CN106467599A - A kind of self-association type linked polymer coil and preparation method thereof - Google Patents
A kind of self-association type linked polymer coil and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of self-association type linked polymer coil and preparation method thereof.Described preparation method comprises the steps：(1) surfactant and oil-soluble initiator are dissolved in base oil as oil phase；(2) hydrophobic monomer, water-soluble cross-linked monomer, conventional water-soluble monomer and water soluble starter are dissolved in the water, are made into the aqueous solution that gross mass percentage composition is 20%-70% as aqueous phase；(3) aqueous phase described in step (2) is mixed with the oil phase described in step (1) and carries out emulsifying, formed dispersion phase be aqueous phase, continuous phase be oil phase w/o type microemulsion；(4) it is passed through noble gases initiated polymerization in the described w/o type microemulsion being formed to step (3), described w/o type microemulsion obtains final product described self-association type linked polymer coil.Self-association type linked polymer coil microemulsion profile control agent water solution system provided by the present invention is particularly suitable for higher permeability oil reservoir.
Description
Technical field
The present invention relates to a kind of self-association type linked polymer coil and preparation method thereof, belong to technical field of petroleum extraction.
Background technology
Polyamide, as one of topmost engineering plastics and textile fiber material, has the many such as high-strength, wear-resisting excellent
At present, early development oil field has stepped into the water flood recovery intermediary and later stages, how to improve the body of injection water further
Displacement efficiency in long-pending sweep efficiency and water swept volume, economical, effectively exploit existing oil field be petroleum industrial circle urgently
One of key subjects to be solved, the wherein development of intensified oil reduction technology and application played an important role.
Intensified oil reduction technology is related to a lot of aspects, and can be divided into the body improving injection liquid based on the method improving Flooding Efficiency
Displacement efficiency two class in long-pending sweep efficiency and raising swept volume.
With going deep into of research, the impact to water drive, chemical flooding displacing fluid sweep efficiency of the anisotropism of oil reservoir is increasingly drawn
Rise and pay close attention in the industry, people recognize that ability is more economical only by deep profile controlling, effectively adjust, improve oil reservoir
Anisotropism, thus improve injection liquid volumetric sweep efficiency it is ensured that chemical flooding realizes high displacement efficiency, raisingization
Learn and drive displacing fluid and the oil recovery factor in sequent water flooding stage.Among these, poly- with cross linked polymer flow-gel, crosslinking
Polymer solution, cross-linked polymer microsphere are the Novel technique of in-depth profile control of representative is economically advantageous, and effect substantially, meets
Long-term injection, the technology beneficial to environmental protection, the research to the method and improvement on deeper level, to adjustment, improve oil
The anisotropism hidden has very important meaning.
The method preparing the linked polymer coil for tertiary oil recovery at present, one kind is using linear partial hydrolysiss poly- third
Acrylamide (HPAM) weak solution (mass fraction is below its critical overlapping mass fraction) is reacted with cross-linking agent, shape
Become the aqueous dispersion (that is, cross-linked polymer solution) of linked polymer coil；Another method is to manage to be formed
Nanometer or the moisture dephasing of micro-meter scale, the copolymerization of the various of monomer carrying out comprising cross-linking monomer in moisture dephasing
Close reaction, formed polymer micelle, these micelles in water swelling, dissolving after formed different scale crosslinking gather
A compound ball of string.Theoretically, only poly- using forming, after injection, the crosslinking that particle diameter matches with stratum pore size
A compound ball of string, could effectively be detained and block venturi, cause Indepth Fluid Diversion, and real realization adjustment and improvement are oily
The anisotropism hidden, improves the recovery ratio of waterflooding extraction crude oil.
The size of the cross linked water soluble polymer ball of string obtaining in the preparation method of the open report of ZL 200410006334.6
Usually hundreds of nanometer, particle diameter are less, and obtain in the preparation method of the open report of ZL 200710063645.X is water-soluble
Property linked polymer coil size increase to several microns, using above two method preparation water-soluble cross-linked polymerization
During a thing ball of string disclosure satisfy that, the use requirement of low-permeability oil pool, the test of ore deposit factory obtains good raising recovery ratio effect
Really.But it was also found that for higher permeability oil reservoir (permeability be more than 1000 millidarcies) in the application of ore deposit factory, or deposit
In higher permeability band, low-permeability oil pool, in order to obtain preferable plugging effect, test early stage needs to increase
Fill the mass fraction of a cross linked water soluble polymer ball of string in liquid, reduce the economy of injection system.
Content of the invention
It is an object of the invention to provide a kind of self-association type linked polymer coil and preparation method thereof.
The preparation method of the self-association type linked polymer coil that the present invention provides, comprises the steps：
(1) surfactant and oil-soluble initiator are dissolved in base oil as oil phase, the boiling point of described base oil
For 60 DEG C -300 DEG C；
(2) hydrophobic monomer, water-soluble cross-linked monomer, conventional water-soluble monomer and water soluble starter are dissolved in water
In, it is made into the aqueous solution that total mass fraction is 20%-70% as aqueous phase；Described hydrophobic monomer is to contain in molecular structure
By C12-C18Carbochain constitutes the water-soluble monomer molecule of hydrophobic group；Described water-soluble cross-linked monomer is to contain in molecular structure
There is the monomer molecule of two or more double bonds and water soluble group；Described conventional water-soluble monomer is molecular structure
In contain only the monomer molecule of single double bond and water soluble group；
(3) aqueous phase described in step (2) is mixed with the oil phase described in step (1) and carry out emulsifying, form dispersion phase
It is the w/o type microemulsion of oil phase for aqueous phase, continuous phase；In described w/o type microemulsion, described base oil, surface
Activating agent, oil-soluble initiator, water soluble starter, the water solublity of hydrophobic monomer, water-soluble cross-linked monomer and routine
The weight/mass percentage composition of monomer be respectively 10.0%-40.0%, 10.0%-30.0%, 0.01%-5.0 ‰, 0.01%-30.0 ‰,
0.1%-50.0%, 0.1%-50.0% and 10.0%-40.0%, balance of water；
(4) it is passed through noble gases initiated polymerization, in institute in the described w/o type microemulsion being formed to step (3)
State and in w/o type microemulsion, obtain final product described self-association type linked polymer coil.
