CN106317324B - Prepare drag reducer stabilizer and shale gas pressure break drag reducer and their preparation method - Google Patents
Prepare drag reducer stabilizer and shale gas pressure break drag reducer and their preparation method Download PDFInfo
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Abstract
The present invention relates to shale gas exploitation fracturing yield increasing fields, it discloses and a kind of prepares drag reducer stabilizer and shale gas pressure break drag reducer and their preparation method, containing structural unit, the structural unit shown in formula (2) and the structural unit shown in formula (3) shown in formula (1) in the stabilizer, the viscosity average molecular weigh of the stabilizer is 100,000 to 500,000.Shale gas pressure break provided by the invention drag reducer has the advantages of drag reduction efficiency and anti-shear performance are high, and stability is good, viscosity is low, good fluidity, fast and environmentally friendly solution rate.
Description
Technical field
The present invention relates to shale gas exploitation fracturing yield increasing fields, and in particular, to it is a kind of prepare drag reducer stabilizer and
Preparation method, a kind of preparation method of shale gas pressure break drag reducer and the shale gas pressure break that is prepared by this method are used
Drag reducer.
Background technology
Shale gas resource is very abundant, very low (being generally less than 1mD) however, as the permeability of shale matrix, development technique
Difficult, more than 90% shale gas well needs that more satisfactory yield could be obtained by fracturing reform.
At present, shale gas fracture stimulation operations carry out fracture stimulation operations frequently with drag reduction water.It is in water that drag reduction hydraulic pressure, which is split,
The middle additives such as a small amount of pressure break drag reducer, cleanup additive, fungicide that add in are as the pressure break fracturing work carried out.With gel pressure
Split liquid difference, drag reduction hydraulic pressure, which is split, can be substantially reduced pressure break cost, reduce formation damage, and gel fracture can be obtained cannot be real
Existing volume fracturing, so as to improve the exploitation yield of shale gas.
Since natural polymer is in acid condition because losing resistance reducing performance during degradation, the drag reducer used at present is mainly
Some synthesising macromolecule copolymers, CN103820099A disclose a kind of acid solution drag reducer and preparation method thereof, it is by propylene
Amide, 2- acrylamide-2-methylpro panesulfonic acids and long chain cation monomer polymerize, dry, crushing preparation in aqueous solution,
In application, drag reducer dissolution time is up to 1-2h, shale gas pressure break huge discharge can not be met, the needs that big flow is prepared online.
CN103694984A discloses a kind of shale gas acid fracturing drag reducer and preparation method thereof, which passes through anti-
Prepared by phase emulsion method, injected in reversed-phase emulsion containing a large amount of organic solvent and surfactant, this pressure break with drag reducer
The pollution of underground water can be caused behind stratum, the requirement of environmental protection can not be met.
CN102977877A also discloses that a kind of shale gas pressure break drag reducer and preparation method thereof, it is in saline solution
In, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids sodium and acrylic acid are caused by free radical under the protection of dispersant
Three kinds of monomers of sodium carry out shale gas pressure break drag reducer that random copolymerization obtains and preparation method thereof, and this method is without organic molten
Agent, it is environmentally friendly, but lead to since effective content is low to need to reach 0.2% using concentration that just there is preferable resistance-reducing performance,
And 2- acrylamide-2-methylpro panesulfonic acid sodium has certain dissolubility to cause the emulsion viscosity prepared big in brine,
It is unfavorable for practical application.
Therefore, there is an urgent need for find a kind of new shale gas pressure break drag reduction that can overcome prior art defect in the art
Agent.
Invention content
The defects of the purpose of the present invention is overcoming the prior art, provides a kind of drag reduction efficiency and anti-shear performance is high, stablizes
The new shale gas pressure break drag reducer that property is good, viscosity is low, good fluidity, solution rate are fast and environmentally friendly.
