CN106046253A - Supermolecular surface active micro-electrical type clean fracturing fluid thickening agent specially used for shale gas and preparation method thereof - Google Patents
Supermolecular surface active micro-electrical type clean fracturing fluid thickening agent specially used for shale gas and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a supermolecular surface active micro-electrical type clean fracturing fluid thickening agent specially used for shale gas and a preparation method thereof. The preparation method comprises the following steps: introducing a temperature-resistant and anti-shear 2-(dimethylamino)ethyl methylacrylate group and a salt-resistant, hypersalinity-resistant and polymerizable surface active micro-electrical functional monomer sodium 3-iodo-3-methyl-1-butyl allyl maleate as well as a fluoride 2,2,3,3,4,4-hexafluorobutyl methylacrylate group with relatively low surface energy and good repellency to oil and water on a macromolecular main chain, and then carrying out copolymerization with acrylamide under certain condition, so that the supermolecular surface active micro-electrical type clean fracturing fluid thickening agent specially used for the shale gas is formed. The supermolecular surface active micro-electrical type clean fracturing fluid thickening agent specially used for the shale gas has obvious beneficial effects of being good in water solubility, viscosifying capability, heat resistance and salt tolerance as well as shear resistance and easy to use and low in cost, and sweep coefficient and fracturing efficiency can be effectively improved, so that the supermolecular surface active micro-electrical type clean fracturing fluid thickening agent specially used for the shale gas has a good application prospect.
Description
Technical field
The present invention relates to a kind of clean fracturing fluid thickener and preparation method thereof, especially a kind of special supermolecule of shale gas
Surface activity micro-electricity type clean fracturing fluid thickener and preparation method thereof, belongs to supermolecule polymer thickening agent technical field.
Background technology
Pressure break has been developed rapidly as Main Yield-increasing, the well stimulation of oil-gas reservoir and has extensively been applied.Fracturing fluid is profit
Being pressed off on stratum with pressure, form crack, it is supported by main support agent, to reduce the volume increase of fluid flow resistance, increasing
Note measure.Proppant therein is also called fracturing fluid.Fracturing fluid can be divided into following two classes: A aqueous fracturing fluid, such as viscous water, water
Frozen glue, oil-in-water emulsion, water base foam and some acid solution etc.；B oil base fracturing fluid, such as thickened oil, water-in-oil emulsion,
Oil-based foam etc..Fracturing fluid is the important component part of fracturing technique, and thickening agent is the main additive in aqueous fracturing fluid, closes
It is tied to serviceability and the pressure break success or failure of fracturing fluid.The most the most frequently used fracturing fluid is mainly with natural plant, cellulose
It is the aqueous fracturing fluid of thickening agent with synthetic polymer, has the most achieved in each oil field and be widely applied, and obtained good
Effect of increasing production.
Currently used fracturing fluid thickener kind is a lot, can be divided into natural polysaccharide and derivant thereof and synthetic polymer
Two big classes, wherein guanidine glue and derivant thereof is most widely used.But its applied defect is to use guanidine glue and derivant thereof as thickening
The fracturing liquid rubber-breaking of agent is incomplete, and residue can be stayed in crack after breaking gel, and remaining in the polymer in crack will seriously drop
The permeability of low proppant pack, thus injure stratum, cause fracturing effect to be deteriorated, take husky reduced capability, limit it and make
Abundant development.Composition principle and technique using synthetic polymer as this series products of thickening agent are relatively simple at present, and it lacks
Point performance is it is also obvious that temperature resistance (less than 85 DEG C) limited in one's ability, and needs to add cross-linking agent in use and improve fracturing fluid
Viscosity, strengthens it and takes husky ability.Therefore use cost increases.And be not easy to preparation, store and pump, it is unfavorable for promoting at the scene and answers
With.Although these fracturing fluids can be by mixing brokenly glue with formation hydrocarbon or water, but this process required time is longer.
And after oil field compression fracture, mostly use the quickly row's of returning technique at present, and after pressing crack construction terminates, open flow immediately, as far as possible
Reduce the fracturing fluid residence time on stratum.In order to meet oil field needs, therefore create the demand to clean fracturing fluid thickener.
Clean fracturing fluid thickener uses strong oxidizer to force broken glue.Do not injure stratum after breaking gel without residue, the injury to core is relatively low.
In a word, in recent years, fracturing fluid thickener research and application are towards variation, high temperature resistance, the direction of low cost
Development, and different types of fracturing fluid thickener is all in constantly abundant and development, but major part research is limited to indoor real
Testing the stage, by synthesis technique, the restriction of the conditions such as cost, new product hardly enters scene.So that clean fracturing fluid thickening
The production application of agent does not reach should be effective.
