CN105384868B - Preparation method and pressure break drag reducer of the pressure break with drag reducing agent composition and pressure break with drag reducer - Google Patents
Preparation method and pressure break drag reducer of the pressure break with drag reducing agent composition and pressure break with drag reducer Download PDFInfo
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Abstract
The invention discloses a kind of pressure break drag reducing agent composition, in said composition containing acrylamide, formula (I) shown in structures alone and the methyl propane sulfonic acid of 2 acrylamido 2 or its salt, wherein, in formula (I), R1And R2It is identical or different, it is each independently H or C1 C3 alkyl；N is 4 24 integer.The invention also discloses a kind of method for preparing pressure break drag reducer with drag reducing agent composition using pressure break disclosed by the invention, and the pressure break drag reducer being prepared by this method.Pressure break drag reducer disclosed by the invention has the advantages of resistant to shearing, salt tolerant and function admirable.
Description
Technical field
The present invention relates to oil and gas exploitation field, in particular it relates to a kind of pressure break drag reducing agent composition, a kind of pressure
Split the preparation method and pressure break drag reducer with drag reducer.
Background technology
The reservoir of shale gas has the characteristics of low porosity and low-permeability, and exploitation difficulty is big, at present mainly using smooth
Water fracturing technology is exploited, and after fracturing fluid is pressurized by high-pressure pump injection device, stratum is pumped at a high speed by tubing string, high
Fluid turbulent flow phenomenon during Bottomhole pressure is serious under pressure high-speed condition, there is larger friction resistance between fracturing fluid and tube wall
Power, the frictional resistance of fluid limit the flowing of fluid in the duct, cause the reduction of pipeline throughput rate and energy loss increase.Cause
This using the method for adding drag reducer in a fluid, it is necessary to reduce the influence of frictional resistance, so as to improve efficiency of construction.
Since since the U.S., Mitchell energy companies apply slippery water in the pressure break of shale gas first, smooth hydraulic pressure
Split liquid system north America region obtain significant economic benefit and instead of traditional gelatinous fracturing fluid and as most
Welcome fracturing fluid.Slippery water fracturing fluid is because viscosity is low, and prop-carrying capacity is weak, pressure break radius is small, shale gas slippery water pressure break
The big liquid measure of generally use (individual well fluid volume 15000m3Left and right), big flow (construction flow 10m3/ more than min) constructed.According to
By big liquid measure to produce more complicated fracture network, the flow conductivity of reservoir is improved；Turbulent flow is produced by big flow to carry branch
Support agent.But liquid shear speed is larger under the conditions of big flow, the drag reducer of high molecular polymer, which is sheared rear molecular weight, to be reduced, and is subtracted
Hydraulic performance decline is hindered, causes pressure change in fracturing process larger.
CN102977877A discloses a kind of shale gas pressure break drag reducer and preparation method thereof, and it discloses water-soluble in salt
In liquid, under the protection of dispersant, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids sodium and third are triggered by free radical
Three kinds of monomers of olefin(e) acid sodium carry out the shale gas pressure break drag reducer that random copolymerization obtains, and this method needs to first pass through aqueous solution polymerization
Reaction prepares stabilizer, then prepares drag reducer by dispersion polymerization, complex manufacturing, prepares total reaction time in 20h
More than, it is unfavorable for industrialized production, while the drag reducer effective content is low, chemical feeding quantity is larger when in use.
CN103333672A discloses a kind of PAMC salt tolerant drag reducer of low molecule amount, and it is specific open
It is polymerize in aqueous by acrylamide, alkyl based quaternary ammonium salt to obtain low molecule amount drag reducer, this method
The drag reducer of preparation is pulvis, it is impossible to be used in the extensive shale gas fracturing fluid construction using the construction technology of continuous mixture.
Therefore, need badly at present and find a kind of preparation method simplicity, be suitable for resistant to shearing, salt tolerant and the property of shale gas pressure break
The excellent drag reducer of energy.
The content of the invention
The defects of purpose of the present invention is present in prior art and deficiency, there is provided a kind of to increase in shale gas reservoir pressure break
The drag reducer applied in production.The pressure break drag reducer being prepared by the method for the present invention has resistant to shearing, salt tolerant and performance
The advantages of excellent, and it is provided by the invention prepare pressure break drag reducer method it is simple and cost is low.
To achieve these goals, on the one hand, the present invention provides a kind of pressure break drag reducing agent composition, contains in said composition
There are acrylamide, structures alone and 2- acrylamide-2-methylpro panesulfonic acids or its salt shown in formula (I),
Formula (I),
Wherein, in formula (I), R1And R2It is identical or different, it is each independently H or C1-C3 alkyl；N is 4-24's
Integer.
