 4-8 is small
When.
According to method of the present invention, in step（4）In, the bar that the mixture that polymerisation is obtained is contacted with phase inversion agent
Part can be to be stirred at conventional temperatures, it is preferable that the condition of contact includes：Temperature is 20-40 DEG C, and mixing speed is
50-100rpm, mixing time is 20-40min.
On the other hand, present invention also offers the pressure break friction reducer prepared according to method as described above.
Embodiment
The reagent used in embodiment and comparative example is commercially available product, and identical rule of origin is identical,
In embodiment and comparative example, molecular weight refers to viscosity average molecular weigh；Span-80 hydrophilic lipophilic balance
（HLB）For 4.3, Tween-80 hydrophilic lipophilic balance（HLB）For 10, the HLB of blended emulsifier is according to following formula meter
Calculate：
HLB=Span-80 of blended emulsifier mass fraction × 4.3+Tween-80 mass fraction × 10
Embodiment 1
The present embodiment is used to illustrate pressure break friction reducer of the present invention and preparation method thereof.
（1）Under the conditions of 15 DEG C, by 100g acrylamides, 43.75g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides（80%
The aqueous solution）, the poly- 2- acrylamide-2-methylpro panesulfonic acids sodium of 2g（Molecular weight is 150,000）, 0.1g disodium ethylene diamine tetraacetates,
0.05g sodium formates and 111.25g deionized waters are mixed in 1000mL beakers, are stirred to being completely dissolved, then slow thereto
The aqueous hydrochloric acid solution for adding 10 weight % adjusts pH value to 4, obtains the aqueous solution that pH value is 4；
（2）10.5g Span-80 and 1.5g Tween-80 are mixed to get blended emulsifier, the mixing and emulsifying is calculated
The hydrophilic lipophilic balance of agent is 5, then by blended emulsifier and 120g white oils（Boiling point boiling range is 220-255 DEG C, and flash-point is 80
℃）Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
（3）By step（1）The obtained aqueous solution is added to and step（2）It is scattered with high speed shear in obtained oil solution
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
（4）Then by step（3）Obtained water-in-oil emulsion is added to equipped with condenser pipe, thermometer, nitrogen inlet and stirred
In the 1000mL polymerization reaction kettles for mixing device, after being 400mL/min nitrogen deoxygenation 30 minutes with flow, under the conditions of 16 DEG C, to oil
Point 3 10 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution in bag aqueous emulsion
1.0g, the amount added every time is respectively 0.3g, 0.3g and 0.4g, under the conditions of 45 DEG C, react 4 hours, then at 30 DEG C to
Polyoxyethylene sorbitan fatty acid ester is added in mixture（Tween-85）5g, with 80rpm mixing speeds, stirs 30min,
Then it is to obtain pressure break friction reducer P1 with 80 mesh filter-cloth filterings.
Embodiment 2
The present embodiment is used to illustrate pressure break friction reducer of the present invention and preparation method thereof.
（1）Under the conditions of 25 DEG C, by 100g acrylamides, 62.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides（80%
The aqueous solution）, the poly- 2- acrylamide-2-methylpro panesulfonic acids sodium of 5g（Molecular weight is 50,000）, 0.2g disodium ethylene diamine tetraacetates,
0.1g sodium formates and 137.5g deionized waters are mixed in 1000mL beakers, are stirred to being completely dissolved, then slow thereto to add
The aqueous hydrochloric acid solution for entering 10 weight % adjusts pH value to 3, obtains the aqueous solution that pH value is 3；
（2）10.5g Span-80 and 4.5g Tween-80 are mixed to get blended emulsifier, the mixing and emulsifying is calculated
The hydrophilic lipophilic balance of agent is 6, then by blended emulsifier and 150g white oils（Boiling point boiling range is 240-280 DEG C, and flash-point is 100
℃）Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
（3）By step（1）The obtained aqueous solution is added to and step（2）It is scattered with high speed shear in obtained oil solution
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
（4）Then by step（3）Obtained water-in-oil emulsion is added to equipped with condenser pipe, thermometer, nitrogen inlet and stirred
In the 1000mL polymerization reaction kettles for mixing device, after being 400mL/min nitrogen deoxygenation 30 minutes with flow, under the conditions of 24 DEG C, to oil
Point 4 10 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution in bag aqueous emulsion
1.0g, the amount added every time is 0.25g, under the conditions of 45 DEG C, reacts 8 hours, is then added at 20 DEG C into mixture
NPE（NP-10）7.5g, with 100rpm mixing speeds, stirs 20min, is then produced with 80 mesh filter-cloth filterings
To pressure break friction reducer P2.