Summary of the invention
The main object of the present invention be limited in one's ability for fracturing fluid thickener temperature resistance present in above-mentioned prior art, need
Cross-linking agent to be added, use cost high and be difficult to preparation, store and pump, the problem such as the broken glue time is longer, it is provided that a kind of shale
Gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener, its resistance to elevated temperatures is obviously enhanced, it is not necessary to add crosslinking
Agent, easy to use and low cost, it is easy to prepare, store and pump, and broken glue is rapid.
The technical solution used in the present invention is as follows:
A kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener, for random copolymerization formed embedding
Section copolymer, has a molecular structure as shown in following formula (1):
In formula (1), m=100-160, n=500-800, p=200-400；The molecular weight of polymer is 8,000,000-1000
Ten thousand.
The preparation method of a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener, including following
Step:
The first step: the synthesis of surface activity micro-electricity type function monomer:
With acetone as solvent, respectively with 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3, maleic anhydride as reactant, 40
DEG C～60 DEG C at react；After terminating with reaction, add sodium hydroxide solution and be neutralized reaction, after neutralization reaction terminates, cooling
To room temperature, concentrating, filter, more repeatedly wash precipitation with normal hexane, the thick liquid obtained is surface activity micro-electricity type function
Monomer；
Reaction equation is as follows:
Wherein, with 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3, maleic anhydride, acetone quality sum as reaction system
Gross mass 100% is counted:
Consumption is reaction system gross mass 30%～the 40% of 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3,
The consumption of maleic anhydride is the 30%～40% of reaction system gross mass,
Remaining is acetone；
When synthesize gained monomer utilize in alkali and time, above-mentioned gained surface active monomer, sodium hydroxide, acetone are that raw material closes
Quality sum when becoming surface activity micro-electricity type function monomer is that reaction system gross mass 100% is counted:
The consumption of surface active monomer is the 40%～45% of reaction system gross mass,
The consumption of sodium hydroxide is the 40%～45% of reaction system gross mass,
Remaining is acetone.
Second step: the synthesis of a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener:
(1) methacrylic acid-2-(dimethylamino) ethyl ester is dissolved in acetone, then potassium chloride is added methacrylic acid-
2-(dimethylamino) ethyl ester solution reacts, and obtains the chlorination charged products containing methacrylic acid-2-(dimethylamino) ethyl ester；
Reaction equation is as follows:
(2) methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester is dissolved in acetone, then sodium hydroxide is added methyl
Acrylic acid-(2,2,3,3,4,4-hexafluoro) butyl acetate solution is neutralized reaction, obtains containing methacrylic acid-(2,2,3,3,4,4-
Hexafluoro) neutralized reaction product of butyl ester；
Reaction equation is as follows:
(3) methacrylic acid-2-(dimethylamino) ethyl ester obtained to above-mentioned (1), (2) and methacrylic acid-(2,2,3,
3,4,4-hexafluoros) butyl ester pretreatment product in add the sodium salt of surface active monomer that the first step prepares, and acrylamide,
Acetone is thoroughly mixed to form hybrid reaction system；
In above-mentioned hybrid reaction system, add initiator, control after temperature is 22 DEG C～33 DEG C of abundant reactions, to obtain glue
Body shape product；
Reaction equation is as follows:
Wherein, in above-mentioned hybrid reaction system, with surface activity micro-electricity type function monomer, methacrylic acid-2-(diformazan ammonia
Base) ethyl ester pretreatment product, methacrylic acid-(2,2,3,3,4,4-hexafluoro) pretreatment product of butyl ester, acrylamide, acetone
Quality sum be that gross mass 100% is counted:
The consumption of the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 25%～30% of gross mass,
The consumption of the pretreatment product of methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester account for gross mass 12%～
15%,
Surface activity micro-electricity type function monomer consumption accounts for the 28%～30% of gross mass,
Acrylamide consumption accounts for the 10%～15% of gross mass,
Remaining is acetone；
Described initiator is redox system initiator or azo-initiator, described redox system initiator by
Ammonium persulfate. mixes with sodium sulfite, and described azo-initiator is azodiisobutyronitrile；
3rd step: post processing:
By second step gained colloidal product pelletize, dry, pulverizing, obtain the shale gas special supermolecule micro-electricity of surface activity
Type clean fracturing fluid thickener.