On the other hand, the present invention provides a kind of preparation method of pressure break drag reducer, and this method includes：It will contain organic molten
The oil solution of agent and emulsifying agent carries out first with drag reducing agent composition with pressure break and contacted, and obtains mixture；Then in polymerisation
Under the conditions of, under an inert atmosphere, the mixture is carried out second with initiator and contacted, wherein, contain third in the composition
Structures alone and 2- acrylamide-2-methylpro panesulfonic acids or its salt shown in acrylamide, formula (I),
Formula (I),
Wherein, in formula (I), R1And R2It is identical or different, it is each independently H or C1-C3 alkyl；N is 4-24's
Integer.
The third aspect, the present invention provide the pressure break drag reducer that a kind of above method by the present invention is prepared.
For the present invention by introducing the hydrophobic monomer units shown in a small amount of formula (I) in drag reducer strand, utilization is hydrophobic
The structural stability of Interaction enhanced drag reducer strand, improve its resistant to shearing ability and drag reduction efficiency；In addition, in drag reduction
2- acrylamide-2-methylpro panesulfonic acids or its salt are introduced in agent molecule chain as anti-salt type monomeric unit, improves its salt resistance
Ability.
Meanwhile the preparation method of pressure break drag reducer provided by the invention, it uses inverse emulsion polymerization method, effectively contained
Amount is high, and the drag reducer of gained can just reach good drag-reduction effect under conditions of low dose, while the drag reducer is emulsion
Product, product dissolve soon in water, will not form " flake ", disclosure satisfy that the extensive shale gas of the construction technology of continuous mixture
Fracturing fluid is constructed.
Compared with present technology, effective effect that technical scheme can be reached is as follows：
1st, pressure break provided by the invention is product emulsion with drag reducer, and effective content is high, and obtained drag reducer is in low dose
Under conditions of can just reach good drag-reduction effect.Such as：The 0.05 mass % drag reduction aqueous solution, its drag reducing efficiency just can reach
73.5% or so.
2nd, dissolved by test, pressure break drag reducing agent product provided by the invention in water soon, " flake ", example will not be formed
The apparent viscosity of the aqueous solution can reach more than the 90% of stable viscosity such as in 3min.Therefore carrying out matching somebody with somebody liquid using continuous processing
During the shale gas massive hydraulic fracture of construction, drag reducing agent product is pumped directly into manifold by the chemical feeding quantity of design, can drop significantly
Low workload of the construction with liquid, significantly improves efficiency of construction.
3rd, drag reducer provided by the invention is in drag reducer strand by introducing a small amount of hydrophobic monomer units, using dredging
The structural stability of the strand of water Interaction enhanced drag reducer, improve its resistant to shearing ability and drag reduction efficiency；In high pump
There is good molecular structure stabilized under the conditions of beam speed (6-15m/s)；Introduced in addition in the drag reducer strand of the present invention
2- acrylamide-2-methylpro panesulfonic acids or its salt improve its saline-alkaline tolerance, such as 2 as anti-salt type monomeric unit
Good resistance reducing performance is still shown in the weight % KCl aqueous solution.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is 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.
In the present invention, described " first ", " second " do not represent sequencing, the present invention use which express only be for
Distinguish, those skilled in the art should not be construed as limitation of the invention.
On the one hand, the invention provides a kind of pressure break drag reducing agent composition, acrylamide, formula are contained in said composition
(I) structures alone and 2- acrylamide-2-methylpro panesulfonic acids or its salt shown in,
Formula (I),
Wherein, in formula (I), R1And R2It is identical or different, it is each independently H or C1-C3 alkyl；N is 4-24's
Integer.
In the present invention, the alkyl of the C1-C3 can include any one in methyl, ethyl, n-propyl and isopropyl
Kind.
In the present invention, the integer of the 4-24 can include 4,24 and from 4 to 24 between arbitrary integer, and this hair
It is bright it should be strongly noted that 4,24 and from 4 to 24 between arbitrary integer can realize the purpose of the present invention, this
In the protection domain of the technical scheme of invention.
In the present invention, the 2- acrylamide-2-methylpro panesulfonic acids or its salt preferably include 2- acrylamidos -2-
At least one in methyl propane sulfonic acid, 2- acrylamide-2-methylpro panesulfonic acids sodium and 2- acrylamide-2-methylpro panesulfonic acid potassium
Kind.
Under preferable case, in composition of the present invention, in formula (I), R1And R2It is identical or different, can be respective
It independently is H or methyl；N can be between 6,22 and 6-22 arbitrary integer.
In the case of more preferably, in composition of the present invention, in formula (I), R1For H or methyl；R2For H；N can be with
For the arbitrary integer between 10,16 and 10-16.
In the case of particularly preferably, in composition of the present invention, in formula (I), R1For H；R2For H；N can be 10,
Arbitrary integer between 16 and 10-16.
Specifically, the structures alone shown in the formula (I) can be dodecyl acrylate, Process Conditions of Cetane Acrylate, acrylic acid
At least one of octadecyl ester.