Embodiment 3
The present embodiment is used to illustrate pressure break friction reducer of the present invention and preparation method thereof.
（1）Under the conditions of 20 DEG C, by 100g acrylamides, 25g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides（80% water
Solution）, the poly- 2- acrylamide-2-methylpro panesulfonic acids sodium of 1g（Molecular weight is 800,000）, 0.02g disodium ethylene diamine tetraacetates,
0.01g sodium formates and 100g deionized waters are mixed in 1000mL beakers, are stirred to being completely dissolved, are then slowly added to thereto
10 weight % aqueous hydrochloric acid solution adjusts pH value to 5, obtains the aqueous solution that pH value is 5；
（2）8g Span-80 are taken, Span-80 hydrophilic lipophilic balance is 4.3, then by Span-80 and 90g white oils
（Boiling point boiling range is 200-250 DEG C, and flash-point is 80 DEG C）Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
（3）By step（1）The obtained aqueous solution is added to and step（2）It is scattered with high speed shear in obtained oil solution
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
（4）Then by step（3）Obtained water-in-oil emulsion is added to equipped with condenser pipe, thermometer, nitrogen inlet and stirred
In the 1000mL polymerization reaction kettles for mixing device, after being 400mL/min nitrogen deoxygenation 30 minutes with flow, under the conditions of 21 DEG C, to oil
Point 51 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution 1.0g in bag aqueous emulsion,
The amount added every time is 0.2g, under the conditions of 45 DEG C, reacts 6 hours, octyl phenol is then added into mixture at 40 DEG C
APEO（OP-10）10g, with 50rpm mixing speeds, stirs 40min, is then to obtain pressure break to use with 80 mesh filter-cloth filterings
Friction reducer P3.
Embodiment 4
The present embodiment is used to illustrate pressure break friction reducer of the present invention and preparation method thereof.
（1）Under the conditions of 25 DEG C, by 100g acrylamides, 100g acrylyl oxy-ethyl-trimethyl salmiacs（80% is water-soluble
Liquid）, 2g Sodium Polyacrylates（Molecular weight is 500,000）, 0.5g disodium ethylene diamine tetraacetates, 0.5g sodium formates and 50g deionized waters exist
Mix, stirred to being completely dissolved in 1000mL beakers, 10 weight % aqueous hydrochloric acid solution regulation pH value is then slowly added to thereto
To 5, the aqueous solution that pH value is 5 is obtained；
（2）10.5g Span-80 and 4.5g Tween-80 are mixed to get blended emulsifier, the mixing and emulsifying is calculated
The hydrophilic lipophilic balance of agent is 6, then by blended emulsifier and 200g white oils（Boiling point boiling range is 220-255 DEG C, and flash-point is 80
℃）Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
（3）By step（1）The obtained aqueous solution is added to and step（2）It is scattered with high speed shear in obtained oil solution
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
（4）Then by step（3）Obtained water-in-oil emulsion is added to equipped with condenser pipe, thermometer, nitrogen inlet and stirred
In the 1000mL polymerization reaction kettles for mixing device, after being 400mL/min nitrogen deoxygenation 30 minutes with flow, under the conditions of 24 DEG C, to oil
2g10 weight % ammonium persulfate aqueous solution is added in bag aqueous emulsion, then divides 4 addition 2g10 weight % sodium hydrogensulfite water
Solution, the amount added every time is 0.5g, under the conditions of 35 DEG C, reacts 6 hours, is then added at 35 DEG C into mixture poly-
Oxygen ethene sorbitan fatty acid ester（Tween-85）15g, with 80rpm mixing speeds, stirs 25min, is then filtered with 80 mesh
Cloth filtering obtains pressure break friction reducer P4.
Embodiment 5
The present embodiment is used to illustrate pressure break friction reducer of the present invention and preparation method thereof.
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, replace poly- 2- third with sodium polymethacrylate
Acrylamide base -2- methyl propane sulfonic acid sodium, is made pressure break friction reducer P5.