The researcher of the present invention has found by experiment：In water-in-water emulsion polymerization process, stabilizer obtains polymerization
Emulsion viscosity has an important influence, and the polyacrylamide polymers in polymerization process in brine are precipitated into after particle, stabilizer
A part is adsorbed by physical action on particle, and another part is stretched in aqueous solution, so as to form one layer of water in particle surface
Change adsorption layer, by electrical charge rejection and space steric effect, micelle is protected not coalesce, make to be suspended in aqueous solution particle-stabilisedly
In.But stabilizer can be from particle surface after lotion is placed by mechanical agitation process or for a long time for the mode of this physical absorption
It is detached from, causes to coalesce between particle, viscosity is caused to rise rapidly, even resulting in product can not use.The present inventor is based on
The studies above finds and completes technical scheme of the present invention after carrying out creative research.
In a first aspect, the present invention provides a kind of knot for preparing drag reducer stabilizer, containing shown in formula (1) in the stabilizer
The structural unit shown in structural unit and formula (3) shown in structure unit, formula (2), the viscosity average molecular weigh of the stabilizer is 100,000
To 500,000,
Wherein, in formula (1), R1Alkyl for H or C1-C4；M is the integer of 1-4；
In formula (2), R2Alkyl for H or C1-C4；
In formula (3), R3、R4And R5It is each independently the alkyl of H or C1-C4；N is the integer of 1-3；M for Li, Na, K,
Rb or Cs.
Second aspect, the present invention provide a kind of preparation method for preparing drag reducer stabilizer, and this method includes：In alkene
Solution polymerization under the conditions of, in the presence of initiator, monomer mixture is made to carry out polymerisation in water, the monomer mixes
Close object and contain monomer A, monomer B and monomer C, the monomer A is the monomer with structure shown in formula (4), the monomer B be with
The monomer of structure shown in formula (5), the monomer C are the monomer with structure shown in formula (6), and the condition of the polymerisation causes
The viscosity average molecular weigh of gained stabilizer is 100,000-50 ten thousand after polymerisation,
Wherein, R1-R5, M, n and m as the present invention it is aforementioned defined in.
The third aspect, the present invention provide a kind of preparation method of shale gas pressure break drag reducer, and this method includes：In alkene
Solution polymerization under the conditions of, in the presence of initiator, by polymerized monomer, stabilizer, inorganic salts and chelating agent in water into
Row hybrid reaction, wherein, the stabilizer is stabilizer of the present invention.
Fourth aspect, the present invention is provided to be prepared by the preparation method of the above-mentioned shale gas pressure break drag reducer of the present invention
Shale gas pressure break drag reducer.
The method of the present invention passes through grafting and physical absorption by introducing a small amount of double-strand unit in stabilizers, by stabilizer
Two ways is anchored on polymer particle, prevents stabilizer from being detached from from particle surface, so as to obtain resting period length, viscosity
Low environment-friendly type shale gas pressure break drag reducer.
Pressure break drag reducer provided by the invention has fabulous stability, splendid mobility and good environmental-protecting performance；
It at room temperature can be with storage-stable 12 months or more；Drag-reduction effect is apparent, and the drag reducing efficiency of 0.1% dreg reducer solution may be up to
75%；Pressure break reduces that production cost is cheap, raw material is easy to get, instant effect is good with drag reducer by reaction medium of water.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, the alkyl of the C1-C4 include methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
New butyl.
In the present invention, the integer of the 1-4 includes 1,2,3 and 4.
In the present invention, the integer of the 1-3 includes 1,2 and 3.
In a first aspect, drag reducer stabilizer is prepared the present invention provides a kind of, containing shown in formula (1) in the stabilizer
The structural unit shown in structural unit and formula (3) shown in structural unit, formula (2), the viscosity average molecular weigh of the stabilizer is 10
Ten thousand to 500,000,
Wherein, in formula (1), R1Alkyl for H or C1-C4；M is the integer of 1-4；
In formula (2), R2Alkyl for H or C1-C4；
In formula (3), R3、R4And R5It is each independently the alkyl of H or C1-C4；N is the integer of 1-3；M for Li, Na, K,
Rb or Cs.
Under preferable case, in the present invention, in formula (1), R1For H, methyl, ethyl, n-propyl or isopropyl；M is 1,2
Or 3；
In formula (2), R2For H, methyl, ethyl, n-propyl or isopropyl；
In formula (3), R3、R4And R5It is each independently H, methyl, ethyl, n-propyl or isopropyl；N is 1 or 2；M is
Li, Na or K.