Under preferable case, in composition of the present invention, relative to the acrylamide of 100 parts by weight, the formula (I)
The dosage of shown structures alone is 0.1-10 parts by weight, preferably 0.5-5 parts by weight, more preferably 0.5-2 parts by weight.
Under preferable case, in composition of the present invention, relative to the acrylamide of 100 parts by weight, the 2- third
The dosage of acrylamide base -2- methyl propane sulfonic acids or its salt is 10-100 parts by weight, preferably 20-50 parts by weight.
In composition of the present invention, chelating agent, molecular weight regulator and water can also be contained.
Preferably, in composition of the present invention, relative to the acrylamide of 100 parts by weight, the chelating agent
Dosage can be 0.001-5 parts by weight, preferably 0.02-0.1 parts by weight.
Preferably, in composition of the present invention, relative to the acrylamide of 100 parts by weight, the molecular weight is adjusted
The dosage for saving agent is 0.001-1 parts by weight, preferably 0.01-0.05 parts by weight.
Preferably, in composition of the present invention, relative to the acrylamide of 100 parts by weight, the dosage of the water
For 50-200 parts by weight, preferably 100-150 parts by weight.
In composition of the present invention, any one chelating agent that the chelating agent can be known in the art, but
Be in order that drag reducer of the invention dissolution velocity faster, drag reducing efficiency is higher, shear resistant is higher and salt tolerance is more preferable, excellent
The chelating agent is selected to be selected from disodium ethylene diamine tetraacetate, triethylenediamine pentaacetic acid, citric acid, citrate and poly- hydroxyl third
At least one of olefin(e) acid；More preferably disodium ethylene diamine tetraacetate and/or citrate.In the present invention, the citric acid
Salt preferably is selected from least one of potassium citrate, sodium citrate, calcium citrate and ammonium citrate.
In composition of the present invention, to the species of the molecular weight regulator, there is no particular limitation, in order that
Drag reducer drag reducing efficiency of the invention and shear resistant it is higher, preferably the molecular weight regulator of the invention be selected from sodium formate,
At least one of sodium acetate, glycerine and isopropanol；More preferably sodium formate.
In composition of the present invention, the water can be the conventional experimental water in this area, such as can be to steam
Distilled water and/or deionized water.
On the other hand, the present invention provides a kind of preparation method of pressure break drag reducer, and this method includes：It will contain organic molten
The oil solution of agent and emulsifying agent carries out first with drag reducing agent composition with pressure break and contacted, and obtains mixture；Then in polymerisation
Under the conditions of, under an inert atmosphere, the mixture is carried out second with initiator and contacted, wherein, contain third in the composition
Structures alone and 2- acrylamide-2-methylpro panesulfonic acids or its salt shown in acrylamide, formula (I),
Formula (I),
Wherein, in formula (I), R1And R2It is identical or different, it is each independently H or C1-C3 alkyl；N is 4-24's
Integer.
In the preparation method of the pressure break drag reducer of the present invention, the pressure break drag reducing agent composition can be the present invention
Any one above-mentioned composition, the present invention will not be repeated here.
Under preferable case, in the preparation method of the pressure break drag reducer of the present invention, it can also contain in the composition
Chelating agent, molecular weight regulator and water.
According to a kind of specific preferred embodiment of the present invention, the preparation method of the pressure break drag reducer can wrap
Include：
(1) by the structures alone shown in acrylamide, formula (I) and 2- acrylamide-2-methylpro panesulfonic acids or its salt, chela
Mixture, molecular weight regulator and water mixing, obtain the aqueous solution；
(2) organic solvent is mixed with emulsifying agent, obtains oil solution；
(3) aqueous solution that step (1) obtains is carried out into first with the oil solution that step (2) obtains to contact, obtained described mixed
Compound；
(4) under the polymerization conditions, mixture that under an inert atmosphere, step (3) is obtained and initiator carry out the
Two contacts.
In the step (1) of the present invention, to the structures alone shown in acrylamide, formula (I) and 2- acrylamido -2- first
Base propane sulfonic acid or its salt, chelating agent, molecular weight regulator and the condition of water mixing do not require particularly, in order that obtaining of the invention
Faster, and salt tolerance is more preferable for the dissolution velocity of described drag reducer, and the condition of the present invention preferably mixing can be：In room temperature
Under be stirred；It is highly preferred that the condition of mixing includes：Under the conditions of temperature is 15-30 DEG C, stir complete to above-mentioned various raw materials
Fully dissolved.
There is no particular limitation for condition of the present invention to the described first contact, and those skilled in the art can use conventional
Method is mixed the aqueous solution that step (1) obtains with the oil solution that step (2) obtains, and to obtain water-in-oil emulsion, is
The mixture.