Embodiment 6
The present embodiment is used to illustrate pressure break friction reducer of the present invention and preparation method thereof.
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, by methylacryoyloxyethyl trimethyl chlorine
Change ammonium（80% aqueous solution）, poly- 2- acrylamide-2-methylpro panesulfonic acids sodium（Molecular weight 150,000）, disodium ethylene diamine tetraacetate, first
Sour sodium, water, Span-80, Tween-80, white oil, 10 weight % 2,2 '-azo [2- (2- imidazoline -2- propane)-two hydrochloric acid
Salt] aqueous solution and polyoxyethylene sorbitan fatty acid ester consumption replace with respectively 70g, 7g, 1g, 0.5g, 180g, 8g,
8g, 190g, 1g and 15g, are made pressure break friction reducer P6.
Comparative example 1
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, not addition polymerization 2- acrylamidos -2- methyl
Propanesulfonate, is made pressure break friction reducer N1.
Comparative example 2
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, replace poly- 2- third with kayexalate
Acrylamide base -2- methyl propane sulfonic acid sodium, is made pressure break friction reducer N2.
Comparative example 3
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, replace poly- 2- acrylamides with polyglutamic acid
Base -2- methyl propane sulfonic acid sodium, is made pressure break friction reducer N3.
Test case
Test case 1
This test case is used for the resistance-reducing performance of mini-frac friction reducer.
Friction-reducing agent of fracturing fluid P1-P6 and N1-N3 resistance-reducing performance test determine device by friction-reducing agent of fracturing fluid（Model sea
Pacify oil scientific research Instrument Ltd. fracturing fluid drop friction test instrument）Determine, condition is as follows：Under normal temperature, friction-reducing agent of fracturing fluid is molten
The aqueous solution that solution is made into 1 weight % in clear water is added in dissolving tank, and solution is conveyed by pump to flow out, and enters through spinner flowmeter
Test section.Spinner flowmeter metered flow is used, uninterrupted determines pressure drop of the solution by test section by Frequency Converter Control.Survey
A diameter of 0.635 centimetre of pipe is tried, test length of pipe section is 3 meters, resistance-reducing yield（DR, %）It is calculated as follows：
In formula, Δ P0The pressure drop produced when flowing through test pipeline section for clear water under certain flow, unit is Pa；Δ P is certain
Friction reducer solution flows through the pressure drop produced during test pipeline section under flow, and unit is Pa.
The friction reducer prepared in 40g embodiments 1-6 and comparative example 1-3 is taken respectively, is added to fills 40L under agitation
In the stainless steel dissolving tank of water, stirring, which was conveyed the 1 weight % friction reducers aqueous solution prepared by pump after 1 minute, flows out, through rotor
Flowmeter enters test section, determines resistance-reducing yield of the friction reducer aqueous solution under different flow.Experiment is from 10 millimeters of test pipeline sections
Tested, the aqueous solution that clear water and 1 weight % friction reducers are recorded respectively flows through the pressure drop that test pipeline section is produced, and calculates resistance-reducing yield,
Experimental result is shown in Fig. 1.
Embodiment 1-6 and comparative example 1-3 is compared as can be seen that the resistance-reducing yield of friction reducer produced by the present invention compares
The resistance-reducing yield of friction reducer made from comparative example is high.The reason for comparative example resistance-reducing yield is low be：Comparative example friction reducer N1 is single due to polymerization
The distribution of first block, molecular configuration, space structure can not rationally design control, and maximum resistance-reducing yield is only 56%, comparative example friction reducer
The template polystyrene sodium sulfonate added in N2 hampers template effect, maximum resistance-reducing yield due to the larger steric effect of phenyl ring
For 56.5%, the product resistance-reducing performance prepared do not have the template polyglutamic acid that is added in significant change, comparative example friction reducer N3 by
Amide group has weak interaction to play template effect with acrylamide in glutamic acid, and the product drop prepared is resistive
Can not there is significant change, maximum resistance-reducing yield is only 56.8%.
Embodiment 1 is compared with embodiment 5 as can be seen that anionic polymer template is poly- 2- acrylamidos -2- first
During base propanesulfonate, the resistance-reducing yield of obtained friction reducer can be further improved.