In the case of more preferably, in the present invention, in formula (1), R1For H, methyl or ethyl；M is 1 or 2；
In formula (2), R2For H, methyl or ethyl；
In formula (3), R3、R4And R5It is each independently H, methyl or ethyl；N is 1 or 2；M is Na or K.
In the case of particularly preferably, in the present invention, in formula (1), R1For H；M is 1；
In formula (2), R2For H；
In formula (3), R3、R4And R5It is methyl；N is 1；M is Na.
Second aspect, the present invention provides a kind of preparation method for preparing drag reducer stabilizer, this method includes：In alkene
Under the conditions of the solution polymerization of hydrocarbon, in the presence of initiator, make containing monomer A, monomer B and monomer C/monomer mixture in water
Middle to carry out the first reaction, the monomer A is the monomer with structure shown in formula (4), and the monomer B is with knot formula (5) Suo Shi
The monomer of structure, the monomer C are the monomer with structure shown in formula (6), and then being added in into reaction system has shown in formula (7)
The monomer D of structure carries out the second reaction, and the condition of the polymerisation causes the viscous equal molecule of gained stabilizer after polymerisation
It is 100,000-50 ten thousand to measure,
Wherein, R1-R5, M, n and m as the present invention it is aforementioned defined in.
In the present invention, it is preferred to the polymerisation is reacted for random copolymerization.
In the present invention, it should be strongly noted that the correlation of the stabilizer involved in the preparation method of the stabilizer
Definition is identical with the aforementioned definitions of the present invention, and in order to avoid repeating, details are not described herein by the present invention.
In the present invention, it is preferred to the dosage weight ratio of the monomer A, monomer B and monomer C are 1：0.1-30：5-40；It is more excellent
It is selected as 1：0.5-25：10-30.
In the present invention, it is preferred to the dosage molar ratio of the monomer A and monomer D is 1：0.8-1.5.
In the present invention, it is preferred to the initiator is selected from azo initiator and redox initiator；The azo causes
Agent is selected from azodiisobutyronitrile, 4,4 '-azo bis- (4- cyanopentanoic acids), 2,2 '-azo diisobutyl amidine hydrochloride and azo two
At least one of imidazolinyl propane dihydrochloride；The redox initiator includes Oxidizing and Reducing Agents, the oxygen
Agent and the molar ratio of the reducing agent are 0.1-10:1, the oxidant be selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and
At least one of hydrogen peroxide, the reducing agent are inorganic reducing agent and/or organic reducing agent, and the inorganic reducing agent is selected from
At least one of sodium hydrogensulfite, sodium sulfite, rongalite, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite, it is described it is organic also
Former agent is selected from N, N '-dimethyl ethylenediamine, N, N '-dimethyl -1,3- propane diamine, N, N, N ', N '-tetramethylethylenediamine, N, N-
At least one of dimethyl amine and 3- methylamino propylamine.
In the present invention, it is preferred to which the polymerisation carries out in the presence of auxiliary agent, the auxiliary agent is selected from chelating agent, chain extender
With it is one or more in other auxiliary agents；The chelating agent is selected from disodium ethylene diamine tetraacetate, triethylenediamine pentaacetic acid, lemon
At least one of acid, citrate and poly- hydroxy acrylic acid；The chain extender is selected from N, N '-dimethyl ethylenediamine, N, N, N ',
N '-tetramethylethylenediamine, N, N- dimethyl amines, 3- methylaminos propylamine, N, N '-dimethyl -1,3- propane diamine, 1- (dimethyl
Amino) at least one of -2- propylamine and diethylenetriamines；Other auxiliary agents are selected from urea, sodium formate, isopropanol and secondary
At least one of sodium phosphate.
In the present invention, it is preferred to which the polymerisation carries out in the presence of an inert gas, the polymerisation includes first
Reaction and the second reaction.
It is preferred that the condition of first reaction includes：Temperature is 45-60 DEG C, reaction time 3-10h, pH value 6-8.
It is preferred that the condition of second reaction includes：Temperature is 25-40 DEG C, reaction time 0.5-5h, pH value 9-12.
When needing to add in sour regulation system pH value, the acid is preferably inorganic acid, and the inorganic acid can be hydrochloric acid, sulphur
At least one of acid, sulfonic acid, nitric acid and phosphoric acid.When needing to add in alkali regulation system pH value, the alkali can be inorganic base
Or organic amine compound, it can such as be selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, methylamine, ethamine, ethanol amine and triethanolamine
At least one of, preferably sodium hydroxide.