In the step (1) of the present invention, to the structures alone shown in acrylamide, formula (I) and 2- acrylamido -2- first
Base propane sulfonic acid or its salt, chelating agent, molecular weight regulator and the order of water mixing are not particularly limited, as long as enabling to propylene
Structures alone and 2- acrylamide-2-methylpro panesulfonic acids or its salt, chelating agent, molecular weight regulator shown in acid amides, formula (I)
It is present in simultaneously in reaction system with water.
In the preparation method of the pressure break drag reducer of the present invention, the dosage of the organic solvent is not limited particularly
It is fixed, in order that the dissolution velocity for the drag reducer that must be prepared faster, drag reducing efficiency is higher, shear resistant is higher and salt tolerance
More preferably, relative to the acrylamide of 100 parts by weight, the dosage of preferably described organic solvent is 50-200 parts by weight, more preferably
90-150 parts by weight.
According to method of the present invention, the organic solvent can be it is well known by persons skilled in the art any one or
A variety of organic solvents, the organic solvent can be selected from toluene, dimethylbenzene, hexane, hexamethylene, normal heptane, isoparaffin, vapour
At least one of oil, kerosene and white oil；In order that obtained drag reducer dissolution velocity faster, drag reducing efficiency is higher, clay
Expand inhibition it is higher, shear resistant is higher and formation damage is lower, preferably described organic solvent be selected from toluene, dimethylbenzene,
At least one of normal heptane, isoparaffin, gasoline, kerosene and white oil；More preferably described organic solvent be isoparaffin and/or
White oil；More preferably boiling point is more than 60 DEG C of isoparaffin and/or white oil higher than 150 DEG C, flash-point.
In the preparation method of the pressure break drag reducer of the present invention, to the dosage of the emulsifying agent, there is no particular limitation,
But in order that the dissolution velocity for the drag reducer that must be prepared faster, drag reducing efficiency is higher, shear resistant is higher and salt tolerance
More preferably, relative to the acrylamide of 100 parts by weight, the dosage of preferably described emulsifying agent is 5-20 parts by weight, more preferably 8-15
Parts by weight.
In the case of more preferably, in the preparation method of the pressure break drag reducer of the present invention, in order that obtaining obtained drag reducer
Dissolution velocity faster, drag reducing efficiency is higher, shear resistant is higher and salt tolerance is more preferable, the emulsifying agent is nonionic emulsifier,
More preferably described emulsifying agent is selected from sorbitan oleate, sorbitan monooleate APEO, Sorbitan
Polyol fatty acid methyl esters (Span-80), OPEO (OP-7), benzylphenol oxygen APEO, phenethyl phenol polyoxy
At least one of vinethene and aliphatic amine polyoxyethylene ether.
Under preferable case, in order that it is water-in-oil emulsion to obtain the mixture being prepared in above-mentioned steps (3), it is preferably described
The hydrophilic lipophilic balance of emulsifying agent is 5-7.
In the case of more preferably, in order that the hydrophilic lipophilic balance for obtaining the emulsifying agent is 5-7, present invention preferably employs two
Kind or two or more emulsifying agents are used in mixed way to obtain blended emulsifier of the hydrophilic lipophilic balance as 5-7.In the present invention
In, to the dosage of various emulsifying agents that forms the blended emulsifier, there is no particular limitation, as long as enabling to resulting
The hydrophilic lipophilic balance of blended emulsifier is 5-7.
In the preparation method of the pressure break drag reducer of the present invention, the dosage of the initiator can be conventional amount used, but
Be in order that the drag reducer that must be prepared dissolution velocity faster, drag reducing efficiency is higher, shear resistant is higher and salt tolerance is more preferable,
Relative to the acrylamide of 100 parts by weight, the dosage of preferably described initiator is 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, the oxidant be selected from hydrogen peroxide,
Persulfate, potassium permanganate, bromate, benzoyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide and diisopropyl
At least one of benzene peroxide, the reducing agent are selected from bisulfites, sulphite, rongalite, sodium thiosulfate, guarantor
At least one of dangerous powder, triethylamine and tetramethylethylenediamine.Azo-initiator can be selected from 2,2 '-azo diisobutyl amidine
At least one of hydrochloride and 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride].
Under preferable case, the mixture that initiator of the present invention obtains by the way of several times with step (3) is (i.e.
Water-in-oil emulsion) contact.The present invention is not limited the number, and those skilled in the art can be selected according to conventional practice
Select.