Embodiment 1 is compared with embodiment 6 as can be seen that relative to the acrylamide monomer of 100 parts by weight, institute
The consumption for stating double bond containing cationic monomer is 20-50 parts by weight；The consumption of the anionic polymer template is 1-5 weight
Part；The consumption of the chelating agent is 0.02-0.2 parts by weight；The consumption of molecular weight regulator is 0.01-0.1 parts by weight；The use of water
Measure as 100-150 parts by weight；The consumption of the organic solvent is 90-150 parts by weight；The consumption of the emulsifying agent is 8-15 weight
Part；The consumption of the initiator is 0.01-0.2 parts by weight；, can be further when the consumption of the phase inversion agent is 5-10 parts by weight
Improve the resistance-reducing yield of obtained friction reducer.
Test case 2
This test case is used for the core damage of mini-frac friction reducer.
The friction reducer prepared in 1.0g embodiments 1-6 and comparative example 1-3 is taken respectively, is added to fills 1L under agitation
In the glass beaker of water, stirring adds 0.2g ammonium persulfates after 1 minute, and core damage test, rock are used for after stirring half an hour
The test of heart nocuity is determined according to SY/T5107-2005 aqueous fracturing fluids method of evaluating performance, and measurement result is shown in Table 1.
Embodiment 1-6 and comparative example 1-3 are compared the core damage rate as can be seen that friction reducer produced by the present invention
Core damage rate than friction reducer made from comparative example is low.The reason for comparative example core damage rate is high be：Comparative example friction reducer
N1 due to the distribution of polymerized unit block, molecular configuration, space structure can not reasonable control design case, 1 weight % friction reducer N1's
The core damage rate of the aqueous solution is up to 18.7%.The template polystyrene sodium sulfonate added in comparative example friction reducer N2 is due to phenyl ring
Larger steric effect, hampers template effect, and the product core damage performance prepared is with being not added with template contrast without substantially change
Change, the core damage rate of the 1 weight % friction reducer N2 aqueous solution is up to the template added in 18.8%, comparative example friction reducer N3 and gathered
Glutamic acid due in glutamic acid amide group and acrylamide there is weak interaction to play template effect, the production prepared
Product are with being not added with template contrast without significant change, and the core damage rate of the 1 weight % friction reducer N3 aqueous solution is up to 18.6%.
Embodiment 1 is compared with embodiment 5 as can be seen that anionic polymer template is poly- 2- acrylamidos -2- first
During base propanesulfonate, the core damage rate of obtained friction reducer can be further reduced.
Embodiment 1 is compared with embodiment 6 as can be seen that relative to the acrylamide monomer of 100 parts by weight, institute
The consumption for stating double bond containing cationic monomer is 20-50 parts by weight；The consumption of the anionic polymer template is 1-5 weight
Part；The consumption of the chelating agent is 0.02-0.2 parts by weight；The consumption of molecular weight regulator is 0.01-0.1 parts by weight；The use of water
Measure as 100-150 parts by weight；The consumption of the organic solvent is 90-150 parts by weight；The consumption of the emulsifying agent is 8-15 weight
Part；The consumption of the initiator is 0.01-0.2 parts by weight；, can be further when the consumption of the phase inversion agent is 5-10 parts by weight
The core damage rate of the obtained friction reducer of reduction.
Table 1
| Sample | Basic permeability K（md） | Friction reducer injury permeability K1（md） | Injury rate（%） |
| P1 | 1.75 | 1.67 | 4.3 |
| P2 | 1.73 | 1.64 | 5.2 |
| P3 | 1.69 | 1.59 | 5.9 |
| P4 | 1.70 | 1.57 | 7.6 |
| P5 | 1.71 | 1.58 | 7.6 |
| P6 | 1.72 | 1.58 | 8.1 |
| N1 | 1.71 | 1.39 | 18.7 |
| N2 | 1.70 | 1.38 | 18.8 |
| N3 | 1.72 | 1.40 | 18.6 |
Test case 3
This test case is used for the clay swell inhibition of mini-frac friction reducer.
The friction reducer P1-P6 and N1-N3 prepared in 1.0g embodiments 1-6 and comparative example 1-3 is taken respectively, under agitation
In the glass beaker for being added separately to fill 1L water, stir 1 minute, P1-P6 the and N1-N3 friction reducers that 1 weight % is made are water-soluble
Liquid, then determines the viscous of the above-mentioned friction reducer aqueous solution according to SY-T5971-1994 water fillings with clay stabilizer method of evaluating performance
Soil expansion inhibiting rate, experimental result is shown in Table 2.