The third aspect, the present invention provides a kind of preparation method of shale gas pressure break drag reducer, this method includes：In alkene
Under the conditions of the solution polymerization of hydrocarbon, in the presence of initiator, by polymerized monomer, stabilizer, inorganic salts and chelating agent in water
Hybrid reaction is carried out, wherein, the stabilizer is stabilizer of the present invention.
In the present invention, it should be strongly noted that involved in the preparation method of the shale gas pressure break drag reducer
Stabilizer, the related definition of initiator are identical with the aforementioned definitions of the present invention, and in order to avoid repeating, the present invention is no longer superfluous herein
It states.
It is in the present invention, described on the basis of the total weight of pressure break drag reducer being finally prepared under preferable case
The dosage of polymerized monomer is 10-35 weight %, more preferably preferably 15-25 weight %, 16-22 weight %.
It is in the present invention, described on the basis of the total weight of pressure break drag reducer being finally prepared under preferable case
The dosage of inorganic salts is 10-35 weight %, more preferably preferably 20-30 weight %, 22-24 weight %.
It is in the present invention, described on the basis of the total weight of pressure break drag reducer being finally prepared under preferable case
The dosage of stabilizer is 0.1-2 weight %, more preferably preferably 0.2-1 weight %, 0.5-0.8 weight %.
It is in the present invention, described on the basis of the total weight of pressure break drag reducer being finally prepared under preferable case
The dosage of chelating agent is 0.001-0.5 weight %, more preferably preferably 0.01-0.1 weight %, 0.04-0.06 weight %.
In the present invention, it is preferred to the polymerized monomer includes non-ionic monomer and/or anionic monomer.
In the present invention, the more preferably non-ionic monomer is acrylamide, the anionic monomer for acrylic acid and/or
Methacrylic acid.
Under preferable case, in the present invention, with the total weight of the polymerized monomer, the content of the non-ionic monomer is
70-99 weight %, preferably 85-95 weight %；The content of the anionic monomer is 1-30 weight %, and preferably 5-15 is heavy
Measure %.
According to the present invention, the inorganic salts are not particularly limited, preferably water-soluble inorganic salt, the water-soluble inorganic salt
Can be at least one of sodium salt, ammonium salt and magnesium salts；Preferably, the water-soluble inorganic salt is ammonium sulfate, sodium sulphate and sulphur
At least one of sour magnesium；It is highly preferred that the water-soluble inorganic salt is ammonium sulfate.
According to the present invention, on the basis of the total weight of pressure break drag reducer being finally prepared, the use of the initiator
It measures as 0.0001-0.05 weight %, preferably 0.001-0.01 weight %, more preferably 0.005-0.008 weight %.
According to the present invention, the chelating agent is preferably disodium ethylene diamine tetraacetate.
Under preferable case, in the present invention, the condition of the hybrid reaction includes：Reaction temperature is 25-60 DEG C, during reaction
Between be 2-8h.
In the case of more preferably, in the present invention, the condition of the hybrid reaction includes：Reaction temperature is 35-45 DEG C, instead
It is 4-6h between seasonable.
Under preferable case, in the present invention, the hybrid reaction carries out in the presence of an inert gas.
Fourth aspect, the present invention is provided to be prepared by the preparation method of the above-mentioned shale gas pressure break drag reducer of the present invention
Shale gas pressure break drag reducer.
The present invention will be described in detail by way of examples below.
According to the present invention, in following embodiment, the resistance reducing performance test condition of pressure break drag reducer is as follows：Pressure break drag reduction
The resistance reducing performance test of agent is measured by pressure break drag reducer measurement device, and condition is as follows：Under room temperature, pressure break drag reducer adds in molten
Tank is solved, after ten minutes, solution enters test section by pump conveying outflow through spinner flowmeter for stirring.It is measured and flowed with spinner flowmeter
Amount, uninterrupted measure pressure drop of the solution by test section by Frequency Converter Control.Test pipe diameter 0.635cm tests pipeline section
Length is 3m, a concentration of 0.1 weight % of the pressure break with drag reducer in deionized water, and drag reducing efficiency (DR) is calculated as follows：
Wherein, Δ P0For deionized water pressure drop, unit Pa；Δ P for pressure break dreg reducer solution with water-soluble liquid phase
Pressure drop under same Reynolds constant, unit Pa.