According to method of the present invention, in step (3), the contact order of addition of the aqueous solution and the oil solution
Do not limit, the oil solution can be added in the aqueous solution, it is molten the aqueous solution can also to be added to the oil
In liquid, the present invention is not particularly limited.But in order that obtained drag reducer dissolution velocity faster, drag reducing efficiency it is higher, anti-
Shearing property is higher and salt tolerance is more preferable, it is preferable that the aqueous solution is added in the oil solution and carries out contact mixing.It is described
Oil solution is also not particularly limited with the contact hybrid mode present invention of the aqueous solution, as long as the two contact mixing can be formed
Stable water-in-oil emulsion, it is preferable that oil solution contact with the aqueous solution is blended in high speed shearing emulsification work
Carried out under, to form stable water-in-oil emulsion.In the present invention, the water-in-oil emulsion of described stabilization is referred in breast
Monomer solution (drop) is equably disperseed in organic solvent in the form of short grained in the presence of agent.
According to method of the present invention, there is provided the mode of the inert atmosphere can be the conventional various sides in this area
Method, for example, the methods of nitrogen and/or argon gas can be passed through into reaction system.
Under preferable case, in the preparation method of pressure break drag reducer of the present invention, for the condition of polymerisation
Without particular/special requirement, the conventional condition in this area can be used, for example, the condition of the polymerisation can include：Temperature is 20-
60 DEG C, the time is 2-8 hours.
The third aspect, the present invention provide the pressure break drag reducer that a kind of above method by the present invention is prepared.
The present invention will be described in detail by way of examples below.In following examples and comparative example, not special
In the case of explanation, used various reagents are all from commercially available chemically pure reagent, 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) hydrophilic lipophilic balance (HLB) for being 4.3, OP-7 is 12, and the HLB of blended emulsifier is calculated according to the following equation：
The HLB=Span-80 of blended emulsifier mass fraction × 4.3+OP-7 mass fraction × 12
Embodiment 1
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is Process Conditions of Cetane Acrylate.
Specifically, the method for the present embodiment includes：
(1) under the conditions of 15 DEG C, by acrylamide (100g), 2- acrylamide-2-methylpro panesulfonic acids sodium (35g), formula
(I) structures alone (1g), disodium ethylene diamine tetraacetate (0.05g) shown in, sodium formate (0.02g) and deionized water (125g) exist
Mixed in 1000mL beakers, stir to being completely dissolved, obtain the aqueous solution；
(2) Span-80 (9.35g) and OP-7 (2.65g) are mixed to get into blended emulsifier (to calculate and obtain the blended emulsifier
Hydrophilic lipophilic balance for 6), then by blended emulsifier and 120g white oils (boiling point boiling range is 220-255 DEG C, and flash-point is 80 DEG C)
Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
(3) aqueous solution that step (1) obtains is added in the oil solution obtained with step (2), disperseed with high speed shear
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
(4) water-in-oil emulsion and then by step (3) obtained 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 deoxygenations 30min with flow, under the conditions of 40 DEG C, Xiang Youbao
Point 3 10 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution is (common in aqueous emulsion
1.0g), the amount added every time is respectively 0.3g, 0.3g and 0.4g, and under the conditions of 40 DEG C, reaction is naturally cooling to ring after 5 hours
Blowing after the temperature of border, that is, obtain homogeneous, stable emulsion-type drag reducer P1.
Embodiment 2
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is Process Conditions of Cetane Acrylate.
(1) under the conditions of 25 DEG C, by acrylamide (100g), 2- acrylamide-2-methylpro panesulfonic acids sodium (50g), formula
(I) structures alone (0.5g), disodium ethylene diamine tetraacetate (0.1g), sodium formate (0.05g) and deionized water (150g) shown in
Mixed in 1000mL beakers, stir to being completely dissolved, obtain the aqueous solution；
(2) Span-80 (13.64g) and OP-7 (1.36g) are mixed to get into blended emulsifier (to calculate and obtain the mixing and emulsifying
5) hydrophilic lipophilic balance of agent is, then (boiling point boiling range is 240-280 DEG C, flash-point 100 by blended emulsifier and 150g white oils
DEG C) mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
(3) aqueous solution that step (1) obtains is added in the oil solution obtained with step (2), disperseed with high speed shear
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
(4) water-in-oil emulsion and then by step (3) obtained 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 deoxygenations 30min with flow, under the conditions of 45 DEG C, Xiang Youbao
Point 4 10 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution 1.0g in aqueous emulsion,
The amount added every time is 0.25g, and under the conditions of 45 DEG C, reaction is naturally cooling to blowing after environment temperature after 4 hours, that is, obtains
Homogeneous, stable emulsion-type drag reducer P2.
Embodiment 3
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is Process Conditions of Cetane Acrylate.