Embodiment 1-6 and comparative example 1-3 are compared as can be seen that the clay swell of friction reducer produced by the present invention presses down
Clay swell inhibiting rate of the rate processed than friction reducer made from comparative example is high.The reason for comparative example clay swell inhibiting rate is low be：
Comparative example friction reducer N1 can not rationally control design case, 1 weight % due to the distribution of polymerized unit block, molecular configuration, space structure
The friction reducer N1 clay swell inhibiting rate of the aqueous solution be only 42.6%；The template polyphenyl second added in comparative example friction reducer N2
Aenoic acid sodium hampers template effect due to the larger steric effect of phenyl ring, and the product prepared is with being not added with template contrast without bright
Aobvious change, the clay swell inhibiting rate of the 1 weight % friction reducer N2 aqueous solution is only 42.8%, is added in comparative example friction reducer N3
Template polyglutamic acid due in glutamic acid amide group and acrylamide there is weak interaction to play template effect, make
Contrasted for the product gone out with being not added with template without significant change, the clay swell inhibiting rate of the 1 weight % friction reducer N3 aqueous solution is only
For 43.1%.
Embodiment 1 is compared with embodiment 5 as can be seen that anionic polymer template is poly- 2- acrylamidos -2- first
During base propanesulfonate, the clay swell inhibiting rate of obtained friction reducer can be further improved.
Embodiment 1 is compared with embodiment 6 as can be seen that relative to the acrylamide monomer of 100 parts by weight, institute
The consumption for stating double bond containing cationic monomer is 20-50 parts by weight；The consumption of the anionic polymer template is 1-5 weight
Part；The consumption of the chelating agent is 0.02-0.2 parts by weight；The consumption of molecular weight regulator is 0.01-0.1 parts by weight；The use of water
Measure as 100-150 parts by weight；The consumption of the organic solvent is 90-150 parts by weight；The consumption of the emulsifying agent is 8-15 weight
Part；The consumption of the initiator is 0.01-0.2 parts by weight；, can be further when the consumption of the phase inversion agent is 5-10 parts by weight
Improve the clay swell inhibiting rate of obtained friction reducer.
Table 2
| Sample | Expand inhibiting rate（%） |
| P1 | 89.0 |
| P2 | 88.6 |
| P3 | 88.5 |
| P4 | 82.4 |
| P5 | 82.1 |
| P6 | 81.5 |
| N1 | 42.6 |
| N2 | 42.8 |
| N3 | 43.1 |
Friction reducer produced by the present invention quickly dissolves in water, will not form flake, meets the online mixture of slippery water pressure break
Requirement；The maximum resistance-reducing yield of the aqueous solution of the friction reducer of mass concentration 1% is 74.5-78%；And friction reducer hydrolysate without
Insoluble matter occurs, very low to stratum nocuity, and the core damage rate of the aqueous solution of the friction reducer of mass concentration 1% is 4.3-8.1%；
The clay swell inhibiting rate of the aqueous solution of the friction reducer of mass concentration 1% is 81.5-89%, has significant suppression to make to clay swell
With, thus new expansion-resisting agent need not be added again in actual use, significantly reduce the cost of slippery water.
Therefore, method of the pressure break friction reducer that prepared by the present invention by adding template polymer, have adjusted polymerized unit
The distribution of block, molecular configuration, space structure, so as to significantly improve the resistance-reducing yield of product, and with the preparation side of the present invention
The friction reducer of method synthesis has the advantages that low formation damage, clay swell inhibition and good water solubility.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (26)
1. a kind of preparation method of pressure break friction reducer, it is characterised in that this method includes：
(1) by acrylamide monomer, double bond containing cationic monomer, anionic polymer template, chelating agent, molecular-weight adjusting
Agent and water mix and adjust pH value, obtain the aqueous solution that pH value is 3-5；
(2) organic solvent is contacted with emulsifying agent, obtains oil solution；
(3) aqueous solution for obtaining step (1) is contacted with the oil solution that step (2) is obtained, and obtains water-in-oil emulsion；
(4) under an inert atmosphere, water-in-oil emulsion step (3) obtained is contacted in batches with initiator, and carries out polymerisation,
Then mixture polymerisation obtained is contacted with phase inversion agent；
Wherein, the hydrophilic lipophilic balance of the emulsifying agent is 4-6, and the molecular weight of the anionic polymer template is less than 80
Ten thousand, shown in the structural formula such as formula (I) of the anionic polymer template：
R is hydrogen or methyl；
A is O, and Z is M；
Or, A is O, and Z is
Or, A is NH, and Z is
Wherein, M is Na, K, NH4。
2. according to the method described in claim 1, wherein, the anionic polymer template be selected from Sodium Polyacrylate, polypropylene
At least one in sour potassium, sodium polymethacrylate, polymethylacrylic acid potassium and poly- 2- acrylamide-2-methylpro panesulfonic acids sodium
Kind.