In above-mentioned preparation method, in described w/o type microemulsion, the weight/mass percentage composition of described base oil is concretely
27.5%；The weight/mass percentage composition of described surfactant concretely 22.5%；The quality hundred of described oil-soluble initiator
Point content concretely 3.13 ‰；The weight/mass percentage composition of described hydrophobic monomer concretely 1.2%, 1.4% or 2.0%；
The weight/mass percentage composition of described water-soluble cross-linked monomer concretely 1.7%；The quality hundred of described conventional water-soluble monomer
Point content concretely 23.2%.
In above-mentioned preparation method, methods described is additionally included in containing described hydrophobic association crosslinked polymer coil
The step that precipitant is precipitated, refined and is dried is added in w/o type microemulsion；Described precipitant be dehydrated alcohol,
Absolute methanol or acetone；Can be stripped refining using petroleum ether or other low boiling point hydrocarbon；The temperature of described drying can
For 40 DEG C -60 DEG C, such as 50 DEG C；The time of described drying can be 12 hours -24 hours, such as 12 hours.
In above-mentioned preparation method, the HLB value of surfactant described in step (1) can be 4-10；Described surface
Activating agent can be at least one of nonionic surfactant, anion surfactant and cationic surfactant,
As Span series non-ionic surfactants or Tween series non-ionic surfactants, concretely Sorbitol
Acid anhydride oleate (Span-80) or sorbitan monostearate polyethylene glycol oxide (Tween-60)；Described base oil can
For at least one of n-alkane, isoparaffin, cycloalkane and aromatic hydrocarbon solvent, such as normal octane, isobutyltrimethylmethane., methyl
Low boiler cut that hexamethylene, dimethylbenzene, technical white oil or hydroisomerization dewaxing device produce etc.；Described oil-soluble
Initiator is heat decomposition type initiator, concretely azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide etc..
In above-mentioned preparation method, by C described in step (2)12-C18It can be anion list that carbochain constitutes hydrophobic monomer
At least one of body, cationic monomer and non-ionic monomer；Shown in described anionic monomer such as formula (1), concretely
2- acrylamido dodecane sulfonic acid, 2- acrylamido tetradecane sulfonic acid, 2- acrylamido hexadecane sulfonic acid or 4 (ω-
Acryl-oyloxyethoxy) benzoic acid；Shown in described cationic monomer such as formula (2) or formula (3), concretely (methyl)
Acryloxyethyldimethyl Tetra-n-decylammonium bromide, (methyl) acrylamido propyl-dimethyl dodecyl bromination
Ammonium, N, N- dimethyl-N-pi-allyl tetradecyl ammonium chloride or N, N- dimethyl-N-is to vinyl benzyl myristyl chlorine
Change ammonium etc.；Shown in described non-ionic monomer such as formula (4), concretely cetyl polyoxyethylene groups (10) pi-allyl
Ether, cetyl polyoxyethylene groups (10) are to styrene benzylic ether, cetyl polyoxyethylene groups (10) acrylic acid
Ester, alkylphenol-polyethenoxy base (10) allyl ether, alkylphenol-polyethenoxy base (10) to styrene benzylic ether or
Alkylphenol-polyethenoxy base (10) acrylate etc.；
Formula (1)
Formula (2)
Formula (3)
Formula (4)
In formula (1), n is the natural number of 5-13；In formula (2) and formula (3), R1And R2Represent benzyl or have
The alkyl of 1-3 carbon atom or alkoxyl；R3Represent and there is the alkyl of 8-22 carbon atom or monosubstituted 6-22 carbon
The alkyl benzyl of atom；R4Represent hydrogen or methyl；A represents oxygen atom or NH；B represents has 2-4 carbon atom
Alkylidene or alkylene oxide group；M represents methylene or monosubstituted benzyl；X1Represent anion；R5Represent hydrogen, 8-22
The alkyl of individual carbon atom or the alkyl phenyl of monosubstituted 6-22 carbon atom；D represents methylene, carbonyl or singly takes
For benzyl；E represents polyoxyethylene groups, polyoxypropylene base or PULLRONIC F68 block chain link；Formula (4)
In, R5Represent the alkyl phenyl of hydrogen, the alkyl of 8-22 carbon atom or monosubstituted 6-22 carbon atom；D represents Asia
Methyl, carbonyl or monosubstituted benzyl；E represents polyoxyethylene groups, polyoxypropylene base or PULLRONIC F68
Block chain link.