Specifically, the method for the present embodiment includes：
(1) under the conditions of 20 DEG C, by acrylamide (100g), 2- acrylamide-2-methylpro panesulfonic acids sodium (20g), formula
(I) structures alone (2g), disodium ethylene diamine tetraacetate (0.02g), sodium formate (0.01g) and deionized water (100g) shown in exist
Mixed in 1000mL beakers, stir to being completely dissolved, obtain the aqueous solution；
(2) Span-80 (5.2g) and OP-7 (2.8g) are mixed to get into blended emulsifier (to calculate and obtain the blended emulsifier
Hydrophilic lipophilic balance is 7), then blended emulsifier and 90g white oils (boiling point boiling range is 200-250 DEG C, and flash-point is 80 DEG C) to be existed
Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
(3) aqueous solution that step (1) obtains is added in the oil solution obtained with step (2), disperseed with high speed shear
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
(4) water-in-oil emulsion and then by step (3) obtained 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 deoxygenations 30min with flow, under the conditions of 35 DEG C, Xiang Youbao
Point 51 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution 1.0g in aqueous emulsion,
The amount added every time is 0.2g, and under the conditions of 35 DEG C, reaction is naturally cooling to blowing after environment temperature after 6 hours, that is, obtains
Homogeneous, stable emulsion-type drag reducer P3.
Embodiment 4
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is dodecyl acrylate.
Specifically, the method for the present embodiment includes：
(1) under the conditions of 20 DEG C, by acrylamide (100g), 2- acrylamide-2-methylpro panesulfonic acids sodium (45g), formula
(I) structures alone (0.9g), disodium ethylene diamine tetraacetate (0.08g) shown in, sodium formate (0.04g) and deionized water (150g)
Mixed in 1000mL beakers, stir to being completely dissolved, obtain the aqueous solution；
(2) Span-80 (9.35g) and OP-7 (2.65g) are mixed to get into blended emulsifier (to calculate and obtain the blended emulsifier
Hydrophilic lipophilic balance for 6), then by blended emulsifier and 120g white oils (boiling point boiling range is 220-255 DEG C, and flash-point is 80 DEG C)
Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
(3) aqueous solution that step (1) obtains is added in the oil solution obtained with step (2), disperseed with high speed shear
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
(4) water-in-oil emulsion and then by step (3) obtained 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 deoxygenations 30min with flow, under the conditions of 60 DEG C, Xiang Youbao
Point 3 10 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution is (common in aqueous emulsion
1.0g), the amount added every time is respectively 0.3g, 0.3g and 0.4g, and under the conditions of 60 DEG C, reaction is naturally cooling to ring after 3 hours
Blowing after the temperature of border, that is, obtain homogeneous, stable emulsion-type drag reducer P4.
Embodiment 5
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is octadecyl acrylate.
Specifically, the method for the present embodiment includes：
(1) under the conditions of 20 DEG C, by acrylamide (100g), 2- acrylamide-2-methylpro panesulfonic acids sodium (30g), formula
(I) structures alone (1.7g), disodium ethylene diamine tetraacetate (0.04g) shown in, sodium formate (0.02g) and deionized water (125g)
Mixed in 1000mL beakers, stir to being completely dissolved, obtain the aqueous solution；
(2) Span-80 (13.64g) and OP-7 (1.36g) are mixed to get into blended emulsifier (to calculate and obtain the mixing and emulsifying
5) hydrophilic lipophilic balance of agent is, then (boiling point boiling range is 240-280 DEG C, flash-point 100 by blended emulsifier and 150g white oils
DEG C) mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
(3) aqueous solution that step (1) obtains is added in the oil solution obtained with step (2), disperseed with high speed shear
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
(4) water-in-oil emulsion and then by step (3) obtained 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 deoxygenations 30min with flow, under the conditions of 20 DEG C, Xiang Youbao
Point 4 10 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution 1.0g in aqueous emulsion,
The amount added every time is 0.25g, and under the conditions of 20 DEG C, reaction is naturally cooling to blowing after environment temperature after 7 hours, that is, obtains
Homogeneous, stable emulsion-type drag reducer P5.
Embodiment 6
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, in the structures alone shown in the formula (I), R1For methyl；R2For H；N is 22.
Specifically, the method for the present embodiment includes：
(1) under the conditions of 25 DEG C, by acrylamide (100g), 2- acrylamide-2-methylpro panesulfonic acids sodium (40g), formula
(I) structures alone (0.8g), disodium ethylene diamine tetraacetate (0.04g), sodium formate (0.03g) and deionized water (140g) shown in
Mixed in 1000mL beakers, stir to being completely dissolved, obtain the aqueous solution；
(2) Span-80 (5.2g) and OP-7 (2.8g) are mixed to get into blended emulsifier (to calculate and obtain the blended emulsifier
Hydrophilic lipophilic balance is 7), then blended emulsifier and 90g white oils (boiling point boiling range is 200-250 DEG C, and flash-point is 80 DEG C) to be existed
Mixed in 1500mL beakers to being completely dissolved, obtain oil solution；
(3) aqueous solution that step (1) obtains is added in the oil solution obtained with step (2), disperseed with high speed shear
Emulsifier emulsifies 1min, the water-in-oil emulsion stablized；
(4) water-in-oil emulsion and then by step (3) obtained 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 deoxygenations 30min with flow, under the conditions of 50 DEG C, Xiang Youbao
Point 51 weight % of addition 2,2 '-azo [2- (2- imidazoline -2- propane)-dihydrochloride] aqueous solution 1.0g in aqueous emulsion,
The amount added every time is 0.2g, and under the conditions of 50 DEG C, reaction is naturally cooling to blowing after environment temperature after 6 hours, that is, obtains
Homogeneous, stable emulsion-type drag reducer P6.