Acrylamide used in the present invention, chemistry is pure, purchased from Shandong Polymer Bio-Chemicals Co., Ltd.；Hydrogen-oxygen
Change sodium, analysis is pure, purchased from Sinopharm Chemical Reagent Co., Ltd.；Used ammonium sulfate, chemistry is pure, recovers essence purchased from Tianjin
Thin chemical institute；Used two isobutyl imidazoline hydrochloride of azo, 2,2 '-azo diisobutyl amidine hydrochloride and azo
Double methylpent hydrochlorates are purchased from aldrich.
Preparation example 1
This preparation example is used to prepare stabilizer of the present invention.
In the 1.5L polymeric kettles equipped with thermometer, stirring rod and condenser pipe, acrylic acid 10g, 20g acrylamide is added in,
2- acrylamide-2-methylpro panesulfonic acid sodium 170g and deionized water 800g, are warming up to 45 DEG C, after being completely dissolved, logical nitrogen removes
Oxygen, add in two isobutyl imidazoline hydrochloride 0.2g of azo, after being stirred to react 6 hours stop reaction, after being then cooled to 30 DEG C
Add in 0.25g allylamines in polymeric kettle, drying after the reaction was continued 2h crushes, and obtains the stabilizer that viscosity average molecular weigh is 30.2 ten thousand
W。
IR spectroscopic assays are carried out to the stabilizer, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to acyl respectively
The amide Ⅰ absorption peak (C=O stretching vibrations) and amide II of amido are with absorption peak (N-H bending vibrations)；In 1430cm-1Place goes out
The stretching vibration absworption peak of existing C-N；1356 and 1401cm-1There is typical methyl symmetric curvature vibration absorption peak；2923cm-1、
2852cm-1Place's appearance is respectively belonging to-CH2-、-CH3C-H stretching vibrations；1467cm-1Appearance belongs to-CH2-、-CH3C-
H bending vibrations；845cm-1The absorption peak at place belongs to C=C stretching vibration peaks.It can be determined by the characteristic peak in above-mentioned IR spectrum
Obtained copolymer molecule is the stabilizer with formula：
Wherein, x, y and z only represent the type and number of structural unit, and do not indicate that the connection mode of structural unit.x、
The concrete numerical value of y and z is determined by inventory.
Embodiment 1
The present embodiment is used for the preparation method for illustrating shale gas pressure break drag reducer of the present invention and prepares the present invention
The shale gas pressure break drag reducer.
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Add in deionized water 583.5g, ammonium sulfate 230g, acrylamide 162g, acrylic acid 18g, stabilizer W 6g, ethylenediamine tetra-acetic acid
Disodium 0.5g, stirring make solid be warming up to 40 DEG C after being completely dissolved；Logical nitrogen is after 30 minutes；Add in 2,2 '-azo diisobutyl
Amidine hydrochloride 0.06g continues logical nitrogen, is stirred to react 5h, obtains the milky that apparent viscosity is 350mPa.s after reaction
Dispersion liquid, at room temperature can be with storage-stable 24 months or more.
Comparative example 1
With embodiment 1 prepare pressure break drag reducer method it is identical, the difference lies in the stabilizations in the preparation method
Polyethylene glycol oxide is selected in agent；As a result the milky viscous fluid that apparent viscosity is 1450mPa.s is obtained, viscosity rises to after a week
5600mPa.s, lotion can not flow.
Embodiment 2
The present embodiment is used for the preparation method for illustrating shale gas pressure break drag reducer of the present invention and prepares the present invention
The shale gas pressure break drag reducer.
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Add in deionized water 591.5g, ammonium sulfate 220g, acrylamide 153g, acrylic acid 27g, stabilizer W 8g, ethylenediamine tetra-acetic acid
Disodium 0.6g, stirring make solid be warming up to 35 DEG C after being completely dissolved；Logical nitrogen is after 30 minutes；Add in 2,2 '-azo diisobutyl
Amidine hydrochloride 0.04g continues logical nitrogen, is stirred to react 4 hours, obtains the breast that apparent viscosity is 375mPa.s after reaction
White dispersion liquid, at room temperature can be with storage-stable 24 months or more.