In above-mentioned preparation method, water-soluble cross-linked monomer described in step (2) can be N, N'- methylene bisacrylamide acyl
Amine, polyethyleneglycol diacrylate, Polyethylene Glycol diallyl ether, N, N- diallyidimethylammonium chloride amine, N, N '-
Diallyl-N, N, N ', N '-tetramethyl own dichloride ammonium, N ,-two couples of vinyl benzyl-N of N ', N, N ', N '-tetramethyl oneself two
Ammonia chloride, three acrylic acid-(propyl group) trimethyl or pentaerythritol triallyl ether；Described conventional water-soluble monomer is
Acrylamide, Methacrylamide, N- vinyl formamide, N- vinyl acetamide, NVP,
N, N- DMAA, acrylonitrile, diacetone acrylamide, (first) HEA acrylamide,
Propenyl, (methyl) acrylic acid, itaconicacid, maleic acid, 2- acrylamide-2-methyl propane sulfonic, vinyl sulfonic acid
Deng the corresponding salt of monomer, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, (methyl) acrylyl oxy-ethyl diethyl
Methyl ammonium, (methyl) acryloxyethyldimethyl benzyl ammonium chloride, (methyl) acrylyl oxy-ethyl two
At least one of ethylbenzylammonium chloride and dimethyl diallyl ammonium chloride；Described water soluble starter is 2,2 '-azo
Two { 2- [1- (2- ethoxy) -2- imidazoline -2- base] propane } dihydrochloride, 2,2 '-azo two (2- amidine propane) disalt
Hydrochlorate (the V50 azo initiator of German Wako Deutschland), 2,2 '-azo two [2- (2- imidazoline -2- base) third
Alkane) dihydrochloride (the V44 azo initiator of German Wako Deutschland) or 2,2 '-azo two [2- (5- methyl
- 2- imidazoline -2- base) propane) dihydrochloride.
In above-mentioned preparation method, the temperature of the described polyreaction of step (4) can be 5 DEG C -85 DEG C, concretely 10 DEG C,
15 DEG C, 20 DEG C or 25 DEG C；The time of described polyreaction can be 4 hours -12 hours, concretely 12 hours.
In above-mentioned preparation method, also include in the described aqueous phase of step (2) oxidative initiator, heat decomposition type initiator,
At least one of chelating agen, pH value regulator and cosolvent；Described oxidative initiator can be Ammonium persulfate., described oxygen
The weight/mass percentage composition that the addition of the property changed initiator accounts for described w/o type microemulsion is 0.001%-0.01%, specifically may be used
For 0.006%；Described heat decomposition type initiator can be 2,2 '-azo two { 2- [1- (2- ethoxy) -2- imidazoline -2- base] third
Alkane } dihydrochloride, 2,2 '-azo two (2- amidine propane) dihydrochloride (V50 of German Wako Deutschland
Azo initiator), 2,2 '-azo two [2- (2- imidazoline -2- base) propane) dihydrochloride (German Wako Deutschland
V44 azo initiator) or 2,2 '-azo two [2- (5- methyl -2- imidazoline -2- base) propane) dihydrochloride；Described chela
Mixture can be disodiumedetate, and the percent mass that the addition of described chelating agen accounts for described w/o type microemulsion contains
Measure as 0.001%-0.01%, concretely 0.0075%；Described pH value regulator can be anhydrous sodium acetate, described pH
The weight/mass percentage composition that the addition of value regulator accounts for described w/o type microemulsion is 1%-10%, concretely 1%；
Described cosolvent can be urea, and the weight/mass percentage composition that the addition of described cosolvent accounts for described w/o type microemulsion is
0.001%-0.01%, concretely 0.005%.
In above-mentioned preparation method, noble gases described in step (4) are high pure nitrogen or argon；Described polyreaction
In also include the step that is passed through reducibility gas, it is bonded oxidation-reduction and is combined with described oxidative initiator and causes
System, makes polyreaction fully carry out；Wherein said reducibility gas are preferably sulfur dioxide gas.
Self-association type linked polymer coil provided by the present invention is present in w/o type microemulsion, this containing
C12-C18The linked polymer coil microemulsion profile control agent of carbochain can directly use；Certain mass fraction can also be passed through
Higher by C12-C18The linked polymer coil powder body that carbochain is constituted swelling, dissolving in water form the crosslinking of self-association type
Polymer coil aqueous solution.In the profile control to oil reservoir is processed, by this self-association type linked polymer coil and its poly-
Collective is in higher permeability (permeability be more than 1000 millidarcies), or exist in higher permeability band, hyposmosis
Machinery in rate oil reservoir is detained, closure large-size venturi, causes Indepth Fluid Diversion, can adjust and improve oil reservoir
Heterogeneous body impact, the closure advantage aquaporin that formed of oil deposit deep part long-term injecting water.Self-association provided by the present invention
Type linked polymer coil microemulsion profile control agent water solution system is particularly suitable for higher permeability oil reservoir, and (permeability is more than
1000 millidarcies), or exist in higher permeability band, low-permeability oil pool application, improve waterflooding extraction in,
The recovery ratio of later stage Reservoir Crude Oil.
Specific embodiment
Below by specific embodiment, the method for the present invention is illustrated, but the invention is not limited in this.
Experimental technique described in following embodiments, if no special instructions, is conventional method；Described reagent and material,
If no special instructions, all commercially obtain.
For further illustrating beneficial effects of the present invention, w/o type micro-emulsion polymerization gained is adopted using the explanation of following example
The new self-association type linked polymer coil arriving and its superior plugging and profile con-trol performance of aggregation：
It is 2.0 μm using the self-association type linked polymer coil aqueous solution determining volume to perm-plug method2Artificial
The plugging and profile con-trol performance of rock core and oil displacement efficiency, simulation self-association type linked polymer coil aqueous solution is to reservoir formation hole
The closure in road is evaluating the plugging and profile con-trol performance of self-association type linked polymer coil.