Embodiment 7
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is Process Conditions of Cetane Acrylate.
Specifically, the present embodiment is carried out using method same as Example 1, except that：
In the present embodiment, the dosage of the structures alone shown in formula (I) is 3g.Remaining with the method phase described in embodiment 1
Together.Obtain homogeneous, stable emulsion-type drag reducer P7.
Embodiment 8
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is Process Conditions of Cetane Acrylate.
Specifically, the present embodiment is carried out using method same as Example 1, except that：
In the present embodiment, the dosage of the structures alone shown in formula (I) is 7g.Remaining with the method phase described in embodiment 1
Together.Obtain homogeneous, stable emulsion-type drag reducer P8.
Embodiment 9
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, the structures alone shown in the formula (I) is Process Conditions of Cetane Acrylate.
Specifically, the present embodiment is carried out using method same as Example 8, except that：
In the present embodiment, the dosage of the structures alone shown in formula (I) is 10g.Remaining with the method phase described in embodiment 8
Together.Obtain homogeneous, stable emulsion-type drag reducer P9.
Embodiment 10
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, in the structures alone shown in the formula (I), R1For methyl；R2For methyl；N is 4.
Specifically, the present embodiment is carried out using method same as Example 1.Obtain homogeneous, stable emulsion-type drag reduction
Agent P10.
Embodiment 11
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, in the structures alone shown in the formula (I), R1For H；R2For methyl；N is 8.
Specifically, the present embodiment is carried out using method same as Example 1.Obtain homogeneous, stable emulsion-type drag reduction
Agent P11.
Embodiment 12
The present embodiment is used to illustrate the pressure break drag reduction for preparing the present invention with drag reducing agent composition using the pressure break of the present invention
Agent and preparation method thereof.In the present embodiment, in the structures alone shown in the formula (I), R1For H；R2For methyl；N is 24.
Specifically, the present embodiment is carried out using method same as Example 1.Obtain homogeneous, stable emulsion-type drag reduction
Agent P12.
Comparative example 1
Pressure break drag reducer is prepared according to the method for embodiment 1, unlike, in this comparative example, it is not added with shown in formula (I)
Structures alone, remaining is same as Example 1, and pressure break drag reducer N1 is made.
Comparative example 2
Pressure break drag reducer is prepared according to the method for embodiment 1, unlike, in this comparative example, it is not added with 2- acryloyls
Amido -2- methyl propane sulfonic acid sodium, remaining is same as Example 1, and pressure break drag reducer N2 is made.
Test case 1-14
This test case, which is used to test, adopts the pressure break being obtained by the present invention with drag reducer P1-P12 and using comparative example
Resistance reducing performance of the pressure break that described method is prepared with drag reducer N1-N2 in clear water and 2 weight % the KCl aqueous solution.
Fracturing fluid drag reducer P1-P12 and pressure break are tested with drag reducer N1-N2 resistance reducing performance to be determined by fracturing fluid drag reducer
Device (model Hai'an oil scientific research Instrument Ltd. fracturing fluid drop friction test instrument) measure, condition are as follows：
At 25 DEG C, above-mentioned fracturing fluid drag reducer is made into the 0.05 weight % aqueous solution respectively and is added in dissolving tank, solution
Conveyed and flowed out by pump, enter test section through spinner flowmeter.With spinner flowmeter metered flow, uninterrupted is by frequency converter control
System, determine pressure drop of the solution by test section.A diameter of 0.635 centimetre of test pipe, test length of pipe section is 3 meters, and caliber is
10 millimeters, drag reducing efficiency (DR, %) is calculated as follows：
In formula, Δ P0Pressure caused by test pipeline section is flowed through for the KCl aqueous solution of clear water under certain flow rate or 2 weight %
Drop, unit Pa；Δ P is that drag reduction agent solution flows through pressure drop caused by test pipeline section, unit Pa under same flow velocity.
Table 1 is the drag reduction efficiency under the conditions of different in flow rate in clear water of 0.05 weight % drag reducers.By embodiment 1-12
As can be seen that the drag reducing efficiency of drag reducer produced by the present invention compared with the test result for the drag reducer that comparative example 1-2 is obtained
Drag reducing efficiency than drag reducer made from comparative example is high.Particularly at high shear rates, the drag reducer that prepared by the present invention compares
Drag reducer resistance reducing performance has significantly improved made from ratio, still has higher drag reducing efficiency at high shear rates, this says
Bright drag reducer resistant to shearing ability of the invention and drag reduction efficiency are significantly improved.