3. method according to claim 2, wherein, the anionic polymer template is poly- 2- acrylamidos -2- first
Base propanesulfonate.
4. according to the method described in claim 1, wherein, it is described to contain relative to the acrylamide monomer of 100 parts by weight
The consumption of the cationic monomer of double bond is 10-100 parts by weight；The consumption of the anionic polymer template is 1-10 parts by weight；
The consumption of the chelating agent is 0.001-5 parts by weight；The consumption of molecular weight regulator is 0.001-1 parts by weight；The consumption of water is
50-200 parts by weight；The consumption of the organic solvent is 50-200 parts by weight；The consumption of the emulsifying agent is 5-20 parts by weight；Institute
The consumption for stating initiator is 0.001-2 parts by weight；The consumption of the phase inversion agent is 1-20 parts by weight.
5. method according to claim 4, wherein, it is described to contain relative to the acrylamide monomer of 100 parts by weight
The consumption of the cationic monomer of double bond is 20-50 parts by weight；The consumption of the anionic polymer template is 1-5 parts by weight；Institute
The consumption for stating chelating agent is 0.02-0.2 parts by weight；The consumption of molecular weight regulator is 0.01-0.1 parts by weight；The consumption of water is
100-150 parts by weight；The consumption of the organic solvent is 90-150 parts by weight；The consumption of the emulsifying agent is 8-15 parts by weight；
The consumption of the initiator is 0.01-0.2 parts by weight；The consumption of the phase inversion agent is 5-10 parts by weight.
6. the method according to any one in claim 1-5, wherein, the acrylamide monomer is selected from acryloyl
Amine, Methacrylamide, N, N- DMAAs, N, N- acrylamides, NIPA, N- hydroxyl first
At least one of base acrylamide and N- hydroxyethyl acrylamides.
7. method according to claim 6, wherein, the acrylamide monomer is acrylamide.
8. the method according to any one in claim 1-5, wherein, the double bond containing cationic monomer is selected from propylene
Amidopropyl benzyl ammonium chloride, dimethyl diallyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloyl
At least one of oxy-ethyl-trimethyl salmiac and methacryiamidopropyl dimethyl benzyl ammonium chloride.
9. method according to claim 8, wherein, the double bond containing cationic monomer is methylacryoyloxyethyl three
Ammonio methacrylate and/or acrylyl oxy-ethyl-trimethyl salmiac.
10. method according to claim 9, wherein, the double bond containing cationic monomer is methylacryoyloxyethyl
Trimethyl ammonium chloride.
11. the method according to any one in claim 1-5, wherein, the chelating agent is selected from ethylenediamine tetra-acetic acid two
At least one of sodium, triethylenediamine pentaacetic acid, citric acid, citrate and poly- hydroxy acrylic acid.
12. method according to claim 11, wherein, the chelating agent is disodium ethylene diamine tetraacetate and/or citric acid
Salt.
13. method according to claim 12, wherein, the citrate is selected from potassium citrate, sodium citrate, citric acid
At least one of calcium and ammonium citrate.
14. the method according to any one in claim 1-5, wherein, the molecular weight regulator is selected from sodium formate, second
At least one of sour sodium, glycerine and isopropanol.
15. method according to claim 14, wherein, the molecular weight regulator is sodium formate.
16. the method according to any one in claim 1-5, wherein, the emulsifying agent is nonionic emulsifier.
17. method according to claim 16, wherein, the emulsifying agent is selected from sorbitan oleate, Sorbitan
Alcohol monoleate APEO, APES, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether and
At least one of aliphatic amine polyoxyethylene ether.