Comparative example 1, the preparation of linked polymer coil
According in embodiment 1 in a kind of preparation method of linked polymer coil of the open report of ZL 200410006334.6
Prepare the w/o type microemulsion of a cross linked water soluble polymer ball of string, comprise the following steps that：
(1) prepare oil phase：Weigh 48 grams of base oil isoparaffin (viscosity 10.85cP), add it to band and stir
In the 250 milliliters of there-necked flasks mixed, add 19.2 grams of sorbitan mono-oleic acid esters (Span-80) and 12.8 Keshans wherein
Two kinds of nonionic surfactants of pears sugar alcohol acid anhydride monostearate polyoxyethylene (20) ether (Tween-60), mix homogeneously
Afterwards as oil phase；
(2) prepare aqueous phase：Weigh 21.8 grams of water-soluble monomer acrylamide, 6.9 grams of the sodium acrylate of routine, water respectively
Dissolubility cross-linking monomer N, N '-diallyl-N, N, N ', 0.62 gram of N '-tetramethyl own dichloride ammonium, its molecular structure contains two
Individual double bond, 1.33 grams of anhydrous sodium acetate, 0.98 milligram of chelating agen disodiumedetate, 1.31 milligrams of cosolvent urea,
0.88 milligram of oxidative initiator Ammonium persulfate., any of the above composition is dissolved in 34.4 grams of deionized water (electrical conductivity
≤ 4 μ S/cm) in stand-by as aqueous phase；
(3) start stirring, above-mentioned aqueous phase is slowly added in above-mentioned oil phase, is formed stable after the two mix homogeneously
W/o type microemulsion (electrical conductivity≤0.15 μ S/cm)；
(4) setting 25 DEG C is initiation temperature, is passed through noble gases first in the stable w/o type microemulsion of above-mentioned formation
High Purity Nitrogen gas drive oxygen, in reduction system, oxygen content (≤0.3 μ g/g) makes polyreaction cause, and then passes to reproducibility gas
Body sulfur dioxide is combined with Ammonium persulfate. in aqueous phase and constitutes redox initiation system, so that polyreaction is fully carried out,
Obtain the w/o type microemulsion containing linked polymer coil；
(5) dehydrated alcohol is added to precipitate as precipitant in the above-mentioned w/o type microemulsion containing linked polymer coil
Go out linked polymer coil, through petroleum ether extracting, linked polymer coil powder body is made in drying.
Mass fraction is that the linked polymer coil of 400mg/kg is little in 60 DEG C of Bohai SZ36-1 oilfield simulation curings in water 96
When obtain linked polymer coil aqueous solution, to perm-plug method be 2.0 μm2Artificial core carry out the Bohai Sea SZ36-1 oil
The displacement test of field simulation oil, records and can improve simulation oil recovery 12.6% under experiment condition.
Embodiment 1, the preparation of self-association type linked polymer coil：
(1) prepare oil phase：Weigh 110.0 grams of base oil isoparaffin (Daqing Refinery company isomerization dewaxing device
Produce) (viscosity 10.85cP, flash-point is 178 DEG C), add it in 250 milliliters of there-necked flasks with stirring,
Wherein add 57.4 grams of sorbitan mono-oleic acid esters (Span-80, HLB value is 4.3) and 32.6 grams sorbitol acid anhydride lists hard
Two kinds of nonionic surfactants of fat acid polyoxyethylene (20) ether (Tween-60, HLB value is 14.9), mixing is all
As oil phase after even；
(2) prepare aqueous phase：Weigh 58.9 grams of water-soluble monomer acrylamide, 33.8 grams of the sodium acrylate of routine respectively,
Water-soluble cross-linked monomer N, N '-diallyl-N, 6.8 grams of N, N ', N '-tetramethyl own dichloride ammonium, its molecular structure contains two
Individual double bond, to 5.4 grams of vinyl benzyl octadecyl ammonium chloride, its molecular structure contains hydrophobic monomer N, N '-dimethyl-N-
There is a chain alkyl, 4.0 grams of anhydrous sodium acetate, 3.0 milligrams of chelating agen disodiumedetate, 2.0 milligrams of cosolvent urea,
2.5 milligrams of oxidative initiator Ammonium persulfate., heat decomposition type initiator 2,2 '-azo two (2- amidine propane) dihydrochloride
12.5 milligrams, any of the above composition is added separately to add the band of 91.1 grams of deionized waters (electrical conductivity≤4 μ S/cm) to stir
In the 250 milliliters of there-necked flasks mixed, stand-by as aqueous phase after dissolving, in this aqueous phase, the gross mass percentage of each composition contains
Measure as 100%；
(3) on adding in equipped with gas gas ingress pipe, thermometer, 500 milliliters of jacketed reactors of constant speed stirrer
State oil phase, start stirring, above-mentioned aqueous phase is slowly added in oil phase, after the two mix homogeneously, form stable W/O
Type microemulsion (electrical conductivity≤0.15 μ S/cm), in this w/o type microemulsion, the weight/mass percentage composition of base oil is 27.5%,
The weight/mass percentage composition of surfactant is 22.5%, and the weight/mass percentage composition of conventional water-soluble monomer is 23.2%, water
The weight/mass percentage composition of dissolubility cross-linking monomer is 1.7%, and the weight/mass percentage composition of hydrophobic monomer is 1.4%, pH value regulator
Weight/mass percentage composition be 1.0%, the mass content of chelating agen is 0.0075%, and the mass content of cosolvent is 0.005%,
The mass content of oxidative initiator is 0.0063%, and the mass content of heat decomposition type initiator is 0.00313%；
(4) setting 15 DEG C is initiation temperature, is passed through noble gases first in the stable w/o type microemulsion of above-mentioned formation
High Purity Nitrogen gas drive oxygen, in reduction system, oxygen content (≤0.3 μ g/g) makes polyreaction cause, and then passes to reproducibility gas
Body sulfur dioxide is combined with Ammonium persulfate. in aqueous phase and constitutes redox initiation system, so that polyreaction is fully carried out,
Reaction 12 hours, obtains containing self-association type linked polymer coil w/o type microemulsion；
(5) add dehydrated alcohol in the above-mentioned type linked polymer coil w/o type microemulsion containing self-association as precipitation
Agent is settled out hydrophobic association crosslinked polymer coil, and through petroleum ether extracting, dry (baking temperature is 50 DEG C；Dry
The dry time is 12 hours) make hydrophobic association crosslinked polymer coil powder body.