The drag reduction efficiency of pressure break friction reducer in the clear water of table 1
Table 2 is the drag reduction effect under the conditions of different in flow rate in the 2 weight % KCl aqueous solution of 0.05 weight % drag reducers
Rate.It is produced by the present invention by embodiment 1-12 compared with comparative example 1-2 as can be seen that in 2 weight % KCl salt solution
Drag reducing efficiency of the drag reducing efficiency of drag reducer than drag reducer made from comparative example is high.The drag reducer that this explanation present invention synthesizes has height
Drag reduction efficiency and resistant to shearing ability.
The drag reduction efficiency of pressure break friction reducer in the weight % of the table 22 KCl aqueous solution
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, 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 its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (13)
- A kind of 1. pressure break drag reducing agent composition, it is characterised in that the knot in said composition containing acrylamide, shown in formula (I) Structure monomer and 2- acrylamide-2-methylpro panesulfonic acids or its salt,Wherein, the structures alone shown in formula (I) is dodecyl acrylate and/or Process Conditions of Cetane Acrylate, is also contained in the composition Have chelating agent, molecular weight regulator and water, wherein the chelating agent be selected from disodium ethylene diamine tetraacetate, triethylenediamine pentaacetic acid, At least one of citric acid, citrate and poly- hydroxy acrylic acid, the molecular weight regulator be selected from sodium formate, sodium acetate, At least one of glycerine and isopropanol.
- 2. composition according to claim 1, wherein, relative to the acrylamide of 100 parts by weight, shown in the formula (I) The dosage of structures alone be 0.1-10 parts by weight；The dosage of the 2- acrylamide-2-methylpro panesulfonic acids or its salt is 10- 100 parts by weight.
- 3. composition according to claim 2, wherein, relative to the acrylamide of 100 parts by weight, shown in the formula (I) The dosage of structures alone be 0.5-5 parts by weight；The dosage of the 2- acrylamide-2-methylpro panesulfonic acids or its salt is 20- 50 parts by weight.
- 4. composition according to claim 1, wherein, relative to the acrylamide of 100 parts by weight, the use of the chelating agent Measure as 0.001-5 parts by weight；The dosage of the molecular weight regulator is 0.001-1 parts by weight；The dosage of the water is 50-200 Parts by weight.
- 5. composition according to claim 1, wherein, the molecular weight regulator is sodium formate.
- 6. a kind of preparation method of pressure break drag reducer, it is characterised in that this method includes：Organic solvent and emulsifying agent will be contained Oil solution carry out first with drag reducing agent composition with pressure break and contact, obtain mixture；Then under the polymerization conditions, lazy Property atmosphere under, the mixture and initiator are carried out into second contacts, wherein, acrylamide, formula (I) are contained in the composition Shown structures alone and 2- acrylamide-2-methylpro panesulfonic acids or its salt,Wherein, the structures alone shown in formula (I) is dodecyl acrylate and/or Process Conditions of Cetane Acrylate, is also contained in the composition There are chelating agent, molecular weight regulator and water.
- 7. preparation method according to claim 6, wherein, this method includes：(1) by the structures alone shown in acrylamide, formula (I) and 2- acrylamide-2-methylpro panesulfonic acids or its salt, chelating Agent, molecular weight regulator and water mixing, obtain the aqueous solution；(2) organic solvent is mixed with emulsifying agent, obtains oil solution；(3) aqueous solution that step (1) obtains is carried out into first with the oil solution that step (2) obtains to contact, obtains the mixture；(4) under the polymerization conditions, the mixture that step (3) obtains under an inert atmosphere, is carried out into second with initiator to connect Touch.
- 8. preparation method according to claim 6, wherein, relative to the acrylamide of 100 parts by weight, the organic solvent Dosage be 50-200 parts by weight, the dosage of the emulsifying agent is 5-20 parts by weight, and the dosage of the initiator is 0.001-2 weights Measure part.
- 9. preparation method according to claim 6, wherein, the hydrophilic lipophilic balance of the emulsifying agent is 5-7.
- 10. preparation method according to claim 9, wherein, the emulsifying agent is nonionic emulsifier.
- 11. preparation method according to claim 10, wherein, the emulsifying agent is selected from sorbitan oleate, dehydration mountain Pears alcohol monoleate APEO, sorbitan fatty acid methyl esters, OPEO, benzylphenol oxygen polyoxy second At least one of alkene ether, phenethyl phenol polyethenoxy ether and aliphatic amine polyoxyethylene ether.
- 12. preparation method according to claim 6, wherein, the condition of the polymerisation includes：Temperature is 20-60 DEG C, Time is 2-8 hours.
- 13. the pressure break drag reducer being prepared as the method described in any one in claim 6-12.
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