Further, in the synthesis of described first step surface active monomer, acetone is solvent, 3-iodo-3-methyl isophthalic acid-butyl
The response time of 1-propenol-3 and maleic anhydride reaction system is 12h～18h.
In the synthetic reaction of described first step surface activity micro-electricity type function monomer, the sodium hydroxide being neutralized reaction is molten
The mass concentration of liquid is 40%～45%.
Further, described second step shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener synthesis
In, the mass concentration of step (1) described methacrylic acid-2-(dimethylamino) ethyl ester is 55%～65%, the addition of potassium chloride
Measuring with methacrylic acid-2-(dimethylamino) ethyl ester degree of neutralization is 15%～25% calculating, and remaining is acetone.
Described second step, in step (2), the mass concentration of methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester is
60%～75%, the addition of sodium hydroxide with methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester degree of neutralization be 15%～
25% calculates, and remaining is acetone.
In the synthesis of described second step shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener, described
Ammonium persulfate. in redox system initiator: sodium sulfite mass ratio=1:1.
Described initiator addition is the 1%～3% of reaction system gross mass.
A kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener of we's invention, can be greatly
Improving existing thickening agent shortcoming in use, the present invention introduces heatproof, shear-stable methyl on high polymer main chain
Acrylic acid-2-(dimethylamino) ethyl ester group, and salt tolerant, the polymerisable surface activity of resistance to high salinity micro-Electricity Functional monomer are along fourth
Enedioic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt, and surface can be relatively low, has the fluorination of good water and oil repellant
Thing methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester group, then carry out copolymerization shape with acrylamide under certain conditions
Become a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener.Our experiments show that: this oil displacement agent has
Good water solublity, tackifying and salt-resistance, stirs by the saline of 5000ppm 400 revs/min of mixing speeds in 45 DEG C of water-baths
To mix dissolving 2h, then be diluted to 1500ppm Brookfield viscometer with 5000ppm saline and detect its viscosity, its Testing index is >=
50mPa.s；Its heat resistance shows as within 6 months, to keep viscosity rate 93% at 150 DEG C of constant temperature；Its anti-shear performance shows as
60 seconds viscosity retention ratios 86% of the rotating speed down cut of 10000 revolution per seconds.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows: described a kind of shale gas is special
Supermolecule surface activity micro-electricity type clean fracturing fluid thickener has good water solublity, adhesion-promoting, heat and salt resistance and shearing resistance
Cut performance, easy to use, low cost, sweep efficiency and pressure break efficiency can be effectively improved, oil field Sustainable high yield can be kept, especially
Late high water content period Exploitation Level of Oilfield can be carried, there is good application prospect.
Detailed description of the invention
All features disclosed in this specification, or disclosed all methods or during step, except mutually exclusive
Feature and/or step beyond, all can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, all can by other equivalence or there is similar purpose
Alternative features is replaced.I.e., unless specifically stated otherwise, an example during each feature is a series of equivalence or similar characteristics
?.
Embodiment 1
New a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener of the present invention is by following
Step:
The first step: the synthesis of surface activity micro-electricity type function monomer:
Weigh 175g maleic anhydride to be dissolved in 150g acetone, add 175g 3-iodo-3-methyl isophthalic acid-butyl allyl
Alcohol, reacts 18 hours at 40 DEG C；After reaction terminates, take 200g maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester, add
Enter acetone 100g to dissolve, add the sodium hydroxide solution that mass concentration is 30% that 200g sodium hydroxide is configured to and be neutralized
Reaction；After neutralization reaction terminates, being cooled to room temperature, filter, the thick liquid obtained is surface activity micro-electricity type function monomer
Maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt；
(in the present embodiment, with 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3, maleic anhydride, the quality sum of acetone
500g is that reaction system gross mass 100% is counted:
Consumption is reaction system gross mass the 35% of 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3,
The consumption of maleic anhydride is the 35% of reaction system gross mass,