Mass fraction is that the above-mentioned self-association type linked polymer coil of 400mg/kg is simulated in 60 DEG C of Bohai SZ36-1 oilfield
Curing in water obtains self-association type linked polymer coil aqueous solution for 96 hours, is 2.0 μm to perm-plug method2Artificial
Rock core carries out the displacement test of Bohai SZ36-1 oilfield simulation oil, records and can improve simulation oil recovery under experiment condition
18.6%.
Embodiment 2, the preparation of self-association type linked polymer coil：
(1) prepare oil phase：Weigh 110.0 grams of base oil isoparaffin (Daqing Refinery company isomerization dewaxing device
Produce) (viscosity 10.85cP, flash-point is 178 DEG C), add it in 250 milliliters of there-necked flasks with stirring,
Wherein add 57.4 grams of sorbitan mono-oleic acid esters (Span-80, HLB value is 4.3) and 32.6 grams sorbitol acid anhydride lists hard
Two kinds of nonionic surfactants of fat acid polyoxyethylene (20) ether (Tween-60, HLB value is 14.9), thermal decomposition
12.5 milligrams of type initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), as oil phase after mix homogeneously；
(2) prepare aqueous phase：Weigh 58.9 grams of water-soluble monomer acrylamide, 33.3 grams of the sodium acrylate of routine respectively,
Water-soluble cross-linked monomer N, N '-diallyl-N, 6.8 grams of N, N ', N '-tetramethyl own dichloride ammonium, its molecular structure contains two
Individual double bond, to 8.1 grams of vinyl benzyl octadecyl ammonium chloride, its molecular structure contains hydrophobic monomer N, N '-dimethyl-N
There is a chain alkyl, 4.0 grams of anhydrous sodium acetate, 3.0 milligrams of chelating agen disodiumedetate, 2.0 milligrams of cosolvent urea,
2.5 milligrams of oxidative initiator Ammonium persulfate., any of the above composition is added separately to add 88.4 grams of deionized waters (electricity
Conductance≤4 μ S/cm) with stirring 250 milliliters of there-necked flasks in, stand-by as aqueous phase after dissolving, in this aqueous phase, respectively
The gross mass percentage composition of individual composition is 100%；
(3) on adding in equipped with gas gas ingress pipe, thermometer, 500 milliliters of jacketed reactors of constant speed stirrer
State oil phase, start stirring, above-mentioned aqueous phase is slowly added in oil phase, after the two mix homogeneously, form stable W/O
Type microemulsion (electrical conductivity≤0.15 μ S/cm), in this w/o type microemulsion, the weight/mass percentage composition of base oil is 27.5%,
The weight/mass percentage composition of surfactant is 22.5%, and the weight/mass percentage composition of conventional water-soluble monomer is 23.2%, water
The weight/mass percentage composition of dissolubility cross-linking monomer is 1.7%, and the weight/mass percentage composition of hydrophobic monomer is 2.0%, pH value regulator
Weight/mass percentage composition be 1.0%, the mass content of chelating agen is 0.0075%, and the mass content of cosolvent is 0.005%,
The mass content of oxidative initiator is 0.0063%, and the mass content of heat decomposition type initiator is 0.00313%；
(4) setting 25 DEG C is initiation temperature, is passed through noble gases first in the stable w/o type microemulsion of above-mentioned formation
High Purity Nitrogen gas drive oxygen, in reduction system, oxygen content (≤0.3 μ g/g) makes polyreaction cause, and then passes to reproducibility gas
Body sulfur dioxide is combined with Ammonium persulfate. in aqueous phase and constitutes redox initiation system, so that polyreaction is fully carried out,
Reaction 12 hours, obtains containing self-association type linked polymer coil w/o type microemulsion；
(5) add dehydrated alcohol in the above-mentioned type linked polymer coil w/o type microemulsion containing self-association as precipitation
Agent is settled out self-association type linked polymer coil, and through petroleum ether extracting, dry (baking temperature is 50 DEG C；It is dried
Time is 12 hours) make self-association type linked polymer coil powder body.
Mass fraction is that the above-mentioned self-association type linked polymer coil of 400mg/kg is simulated in 60 DEG C of Bohai SZ36-1 oilfield
Curing in water obtains self-association type linked polymer coil aqueous solution for 96 hours, is 2.0 μm to perm-plug method2Artificial
Rock core carries out the displacement test of Bohai SZ36-1 oilfield simulation oil, records and can improve simulation oil recovery under experiment condition
17.2%.