18. the method according to any one in claim 1-5, wherein, the organic solvent be selected from toluene, dimethylbenzene,
At least one of hexane, hexamethylene, normal heptane, isoparaffin, gasoline, kerosene and white oil.
19. method according to claim 18, wherein, the organic solvent is selected from toluene, dimethylbenzene, normal heptane, isomery
At least one of alkane, gasoline, kerosene and white oil.
20. method according to claim 19, wherein, the organic solvent is isoparaffin and/or white oil.
21. method according to claim 20, wherein, the organic solvent is that boiling point is more than 60 DEG C higher than 150 DEG C, flash-point
Isoparaffin and/or white oil.
22. the method according to any one in claim 1-5, wherein, the initiator is water soluble, redox body
Series initiators and/or azo-initiator, the water-soluble redox system contain Oxidizing and Reducing Agents.
23. method according to claim 22, wherein, the mass ratio of the Oxidizing and Reducing Agents is 5：1-1：1.
24. the method according to any one in claim 1-5, wherein, the phase inversion agent is selected from polyoxyethylene sorbitan mountain
Pears alcohol fatty acid ester, NPE, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyoxy
Vinethene, heterogeneous ten alcohol polyoxyethylene ether, isomery undecyl alcohol APEO, isomerous tridecanol polyoxyethylene ether and fatty amine are poly-
At least one of oxygen vinethene.
25. method according to claim 24, wherein, the phase inversion agent is selected from polyoxyethylene sorbitan aliphatic acid
Ester, NPE, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyethenoxy ether, isomery
At least one of ten alcohol APEOs, isomery undecyl alcohol APEO and isomerous tridecanol polyoxyethylene ether.
26. pressure break friction reducer prepared by the method according to any one in claim 1-25.
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| CN111471130A (en) * | 2020-03-26 | 2020-07-31 | 北京金圣奥能源技术有限公司 | Resistance reducing agent for online mixing variable viscosity fracturing and preparation method thereof |
| CN111320724B (en) * | 2020-04-16 | 2022-11-04 | 甘肃智仑新材料科技有限公司 | Temperature-sensitive poly-N-isopropyl acrylamide grafted guar gum, preparation method thereof and application thereof in oil field |
| CN115073673B (en) * | 2021-03-12 | 2023-08-22 | 中国石油天然气股份有限公司 | Polymer and double water phase preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002355A (en) * | 2010-11-01 | 2011-04-06 | 中国石油化工股份有限公司西北油田分公司工程技术研究院 | Friction-reducing agent of fracturing fluid and preparation method thereof |
| CN102977877A (en) * | 2012-12-04 | 2013-03-20 | 西南石油大学 | Drag reducer for shale gas fracture and preparation method of drag reducer |
| CN103131404A (en) * | 2013-02-17 | 2013-06-05 | 中国石油化工股份有限公司 | Amphoteric ionic polymer water base fracturing fluid thickening agent and preparation method thereof |
| CN103146372A (en) * | 2013-02-28 | 2013-06-12 | 中国石油化工股份有限公司 | Inverse emulsion polymer thickener for fracturing fluid and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7846878B2 (en) * | 2007-07-17 | 2010-12-07 | Halliburton Energy Services, Inc. | Friction reducer performance in water containing multivalent ions |
-
2014
- 2014-04-10 CN CN201410140965.0A patent/CN104974308B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002355A (en) * | 2010-11-01 | 2011-04-06 | 中国石油化工股份有限公司西北油田分公司工程技术研究院 | Friction-reducing agent of fracturing fluid and preparation method thereof |
| CN102977877A (en) * | 2012-12-04 | 2013-03-20 | 西南石油大学 | Drag reducer for shale gas fracture and preparation method of drag reducer |
| CN103131404A (en) * | 2013-02-17 | 2013-06-05 | 中国石油化工股份有限公司 | Amphoteric ionic polymer water base fracturing fluid thickening agent and preparation method thereof |
| CN103146372A (en) * | 2013-02-28 | 2013-06-12 | 中国石油化工股份有限公司 | Inverse emulsion polymer thickener for fracturing fluid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 以PAAS为模板AM与DMC的模板共聚合反应;吴言等;《功能高分子学报》;20090315;第22卷(第01期);第7-11页 * |
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