The consumption of acetone is the 30% of reaction system gross mass.After reaction further with in alkali liquor and time, gained surface
Activated monomer, sodium hydroxide, acetone are that quality sum 500g during Material synthesis surface activity micro-electricity type function monomer is for reacting
System gross mass 100% is counted:
Consumption is reaction system gross mass the 40% of maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester,
The consumption of sodium hydroxide is the 40% of reaction system gross mass,
The consumption of acetone is the 20% of reaction system gross mass)
Second step: the synthesis of a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener:
(1) weigh 130g methacrylic acid-2-(dimethylamino) ethyl ester to be dissolved in 40g acetone, add 30g potassium chloride and enter
After row neutralizes reaction, obtain the chlorination charged products containing methacrylic acid-2-(dimethylamino) ethyl ester；
(in the present embodiment hybrid reaction system, with methacrylic acid-2-(dimethylamino) ethyl ester, potassium chloride, the matter of acetone
Amount sum 200g is that gross mass 100% is counted:
The consumption of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 65% of gross mass,
The consumption of potassium chloride accounts for the 15% of gross mass,
Acetone consumption accounts for the 20% of gross mass)
(2) weigh 120g methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester and be dissolved in 30g acetone, then by 50g hydrogen-oxygen
Change sodium add methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl acetate solution be neutralized reaction, obtain containing methacrylic acid-
The neutralized reaction product of (2,2,3,3,4,4-hexafluoro) butyl ester；
(in the present embodiment hybrid reaction system, with methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester, sodium hydroxide,
Quality sum 200g of acetone is that gross mass 100% is counted:
The consumption of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 60% of gross mass,
The consumption of sodium hydroxide accounts for the 25% of gross mass,
Acetone consumption accounts for the 15% of gross mass)
(3) weigh 30g acrylamide, be dissolved in 20g acetone, add the surface active monomer maleic obtained by the first step
Diacid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt 60g, the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester
The pretreatment product 30g of 60g, methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester, is thoroughly mixed to form hybrid reaction body
System；
(in the present embodiment hybrid reaction system, with maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt, first
The pretreatment of base acrylic acid-2-(dimethylamino) ethyl ester pretreatment product, methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester
Product, acrylamide, quality sum 200g of acetone are that gross mass 100% is counted:
The consumption of the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 30% of gross mass,
The consumption of the pretreatment product of methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester accounts for the 15% of gross mass,
The consumption of maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt accounts for the 30% of gross mass,
Acrylamide consumption accounts for the 15% of gross mass,
Acetone consumption accounts for the 10% of gross mass)
The initiator 2g mixed by Ammonium persulfate. is added with sodium sulfite 1:1 in above-mentioned hybrid reaction system
(maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt, methacrylic acid-2-(dimethylamino) ethyl ester pretreatment are produced
Thing, methacrylic acid-(2,2,3,3,4,4-hexafluoro) pretreatment product of butyl ester, acrylamide, quality sum 200g of acetone
1%), control temperature be 22 DEG C, fully react；After reaction terminates, obtain colloidal product；
3rd step: post processing:
By second step gained colloidal product pelletize, dry, pulverizing, obtain novel surface activity micro-electricity type clean fracturing fluid
Thickening agent.
The present embodiment products obtained therefrom is white 20 mesh-40 mesh graininess, with the saline of 5000ppm in 45 DEG C of water-baths
400 revs/min of mixing speed stirring and dissolving 2h, then with 5000ppm saline be diluted to 1500ppm Brookfield viscometer detect its glue
Degree, its Testing index is >=50mPa.s；Detecting its molecular weight by capillary viscosimetry, its molecular weight ranges is 1800-
19500000.
Embodiment 2
New a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener of the present invention is by following
Step:
The first step: the synthesis of surface activity micro-electricity type function monomer:
Weigh 150g maleic anhydride to be dissolved in 200g acetone, add 150g 3-iodo-3-methyl isophthalic acid-butyl allyl
Alcohol, reacts 18 hours at 40 DEG C；After reaction terminates, take 150g maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester, add
Enter acetone 200g to dissolve, add the sodium hydroxide solution that mass concentration is 30% that 150g sodium hydroxide is configured to and be neutralized