Embodiment 3, the preparation of self-association type linked polymer coil：
(1) prepare oil phase：Weigh 110.0 grams of base oil isoparaffin (Daqing Refinery company isomerization dewaxing device
Produce) (viscosity 10.85cP, flash-point is 178 DEG C), add it in 250 milliliters of there-necked flasks with stirring,
Wherein add 57.4 grams of sorbitan mono-oleic acid esters (Span-80, HLB value is 4.3) and 32.6 grams sorbitol acid anhydride lists hard
Two kinds of nonionic surfactants of fat acid polyoxyethylene (20) ether (Tween-60, HLB value is 14.9), mixing is all
As oil phase after even；
(2) prepare aqueous phase：Weigh 58.9 grams of water-soluble monomer acrylamide, 33.8 grams of the sodium acrylate of routine respectively,
Water-soluble cross-linked monomer N, N '-diallyl-N, 6.8 grams of N, N ', N '-tetramethyl own dichloride ammonium, its molecular structure contains two
Individual double bond, 4.8 grams of hydrophobic monomer 2- acrylamido sodium cetanesulfonate, its molecular structure contains chain alkyl, no
4.0 grams of water sodium acetate, 3.0 milligrams of chelating agen disodiumedetate, 2.0 milligrams of cosolvent urea, oxidative initiator
2.5 milligrams of Ammonium persulfate., heat decomposition type initiator 2,12.5 milligrams of 2 '-azo two (2- amidine propane) dihydrochloride, with
Upper various compositions are added separately to add 250 milliliters with stirring of 91.7 grams of deionized waters (electrical conductivity≤4 μ S/cm)
In there-necked flask, stand-by as aqueous phase after dissolving, in this aqueous phase, the gross mass percentage composition of each composition is 100%；
(3) on adding in equipped with gas gas ingress pipe, thermometer, 500 milliliters of jacketed reactors of constant speed stirrer
State oil phase, start stirring, above-mentioned aqueous phase is slowly added in oil phase, after the two mix homogeneously, form stable W/O
Type microemulsion (electrical conductivity≤0.15 μ S/cm), in this w/o type microemulsion, the weight/mass percentage composition of base oil is 27.5%,
The weight/mass percentage composition of surfactant is 22.5%, and the weight/mass percentage composition of conventional water-soluble monomer is 23.2%, water
The weight/mass percentage composition of dissolubility cross-linking monomer is 1.7%, and the weight/mass percentage composition of hydrophobic monomer is 1.2%, pH value regulator
Weight/mass percentage composition be 1.0%, the mass content of chelating agen is 0.0075%, and the mass content of cosolvent is 0.005%,
The mass content of oxidative initiator is 0.0063%, and the mass content of heat decomposition type initiator is 0.00313%；
(4) setting 10 DEG C is initiation temperature, is passed through noble gases first in the stable w/o type microemulsion of above-mentioned formation
High Purity Nitrogen gas drive oxygen, in reduction system, oxygen content (≤0.3 μ g/g) makes polyreaction cause, and then passes to reproducibility gas
Body sulfur dioxide is combined with Ammonium persulfate. in aqueous phase and constitutes redox initiation system, so that polyreaction is fully carried out,
Reaction 12 hours, obtains containing self-association type linked polymer coil w/o type microemulsion；
(5) add dehydrated alcohol in the above-mentioned type linked polymer coil w/o type microemulsion containing self-association as precipitation
Agent is settled out self-association type linked polymer coil, and through petroleum ether extracting, dry (baking temperature is 50 DEG C；It is dried
Time is 12 hours), make self-association type linked polymer coil powder body.
Mass fraction is that the above-mentioned self-association type linked polymer coil of 400mg/kg is simulated in 60 DEG C of Bohai SZ36-1 oilfield
Curing in water obtains self-association type linked polymer coil aqueous solution for 96 hours, is 2.0 μm to perm-plug method2Artificial
Rock core carries out the displacement test of Bohai SZ36-1 oilfield simulation oil, records and can improve simulation oil recovery under experiment condition
17.8%.
Embodiment 4, the preparation of self-association type linked polymer coil：
(1) prepare oil phase：Weigh 110.0 grams of No. 10 technical white oils (viscosity 10.35cP, flash-point is 156 DEG C), will
It is added in 250 milliliters of there-necked flasks with stirring, adds 57.4 grams of sorbitan mono-oleic acid esters wherein
(Span-80, HLB value is 4.3) and 32.6 grams sorbitol acid anhydride monostearate polyoxyethylene (20) ethers (Tween-60,
HLB value is 14.9) two kinds of nonionic surfactants, as oil phase after mix homogeneously；
(2) prepare aqueous phase：Weigh 59.0 grams of water-soluble monomer acrylamide, 33.8 grams of the sodium acrylate of routine respectively,
Water-soluble cross-linked monomer N, N '-diallyl-N, 6.8 grams of N, N ', N '-tetramethyl own dichloride ammonium, its molecular structure contains two
Individual double bond, to 7.8 grams of styrene benzylic ether, its molecular structure contains hydrophobic monomer cetyl polyoxyethylene groups (10)
Chain alkyl, 4.0 grams of anhydrous sodium acetate, 3.0 milligrams of chelating agen disodiumedetate, 2.0 milligrams of cosolvent urea,
2.5 milligrams of oxidative initiator Ammonium persulfate., water soluble starter 2,2 '-azo two (2- amidine propane) dihydrochloride 12.5
Milligram, any of the above composition is added separately to add the band of 88.7 grams of deionized waters (electrical conductivity≤4 μ S/cm) to stir
In 250 milliliters of there-necked flasks, stand-by as aqueous phase after dissolving, in this aqueous phase, the gross mass percentage composition of each composition is
100%；
(3) on adding in equipped with gas gas ingress pipe, thermometer, 500 milliliters of jacketed reactors of constant speed stirrer
State oil phase, start stirring, above-mentioned aqueous phase is slowly added in oil phase, after the two mix homogeneously, form stable W/O
Type microemulsion (electrical conductivity≤0.15 μ S/cm), in this w/o type microemulsion, the weight/mass percentage composition of base oil is 27.5%,
The weight/mass percentage composition of surfactant is 22.5%, and the weight/mass percentage composition of conventional water-soluble monomer is 23.2%, water
The weight/mass percentage composition of dissolubility cross-linking monomer is 1.7%, and the weight/mass percentage composition of hydrophobic monomer is 2.0%, pH value regulator
Weight/mass percentage composition be 1.0%, the mass content of chelating agen is 0.0075%g, and the mass content of cosolvent is 0.005%,
The mass content of oxidative initiator is 0.0063%, and the mass content of water soluble starter is 0.00313%；
(4) setting 20 DEG C is initiation temperature, is passed through noble gases first in the stable w/o type microemulsion of above-mentioned formation
High Purity Nitrogen gas drive oxygen, in reduction system, oxygen content (≤0.3 μ g/g) makes polyreaction cause, and then passes to reproducibility gas
Body sulfur dioxide is combined with Ammonium persulfate. in aqueous phase and constitutes redox initiation system, so that polyreaction is fully carried out,
Reaction 12 hours, obtains containing self-association type linked polymer coil w/o type microemulsion；
(5) add dehydrated alcohol in the above-mentioned type linked polymer coil w/o type microemulsion containing self-association as precipitation
Agent is settled out self-association type linked polymer coil, and through petroleum ether extracting, dry (baking temperature is 50 DEG C；It is dried
Time is 12 hours) make self-association type linked polymer coil powder body.