Embodiment 3
The present embodiment is used for the preparation method for illustrating shale gas pressure break drag reducer of the present invention and prepares the present invention
The shale gas pressure break drag reducer.
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Add in deionized water 379.5g, ammonium sulfate 240g, acrylamide 171g, acrylic acid 9g, stabilizer W 5g, ethylenediamine tetra-acetic acid two
Sodium 0.4g, stirring make solid be warming up to 45 DEG C after being completely dissolved；Logical nitrogen is after 30 minutes；Add in 2,2 '-azo diisobutyl amidine
Hydrochloride 0.06g continues logical nitrogen, is stirred to react 6 hours, and it is the milky white of 420mPa.s to obtain apparent viscosity after reaction
Color dispersion liquid, at room temperature can be with storage-stable 24 months or more.
Embodiment 4
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Add in deionized water 583.5g, ammonium sulfate 200g, acrylamide 162g, acrylic acid 18g, stabilizer W 6g, ethylenediamine tetra-acetic acid
Disodium 0.5g, stirring make solid be warming up to 40 DEG C after being completely dissolved；Logical nitrogen is after 30 minutes；Add in 2,2 '-azo diisobutyl
Amidine hydrochloride 0.06g continues logical nitrogen, is stirred to react 5h, obtains the milky that apparent viscosity is 501mPa.s after reaction
Dispersion liquid, at room temperature can be with storage-stable 24 months or more.
Embodiment 5
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Add in deionized water 591.5g, ammonium sulfate 320g, acrylamide 153g, acrylic acid 27g, stabilizer W 8g, ethylenediamine tetra-acetic acid
Disodium 0.6g, stirring make solid be warming up to 35 DEG C after being completely dissolved；Logical nitrogen is after 30 minutes；Add in 2,2 '-azo diisobutyl
Amidine hydrochloride 0.04g continues logical nitrogen, is stirred to react 4 hours, obtains the breast that apparent viscosity is 615mPa.s after reaction
White dispersion liquid, at room temperature can be with storage-stable 24 months or more.
EXPERIMENTAL EXAMPLE
This EXPERIMENTAL EXAMPLE is illustrating the pressure break drag reducer room temperature being prepared in embodiment 1-5 and comparative example 1
It is lower to place 1 day, 7 days and the drag-reduction effect after 12 months in deionized water.A concentration of 0.1 weight % of drag reducer.
The drag reducing efficiency (DR%) of pressure break drag reducer being prepared in testing example 1-5 and comparative example 1 respectively, knot
Fruit is as shown in table 1.
Table 1
It was found from the data in table 1：In embodiment 1-5, the drag reduction agent emulsion prepared stand 1 day, 7 days, even
After 12 months, it is kept approximately constant in pressure break prepared by the present invention with the drag reducing efficiency of drag reducer in aqueous solution, after 12 months
Drag reducing efficiency remains to reach more than 64.1%.And the drag reducer synthesized in comparative example has obvious resistance reducing performance when starting, but
After standing 7 days, since emulsion viscosity is raised to 5600mPa.s, stirring only a small amount of product dissolving in 10 minutes in dissolution kettle is added in, is subtracted
Resistance rate is only 8.8%, it is clear that can not meet pressing crack construction online with liquid requirement, after standing 12 months, comparative example is whole into one
Body blob of viscose can not dissolve, in water no longer with resistance reducing performance.This has absolutely proved the present invention by being improved to stabilizer
The stability of the pressure break obtained afterwards drag reducer is significantly improved, thus when substantially extending the use of pressure break drag reducer
Between.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
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 also be regarded as the disclosure of the present invention.
Claims (16)
1. a kind of prepare drag reducer stabilizer, the structural unit shown in formula (1), the knot shown in formula (2) are contained in the stabilizer
Structural unit shown in structure unit and formula (3), the viscosity average molecular weigh of the stabilizer is 100,000 to 500,000,
Wherein, in formula (1), R1Alkyl for H or C1-C4；M is the integer of 1-4；
In formula (2), R2Alkyl for H or C1-C4；
In formula (3), R3、R4And R5It is each independently the alkyl of H or C1-C4；N is the integer of 1-3；M for Li, Na, K, Rb or
Cs。
2. stabilizer according to claim 1, wherein,
In formula (1), R1For H；M is 1；
In formula (2), R2For H；
In formula (3), R3、R4And R5It is methyl；N is 1；M is Na.