Reaction；After neutralization reaction terminates, being cooled to room temperature, filter, the thick liquid obtained is surface activity micro-electricity type function monomer
Maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt；
(in the present embodiment, with 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3, maleic anhydride, the quality sum of acetone
500g is that reaction system gross mass 100% is counted:
Consumption is reaction system gross mass the 30% of 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3,
The consumption of maleic anhydride is the 30% of reaction system gross mass,
The consumption of acetone is the 40% of reaction system gross mass.After reaction further with in alkali liquor and time, gained surface
Activated monomer, sodium hydroxide, acetone are that quality sum 500g during Material synthesis surface activity micro-electricity type function monomer is for reacting
System gross mass 100% is counted:
Consumption is reaction system gross mass the 30% of maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester,
The consumption of sodium hydroxide is the 30% of reaction system gross mass,
The consumption of acetone is the 40% of reaction system gross mass)
Second step: the synthesis of a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener:
(1) weigh 110g methacrylic acid-2-(dimethylamino) ethyl ester to be dissolved in 50g acetone, add 40g potassium chloride and enter
After row neutralizes reaction, obtain the chlorination charged products containing methacrylic acid-2-(dimethylamino) ethyl ester；
(in the present embodiment hybrid reaction system, with methacrylic acid-2-(dimethylamino) ethyl ester, potassium chloride, the matter of acetone
Amount sum 200g is that gross mass 100% is counted:
The consumption of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 55% of gross mass,
The consumption of potassium chloride accounts for the 20% of gross mass,
Acetone consumption accounts for the 25% of gross mass)
(2) weigh 120g methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester and be dissolved in 40g acetone, then by 40g hydrogen-oxygen
Change sodium add methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl acetate solution be neutralized reaction, obtain containing methacrylic acid-
The neutralized reaction product of (2,2,3,3,4,4-hexafluoro) butyl ester；
(in the present embodiment hybrid reaction system, with methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester, sodium hydroxide,
Quality sum 200g of acetone is that gross mass 100% is counted:
The consumption of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 60% of gross mass,
The consumption of sodium hydroxide accounts for the 20% of gross mass,
Acetone consumption accounts for the 20% of gross mass)
(3) weigh 30g acrylamide, be dissolved in 34g acetone, add the surface active monomer maleic obtained by the first step
Diacid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt 56g, the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester
The pretreatment product 30g of 50g, methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester, is thoroughly mixed to form hybrid reaction body
System；
(in the present embodiment hybrid reaction system, with maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt, first
The pretreatment of base acrylic acid-2-(dimethylamino) ethyl ester pretreatment product, methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester
Product, acrylamide, quality sum 200g of acetone are that gross mass 100% is counted:
The consumption of the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 25% of gross mass,
The consumption of the pretreatment product of methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester accounts for the 15% of gross mass,
The consumption of maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt accounts for the 28% of gross mass,
Acrylamide consumption accounts for the 15% of gross mass,
Acetone consumption accounts for the 17% of gross mass)
The initiator 2g mixed by Ammonium persulfate. is added with sodium sulfite 1:1 in above-mentioned hybrid reaction system
(maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt, methacrylic acid-2-(dimethylamino) ethyl ester pretreatment are produced
Thing, methacrylic acid-(2,2,3,3,4,4-hexafluoro) pretreatment product of butyl ester, acrylamide, quality sum 200g of acetone
1%), control temperature be 22 DEG C, fully react；After reaction terminates, obtain colloidal product；
3rd step: post processing:
By second step gained colloidal product pelletize, dry, pulverizing, obtain the shale gas special supermolecule micro-electricity of surface activity
Type clean fracturing fluid thickener.
The present embodiment products obtained therefrom is white 20 mesh-40 mesh graininess, with the saline of 5000ppm in 45 DEG C of water-baths
400 revs/min of mixing speed stirring and dissolving 2h, then with 5000ppm saline be diluted to 1500ppm Brookfield viscometer detect its glue
Degree, its Testing index is >=50mPa.s；Detecting its molecular weight by capillary viscosimetry, its molecular weight ranges is 1900-
20500000.