Mass fraction is that the above-mentioned self-association type linked polymer coil of 400mg/kg is simulated in 60 DEG C of Bohai SZ36-1 oilfield
Curing in water obtains self-association type linked polymer coil aqueous solution for 96 hours, is 2.0 μm to perm-plug method2Artificial
Rock core carries out the displacement test of Bohai SZ36-1 oilfield simulation oil, records and can improve simulation oil recovery under experiment condition
18.2%.
The result of each embodiment is comprehensively listed in Table 1 below.
The linked polymer coil that table 1, comparative example 1 are prepared with embodiment 1-4 improves recovery ratio and compares
Comparative examples 1 and 2 can be seen that the self-association type cross linked polymer of the hydrophobic monomer containing different quality containing
A ball of string is to 2.0 μm2Artificial core plugging and profile con-trol effect slightly difference, this there is self-association type cross linked polymer line
Group's crosslinking control problem, needs by targetedly adjusting hydrophobic monomer in self-association type linked polymer coil
Mass fraction realizing.
Comparative example 1,3 is with 4 as can be seen that the raising recovery ratio ability of self-association type linked polymer coil can be led to
Overregulate the molecular structure of hydrophobic monomer, preparation method is adjusted.
Above example and comparative result have only pointed out effect that the preparation method of the present invention can reach, i.e. different
Self-association type linked polymer coil can carry out adaptive producing according to characteristics of reservoirs, recovery percent of reserves.
On the other hand, compare comparative example and four specific embodiments and can be seen that mass fraction is identical, salinity phase
The profile control agent aqueous solution for plugging and profile con-trol obtaining under the conditions of, curing time identical identical with, temperature, when to gas
When survey permeability identical rock core carries out oil displacement experiment, the self-association type linked polymer coil water being obtained using this method
The recovery ratio of the preferable raising simulation oil of solution, illustrates the self-association type linked polymer coil obtaining using this method
Aqueous solution is had and the conventional linked polymer coil being obtained using emulsion polymerisation process for higher permeability porous media
Identical or more superior shut-off capacity.
Claims (10)
1. a kind of preparation method of self-association type linked polymer coil, comprises the steps：
(1) surfactant and oil-soluble initiator are dissolved in base oil as oil phase, the boiling of described base oil
Point is 60 DEG C -300 DEG C；
(2) by hydrophobic monomer, water-soluble cross-linked monomer, conventional water-soluble monomer and water soluble starter dissolving
Yu Shuizhong, is made into the aqueous solution that gross mass percentage composition is 20%-70% as aqueous phase；Described hydrophobic monomer is molecule
Contain by C in structure12-C18Carbochain constitutes the water-soluble monomer molecule of hydrophobic group；Described water-soluble cross-linked monomer
For the monomer molecule containing two or more double bonds and water soluble group in molecular structure；Described conventional water-soluble
Property monomer be in molecular structure, to contain only the monomer molecule of single double bond and water soluble group；
(3) aqueous phase described in step (2) is mixed with the oil phase described in step (1) and carry out emulsifying, formed and divide
Dephasing is aqueous phase, continuous phase is the w/o type microemulsion of oil phase；In described w/o type microemulsion, described base oil,
Surfactant, oil-soluble initiator, water soluble starter, hydrophobic monomer, water-soluble cross-linked monomer and routine
The weight/mass percentage composition of water-soluble monomer respectively 10.0%-40.0%, 10.0%-30.0%, 0.01%-5.0 ‰,
0.01%-30.0 ‰, 0.1%-50.0%, 0.1%-50.0% and 10.0%-40.0%, balance of water；
(4) it is passed through noble gases initiated polymerization in the described w/o type microemulsion being formed to step (3),
Described self-association type linked polymer coil is obtained final product in described w/o type microemulsion.
2. preparation method according to claim 1 it is characterised in that：Methods described is additionally included in containing
State the step adding precipitant to be precipitated and be dried in the w/o type microemulsion of self-association type linked polymer coil.
3. preparation method according to claim 2 it is characterised in that：Described precipitant be dehydrated alcohol,
Absolute methanol or acetone.
4. according to described preparation method arbitrary in claim 1-3 it is characterised in that：Described in step (1)
The HLB value of surfactant is 4-10；Described surfactant is nonionic surfactant, anionic surface
At least one of activating agent and cationic surfactant；Described base oil is n-alkane, isoparaffin, cycloalkanes
At least one of hydrocarbon and aromatic hydrocarbon solvent；Described oil-soluble initiator is heat decomposition type initiator.