3. a kind of preparation method for preparing drag reducer stabilizer, wherein, this method includes：In the solution polymerization item of alkene
Under part, in the presence of initiator, make to carry out the first reaction in water containing monomer A, monomer B and monomer C/monomer mixture, it is described
Monomer A is the monomer with structure shown in formula (4), and the monomer B is the monomer with structure shown in formula (5), and the monomer C is
Then monomer with structure shown in formula (6) adds in the monomer D with structure shown in formula (7) into reaction system and carries out second
Reaction, the condition of the polymerisation so that the viscosity average molecular weigh of gained stabilizer after polymerisation is 100,000-50 ten thousand,
Wherein, R1-R5, M, n and m be as defined in above-mentioned claims 1 or 2.
4. preparation method according to claim 3, wherein, the dosage weight ratio of the monomer A, monomer B and monomer C are 1：
0.1-30：5-40.
5. preparation method according to claim 3 or 4, wherein, the condition of first reaction includes：Reaction temperature is
45-60 DEG C, reaction time 3-10h.
6. preparation method according to claim 5, wherein, the condition of second reaction includes：Reaction temperature is 25-40
DEG C, reaction time 0.5-5h.
7. a kind of preparation method of shale gas pressure break drag reducer, this method include：Under the conditions of the solution polymerization of alkene,
In the presence of initiator, polymerized monomer, stabilizer, inorganic salts and chelating agent are subjected to hybrid reaction in water, wherein, it is described steady
Agent is determined for the stabilizer described in claims 1 or 2.
8. according to the method described in claim 7, wherein, the polymerized monomer includes non-ionic monomer and/or anionic monomer.
9. according to the method described in claim 8, wherein, the non-ionic monomer is acrylamide, the anionic monomer is
Acrylic acid and/or methacrylic acid.
10. according to the method described in claim 9, wherein, with the total weight of the polymerized monomer, the non-ionic monomer
Content is 70-99 weight %；The content of the anionic monomer is 1-30 weight %.
11. according to the method described in claim 10, wherein, with the total weight of the polymerized monomer, the non-ionic monomer
Content be 85-95 weight %；The content of the anionic monomer is 5-15 weight %.
12. according to the method described in claim 7, wherein, on the basis of the total weight of pressure break drag reducer being prepared, institute
The dosage for stating polymerized monomer is 10-35 weight %；The dosage of the inorganic salts is 10-35 weight %；The dosage of the stabilizer
For 0.1-2 weight %.
13. the method according to claim 11, wherein, on the basis of the total weight of pressure break drag reducer being prepared,
The dosage of the polymerized monomer is 15-25 weight %；The dosage of the inorganic salts is 20-30 weight %；The use of the stabilizer
It measures as 0.2-1 weight %.
14. the method according to claim 11, wherein, on the basis of the total weight of pressure break drag reducer being prepared,
The dosage of the polymerized monomer is 16-22 weight %；The dosage of the inorganic salts is 22-24 weight %；The use of the stabilizer
It measures as 0.5-0.8 weight %.
15. the method according to any one in claim 7, wherein, the condition of the hybrid reaction includes：Reaction temperature
It is 25-60 DEG C, reaction time 2-8h.
16. the shale gas pressure break drag reducer that the method in claim 7-15 described in any one is prepared.
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| CN114736504B (en) * | 2022-04-18 | 2024-05-24 | 西北工业大学 | Method for dissolving high polymer drag reduction powder |
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| US9611416B2 (en) * | 2010-10-25 | 2017-04-04 | Isp Investments Llc | Salt-tolerant, thermally-stable rheology modifiers |
| CN102977877B (en) * | 2012-12-04 | 2014-08-06 | 西南石油大学 | Drag reducer for shale gas fracture and preparation method of drag reducer |
| CN104610489B (en) * | 2013-11-01 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of pressure break friction reducer and preparation method thereof |
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