Embodiment 3
A kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener of the present invention is by following step
Rapid system:
The first step: the synthesis of surface activity micro-electricity type function monomer:
Weigh 160g maleic anhydride to be dissolved in 180g acetone, add 160g 3-iodo-3-methyl isophthalic acid-butyl allyl
Alcohol, reacts 18 hours at 40 DEG C；After reaction terminates, take 190g maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester, add
Enter acetone 135g to dissolve, add the sodium hydroxide solution that mass concentration is 30% that 175g sodium hydroxide is configured to and be neutralized
Reaction；After neutralization reaction terminates, being cooled to room temperature, filter, the thick liquid obtained is surface activity micro-electricity type function monomer
Maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt；
(in the present embodiment, with 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3, maleic anhydride, the quality sum of acetone
500g is that reaction system gross mass 100% is counted:
Consumption is reaction system gross mass the 32% of 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3,
The consumption of maleic anhydride is the 32% of reaction system gross mass,
The consumption of acetone is the 36% of reaction system gross mass.After reaction further with in alkali liquor and time, gained surface
Activated monomer, sodium hydroxide, acetone are that quality sum 500g during Material synthesis surface activity micro-electricity type function monomer is for reacting
System gross mass 100% is counted:
Consumption is reaction system gross mass the 38% of maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester,
The consumption of sodium hydroxide is the 35% of reaction system gross mass,
The consumption of acetone is the 27% of reaction system gross mass)
Second step: the synthesis of a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener:
(1) weigh 134g methacrylic acid-2-(dimethylamino) ethyl ester to be dissolved in 50g acetone, add 26g potassium chloride and enter
After row neutralizes reaction, obtain the chlorination charged products containing methacrylic acid-2-(dimethylamino) ethyl ester；
(in the present embodiment hybrid reaction system, with methacrylic acid-2-(dimethylamino) ethyl ester, potassium chloride, the matter of acetone
Amount sum 200g is that gross mass 100% is counted:
The consumption of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 62% of gross mass,
The consumption of potassium chloride accounts for the 13% of gross mass,
Acetone consumption accounts for the 25% of gross mass)
(2) weigh 110g methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester and be dissolved in 50g acetone, then by 40g hydrogen-oxygen
Change sodium add methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl acetate solution be neutralized reaction, obtain containing methacrylic acid-
The neutralized reaction product of (2,2,3,3,4,4-hexafluoro) butyl ester；
(in the present embodiment hybrid reaction system, with methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester, sodium hydroxide,
Quality sum 200g of acetone is that gross mass 100% is counted:
The consumption of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 55% of gross mass,
The consumption of sodium hydroxide accounts for the 20% of gross mass,
Acetone consumption accounts for the 25% of gross mass)
(3) weigh 26g acrylamide, be dissolved in 28g acetone, add the surface active monomer maleic obtained by the first step
Diacid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt 58g, the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester
The pretreatment product 24g of 64g, methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester, is thoroughly mixed to form hybrid reaction body
System；
(in the present embodiment hybrid reaction system, with maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt, first
The pretreatment of base acrylic acid-2-(dimethylamino) ethyl ester pretreatment product, methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester
Product, acrylamide, quality sum 200g of acetone are that gross mass 100% is counted:
The consumption of the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 32% of gross mass,
The consumption of the pretreatment product of methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester accounts for the 12% of gross mass,
The consumption of maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt accounts for the 29% of gross mass,
Acrylamide consumption accounts for the 13% of gross mass,
Acetone consumption accounts for the 14% of gross mass)
The initiator 2g mixed by Ammonium persulfate. is added with sodium sulfite 1:1 in above-mentioned hybrid reaction system
(maleic acid-3-iodo-3-methyl isophthalic acid-butyl allyl ester sodium salt, methacrylic acid-2-(dimethylamino) ethyl ester pretreatment are produced
Thing, methacrylic acid-(2,2,3,3,4,4-hexafluoro) pretreatment product of butyl ester, acrylamide, quality sum 200g of acetone
1%), control temperature be 22 DEG C, fully react；After reaction terminates, obtain colloidal product；
3rd step: post processing:
By second step gained colloidal product pelletize, dry, pulverizing, obtain a kind of shale gas special supermolecule surface activity
Micro-electricity type clean fracturing fluid thickener.
The present embodiment products obtained therefrom is white 20 mesh-40 mesh graininess, with the saline of 5000ppm in 45 DEG C of water-baths
400 revs/min of mixing speed stirring and dissolving 2h, then with 5000ppm saline be diluted to 1500ppm Brookfield viscometer detect its glue
Degree, its Testing index is >=50mPa.s；Detecting its molecular weight by capillary viscosimetry, its molecular weight ranges is 2050-
21000000.
A kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener of the present invention has good
Water solublity, adhesion-promoting, heat and salt resistance and anti-shear performance, easy to use, low cost, sweep efficiency and pressure can be effectively improved
Split efficiency, oil field Sustainable high yield can be kept, especially can carry late high water content period Exploitation Level of Oilfield, there is good application prospect.
The invention is not limited in aforesaid detailed description of the invention.The present invention expands to any disclose in this manual
New feature or any new combination, and the arbitrary new method that discloses or the step of process or any new combination.
Claims (10)
1. shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener, the block formed for random copolymerization
Copolymer, it is characterised in that there is the molecular structure as shown in following formula (1):
In formula (1), m=100-160, n=500-800, p=200-400, q=300-400；The molecular weight of polymer is 800
Ten thousand-1,000 ten thousand.