5. according to described preparation method arbitrary in claim 1-4 it is characterised in that：Described in step (2)
Hydrophobic monomer is at least one of anionic monomer, cationic monomer and non-ionic monomer；Described anionic monomer is such as
Shown in formula (1)；Shown in described cationic monomer such as formula (2) or formula (3)；Described non-ionic monomer such as formula (4)
Shown；
In formula (1), n is the natural number of 5-13；In formula (2) and formula (3), R1And R2Represent benzyl or tool
There are alkyl or the alkoxyl of 1-3 carbon atom；R3Represent and there is the alkyl of 8-22 carbon atom or monosubstituted 6-22
The alkyl benzyl of individual carbon atom；R4Represent hydrogen or methyl；A represents oxygen atom or NH；B represents has 2-4
The alkylidene of carbon atom or alkylene oxide group；M represents methylene or monosubstituted benzyl；X1Represent anion；, R5
Represent the alkyl phenyl of hydrogen, the alkyl of 8-22 carbon atom or monosubstituted 6-22 carbon atom；D represents methylene
Base, carbonyl or monosubstituted benzyl；It is embedding that E represents polyoxyethylene groups, polyoxypropylene base or PULLRONIC F68
Section chain link；In formula (4), R5Represent hydrogen, the alkyl of 8-22 carbon atom or monosubstituted 6-22 carbon atom
Alkyl phenyl；D represents methylene, carbonyl or monosubstituted benzyl；E represent polyoxyethylene groups, polyoxypropylene base,
Or PULLRONIC F68 block chain link.
6. according to described preparation method arbitrary in claim 1-5 it is characterised in that：Described in step (2)
Water-soluble cross-linked monomer is N, N'- methylene-bisacrylamide, polyethyleneglycol diacrylate, Polyethylene Glycol diene
Propyl ether, N, N- diallyidimethylammonium chloride amine, N, N '-diallyl-N, N, N ', N '-tetramethyl own dichloride ammonium,
- two couples of vinyl benzyl-N of N, N ', N, N ', N '-tetramethyl own dichloride amine, three acrylic acid-(propyl group) trimethyl or
Pentaerythritol triallyl ether；Described conventional water-soluble monomer is acrylamide, Methacrylamide, N- ethylene
Base Methanamide, N- vinyl acetamide, NVP, N, N- DMAA, acrylonitrile,
Diacetone acrylamide, (first) HEA acrylamide, propenyl, (methyl) acrylic acid,
Itaconicacid, maleic acid, 2- acrylamide-2-methyl propane sulfonic, the corresponding salt of vinyl sulfonic acid monomer, (methyl)
Acrylyl oxy-ethyl-trimethyl salmiac, (methyl) acrylyl oxy-ethyl diethylmethyl ammonium chloride, (methyl)
Acryloxyethyldimethyl benzyl ammonium chloride, (methyl) acrylyl oxy-ethyl diethylbenzyl ammonium chloride and diformazan
At least one of base diallyl ammonium chloride；Described water soluble starter is 2,2 '-azo two { 2- [1- (2- ethoxy) -2-
Imidazoline -2- base] propane dihydrochloride, 2,2 '-azo two (2- amidine propane) dihydrochloride, 2,2 '-azo two [2- (2-
Imidazoline -2- base) propane) dihydrochloride or 2,2 '-azo two [2- (5- methyl -2- imidazoline -2- base) propane) two hydrochloric acid
Salt.
7. according to described preparation method arbitrary in claim 1-6 it is characterised in that：Step (4) is described poly-
The temperature closing reaction can be 5 DEG C -85 DEG C；The time of described polyreaction can be 4 hours -12 hours.
8. according to described preparation method arbitrary in claim 1-7 it is characterised in that：The described water of step (2)
Also include in phase in oxidative initiator, heat decomposition type initiator, chelating agen, pH value regulator and cosolvent extremely
Few one kind.
9. according to described preparation method arbitrary in claim 1-8 it is characterised in that：Described in step (4)
Noble gases are nitrogen or argon；The step being passed through reducibility gas is also included in described polyreaction；Described reduction
Property gas be sulfur dioxide.
10. the self-association type linked polymer coil that in claim 1-9 prepared by arbitrary methods described.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106833590A (en) * | 2017-03-28 | 2017-06-13 | 四川光亚聚合物化工有限公司 | A kind of Water-In-Oil association type displacement of reservoir oil concentration thickener and preparation method thereof |
| CN106833591A (en) * | 2017-03-28 | 2017-06-13 | 四川光亚聚合物化工有限公司 | A kind of oil-in-water association type displacement of reservoir oil concentration thickener and preparation method thereof |
| CN106957641A (en) * | 2017-03-28 | 2017-07-18 | 四川光亚聚合物化工有限公司 | A kind of Water-In-Oil association type acidifying concentration thickening agent and preparation method thereof |
| CN110229272A (en) * | 2019-07-06 | 2019-09-13 | 西南石油大学 | A kind of hydrophobic associated polymer and preparation method thereof |
| CN111349426A (en) * | 2018-12-21 | 2020-06-30 | 中国石油天然气股份有限公司 | Diverting acid, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106833590A (en) * | 2017-03-28 | 2017-06-13 | 四川光亚聚合物化工有限公司 | A kind of Water-In-Oil association type displacement of reservoir oil concentration thickener and preparation method thereof |
| CN106833591A (en) * | 2017-03-28 | 2017-06-13 | 四川光亚聚合物化工有限公司 | A kind of oil-in-water association type displacement of reservoir oil concentration thickener and preparation method thereof |
| CN106957641A (en) * | 2017-03-28 | 2017-07-18 | 四川光亚聚合物化工有限公司 | A kind of Water-In-Oil association type acidifying concentration thickening agent and preparation method thereof |
| CN111349426A (en) * | 2018-12-21 | 2020-06-30 | 中国石油天然气股份有限公司 | Diverting acid, preparation method and application thereof |
| CN110229272A (en) * | 2019-07-06 | 2019-09-13 | 西南石油大学 | A kind of hydrophobic associated polymer and preparation method thereof |
| CN110229272B (en) * | 2019-07-06 | 2021-06-04 | 西南石油大学 | Hydrophobic association polymer and preparation method thereof |
| CN115260388A (en) * | 2022-09-05 | 2022-11-01 | 东营市大用石油助剂有限责任公司 | Copolymerization cohydrolysis viscoelastic polymer high molecular material for tertiary oil recovery and preparation method thereof |
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