2. a preparation method for shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener, its feature exists
In, comprise the following steps:
The first step: the synthesis of surface activity micro-electricity type function monomer:
With acetone as solvent, respectively with 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3, maleic anhydride as reactant, at 40 DEG C～
React at 60 DEG C；After terminating with reaction, add sodium hydroxide solution and be neutralized reaction, after neutralization reaction terminates, be cooled to room
Temperature, concentrating, filter, more repeatedly wash precipitation with normal hexane, the thick liquid obtained is surface activity micro-electricity type function monomer；
Reaction equation is as follows:
Second step: the synthesis of a kind of shale gas special supermolecule surface activity micro-electricity type clean fracturing fluid thickener:
(1) methacrylic acid-2-(dimethylamino) ethyl ester is dissolved in acetone, then potassium chloride is added methacrylic acid-2-(two
Methylamino) ethyl ester solution reacts, and obtains the chlorination charged products containing methacrylic acid-2-(dimethylamino) ethyl ester；
(2) methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester is dissolved in acetone, then sodium hydroxide is added metering system
Acid-(2,2,3,3,4,4-hexafluoro) butyl acetate solution is neutralized reaction, obtains containing methacrylic acid-(2,2,3,3,4,4-hexafluoro)
The neutralized reaction product of butyl ester；
Reaction equation is as follows:
(3) methacrylic acid-2-(dimethylamino) ethyl ester obtained to above-mentioned (1), (2) and methacrylic acid-(2,2,3,3,4,
4-hexafluoro) butyl ester pretreatment product in add the sodium salt of surface active monomer that the first step prepares, and acrylamide, acetone
It is thoroughly mixed to form hybrid reaction system；
In above-mentioned hybrid reaction system, add initiator, control after temperature is 22 DEG C～33 DEG C of abundant reactions, to obtain colloidal
Product；
Reaction equation is as follows:
3rd step: post processing:
By second step gained colloidal product pelletize, dry, pulverizing, obtain shale gas special supermolecule surface activity micro-electricity type clear
Clean fracturing fluid thickener.
A kind of shale gas the most according to claim 2 special supermolecule surface activity micro-electricity type clean fracturing fluid thickener
Preparation method, it is characterised in that in the first step, is former with 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3, maleic anhydride, acetone
Quality sum during material synthetic surface activated monomer is that reaction system gross mass 100% is counted:
Consumption is reaction system gross mass 30%～the 40% of 3-iodo-3-methyl isophthalic acid-butyl 1-propenol-3,
The consumption of maleic anhydride is the 30%～40% of reaction system gross mass,
Remaining is acetone.
When synthesize gained monomer utilize in alkali and time, above-mentioned gained surface active monomer, sodium hydroxide, acetone are Material synthesis table
Quality sum during face activity micro-electricity type function monomer is that reaction system gross mass 100% is counted:
The consumption of surface active monomer is the 40%～45% of reaction system gross mass,
The consumption of sodium hydroxide is the 40%～45% of reaction system gross mass,
Remaining is acetone.
A kind of shale gas the most according to claim 2 special supermolecule surface activity micro-electricity type clean fracturing fluid thickener
Preparation method, it is characterised in that in second step, in hybrid reaction system, with surface activity micro-electricity type function monomer, metering system
The pretreatment product of acid-2-(dimethylamino) ethyl ester pretreatment product, methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester,
Acrylamide, the quality sum of acetone are that gross mass 100% is counted:
The consumption of the pretreatment product of methacrylic acid-2-(dimethylamino) ethyl ester accounts for the 25%～30% of gross mass,
The consumption of the pretreatment product of methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester accounts for the 12%～15% of gross mass,
Surface activity micro-electricity type function monomer consumption accounts for the 28%～30% of gross mass,
Acrylamide consumption accounts for the 10%～15% of gross mass,
Remaining is acetone；
Described initiator is redox system initiator or azo-initiator, and described redox system initiator is by over cure
Acid ammonium mixes with sodium sulfite, and described azo-initiator is azodiisobutyronitrile.
A kind of shale gas the most according to claim 2 special supermolecule surface activity micro-electricity type clean fracturing fluid thickener
Preparation method, it is characterised in that in the synthesis of described first step surface active monomer, acetone be solvent, 3-iodo-3-methyl isophthalic acid-
The response time of butyl 1-propenol-3 and maleic anhydride reaction system is 12h～18h.
A kind of shale gas the most according to claim 5 special supermolecule surface activity micro-electricity type clean fracturing fluid thickener
Preparation method, it is characterised in that in the synthetic reaction of described first step surface activity micro-electricity type function monomer, be neutralized reaction
The mass concentration of sodium hydroxide solution be 40%～45%.
A kind of shale gas the most according to claim 2 special supermolecule surface activity micro-electricity type clean fracturing fluid thickener
Preparation method, it is characterised in that in second step, the mass concentration of step (1) described methacrylic acid-2-(dimethylamino) ethyl ester
Being 55%～65%, the addition of potassium chloride is in terms of 15%～25% by methacrylic acid-2-(dimethylamino) ethyl ester degree of neutralization
Calculating, remaining is acetone.
A kind of shale gas the most according to claim 2 special supermolecule surface activity micro-electricity type clean fracturing fluid thickener
Preparation method, it is characterised in that in second step, the matter of step (2) described methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester
Amount concentration is 60%～75%, and the addition of sodium hydroxide is with methacrylic acid-(2,2,3,3,4,4-hexafluoro) butyl ester degree of neutralization
Being 15%～25% calculating, remaining is acetone.
A kind of shale gas the most according to claim 2 special supermolecule surface activity micro-electricity type clean fracturing fluid thickener
Preparation method, it is characterised in that in described second step, Ammonium persulfate. in described redox system initiator: sodium sulfite
Mass ratio=1:1.
10. according to the micro-electricity type clean fracturing fluid thickening of a kind of shale gas special supermolecule surface activity described in claim 2 or 8
The preparation method of agent, it is characterised in that described initiator addition is the 1%～3% of reaction system gross mass.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845301A (en) * | 2010-05-05 | 2010-09-29 | 广汉沃瑞信化工有限公司 | Clean fracturing fluid thickener and preparation method thereof |
| CN102838980A (en) * | 2012-07-26 | 2012-12-26 | 中国石油化工股份有限公司胜利油田分公司采油工艺研究院 | High temperature resistant cleansing emulsion or microemulsion fracturing fluid and preparation method thereof |
| CN103224779A (en) * | 2013-05-16 | 2013-07-31 | 西南石油大学 | Association-type non-crosslinking fracturing fluid and preparation method thereof |
| CN104710969A (en) * | 2015-04-03 | 2015-06-17 | 中国石油大学(北京) | Tackifier for oil-based drilling fluid and preparation method of tackifier |
| CN105385434A (en) * | 2015-11-25 | 2016-03-09 | 中国石油天然气集团公司 | Polymer clean fracturing fluid and preparation method thereof |
| CN105733547A (en) * | 2016-01-29 | 2016-07-06 | 成都佰椿石油科技有限公司 | High-temperature-resistance low-friction weighted clean fracturing fluid and preparation method thereof |
| CN105968258A (en) * | 2016-05-27 | 2016-09-28 | 济南科慧页岩化工技术有限公司 | Clean and environmentally friendly composite polymer for fracturing fluid and preparing method thereof |
| CN106479472A (en) * | 2016-08-29 | 2017-03-08 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | A kind of fracturing fluid and preparation method thereof |
-
2016
- 2016-06-28 CN CN201610488276.8A patent/CN106046253A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845301A (en) * | 2010-05-05 | 2010-09-29 | 广汉沃瑞信化工有限公司 | Clean fracturing fluid thickener and preparation method thereof |
| CN102838980A (en) * | 2012-07-26 | 2012-12-26 | 中国石油化工股份有限公司胜利油田分公司采油工艺研究院 | High temperature resistant cleansing emulsion or microemulsion fracturing fluid and preparation method thereof |
| CN103224779A (en) * | 2013-05-16 | 2013-07-31 | 西南石油大学 | Association-type non-crosslinking fracturing fluid and preparation method thereof |
| CN103224779B (en) * | 2013-05-16 | 2015-05-20 | 西南石油大学 | Association-type non-crosslinking fracturing fluid and preparation method thereof |
| CN104710969A (en) * | 2015-04-03 | 2015-06-17 | 中国石油大学(北京) | Tackifier for oil-based drilling fluid and preparation method of tackifier |
| CN105385434A (en) * | 2015-11-25 | 2016-03-09 | 中国石油天然气集团公司 | Polymer clean fracturing fluid and preparation method thereof |
| CN105733547A (en) * | 2016-01-29 | 2016-07-06 | 成都佰椿石油科技有限公司 | High-temperature-resistance low-friction weighted clean fracturing fluid and preparation method thereof |
| CN105968258A (en) * | 2016-05-27 | 2016-09-28 | 济南科慧页岩化工技术有限公司 | Clean and environmentally friendly composite polymer for fracturing fluid and preparing method thereof |
| CN106479472A (en) * | 2016-08-29 | 2017-03-08 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | A kind of fracturing fluid and preparation method thereof |
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