CN106866878A - Polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir and preparation method thereof - Google Patents
Polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to a kind of polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir and preparation method thereof, gel-like blocking agent present in prior art is mainly solved typically only to be used for improving the anisotropism of oil reservoir, polymer is typically only used for improving oil and water mobility ratio, the two problem that can not be united two into one.The present invention is by using a kind of special construction hydrophobic associated polymer, compounded by a certain percentage with some surfactants, according to the field condition of reservoir formation, the association intensity and viscosity of polymer can be adjusted, be allowed to play the double effects not only adjusted but also drive in injection process.The profile control agent system is in terms of parts by weight, comprising 0.05~1.0 part of hydrophobic associated polymer of special construction, 0.05~1.0 part of surfactant, 99~99.95 parts of technical schemes of water, the problem is preferably resolved, can be used for industrial production and the application of the polymer-type profile control agent of high temperature and high salt harshness oil reservoir.
Description
Technical field
The present invention relates to a kind of polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir and preparation method thereof.
Background technology
Domestic each elephant by once, secondary oil recovery, crude oil water content is continuously increased, and part elephant is first laggard
Enter tertiary phase.There is decline trend year by year by long-term exploitation, current crude output in many oil fields.In order to
Stable yields, some later stages employ adopts injection mode by force, causes underground to form many macropores.Reservoir Heterogeneity and
Unfavorable mobility ratio is the two big key factors for influenceing water-drive pool sweep efficiency and ultimate recovery.For water-drive pool
The above mentioned problem of appearance, profile control and water plugging is to solve Reservoir Heterogeneity more effective method, and polymer flooding can change
The mobility ratio of kind water drive oil, the fingering for solving injection water is now leaned on.
For profile control and water plugging, using it is more be polymer gel class (cross-linked polymer), according to the polymer for using
The difference of concentration, cross-linking polymer system is divided three classes：Body gel (Bulk Gel abbreviation BG), colloidal state point
Gel (Colloidal Dispersion Gel abbreviation CDG) and Weak Gels (Weak Gel abbreviation WG) are dissipated, this three
The concentration limit and formation condition that class polymerization-filling thing is used depend on several factors, such as temperature, salinity, crosslinking
Agent type and pH value etc..Although the scene application of existing certain scale, because system is more complicated, plastic is present
Certain uncertainty, will particularly screen suitable polymer relatively difficult under high temperature and high salinity.
The mechanism of oil displacement of polymer mainly uses the viscosity of water-soluble polyacrylamide strand, improves displacing fluid
Mobility ratio, improves displacement efficiency and swept volume, and the purpose of recovery ratio is improved so as to reach.Polymerization used for tertiary oil recovery
Thing must have good thickening, heatproof, salt resistance, shear resistant, and performance is steady in a long-term.In recent years, it is relevant
The research of temperature-resistant and anti-salt type polyacrylamide is main by introducing big side base or rigid side base raising on main polymer chain
The monomer or the monomer insensitive to salt that the heat endurance of polymer, introducing suppress hydrolysis carry out copolymerization to improve polymerization
The hydrolysis and anti-salt property of thing, or improve the temperature-resistant anti-salt of polymer by the heat resistance and salt tolerance of hydrophobic grouping
Performance.In current tertiary oil recovery, the polymer of high temperature high temperature requirement can be really met seldom, can not particularly meet
More than salinity 100000mg/L, the requirement that more than 85 DEG C of temperature.
Hydrophobic associated water-soluble polymer refers to a small amount of hydrophobic grouping one on polymer hydrophilicity macromolecular chain
Class water-soluble polymer.Due to the SOLUTION PROPERTIES such as the thickening of its uniqueness, salt resistance, anti-shearing, as new polymers
Oil displacement agent is applied to high salt, high shear oil reservoir development and has a good application prospect.Because drawing in polymer molecule
The hydrophobic association type copolymer for entering hydrophobic grouping and generating, its hydrophobic chain link is lived with similar to surface in aqueous medium
Property agent mode assemble and associate, effective hydrodynamic volume of macromolecular ball of string increase, aqueous medium viscosity is improved, compared with
Big side base plays shielding action to polymer molecule backbone, weakens the p- COO of salt ion—The influence of group；And
Larger side base also has certain space steric effect, strengthens chain rigidity.But it is existing to be birdsed of the same feather flock together there are some researches show this
It is conflicting between the associative ability and water solubility of compound, the polymer of good water solubility often hydrophobic monomer carbochain compared with
Short or content is relatively low, and associating effect is not obvious, and certain association effect need to be just shown under polymer concentration higher
Fruit meets heat and salinity tolerance performance；And the polymer associate of the hydrophobic monomer containing long-chain or high content is very capable, resist
Warm anti-salt property is good, but poorly water-soluble, and generally requiring long time can just be completely dissolved, and losing industrialization should
Value.How preferable equalization point is found between, be that can such polymer be widely used in three
The key of secondary oil recovery process.
The country has carried out numerous studies in terms of hydrophobic associated polymer, and wherein Southwest Petroleum Institute, Chengdu science and technology is big
, petrochina exploration and development research institute, University of Petroleum, Northcentral University etc. achieve preferably progress and achievement.
Feng Rusen etc. (CN1793189A) using micella copolymerization method synthesized containing acrylamide, PAA and pi-allyl-
Three kinds of hydrophobic associated polymers of construction unit of alkyl phenyl ether, although have preferable Efficient Adhesive Promotion, but pi-allyl-alkane
The synthesis of base phenyl ether monomer is complex；Zhong Chuanrong etc. (CN101293944A, CN 101148582A) synthesizes
Hydrophobic associated polymer of the condensed-nuclei aromatics containing vinyl as hydrophobic monomer, the polymerization process time is more long, only evaluates
Efficient Adhesive Promotion of the polymer in fresh water and salt solution at 45 DEG C, salt resistance effect assessment NaCl concentration
<100000mg/L、CaC12Concentration<The situation of 1000mg/L；Ou Yangjian etc. (CN1317501) HMW is dredged
Water association polymer, in 75 DEG C of total salinity 12000mg/L, wherein Ca2+And Mg2+It is 300mg/L, sample is dense
It is 1500mg/L to spend, and using Brookfield viscometer, shear rate is 36.7s-1Viscosity is 15.6~12.4mPa.s；Kong Ying
The water-soluble hydrophobic associated type of super high molecular weight containing fluorocarbon group is synthesized Deng (CN1528734, CN1528797)
Polymer, have rated it in triumph salt solution (total salinity 6000mg/L, calcium ions and magnesium ions 500mg/L) 70 DEG C of conditions
Under tackifying, wherein fluorinated acrylate hydrophobic monomer is expensive；(new family's hydrophobic association gathers Jiang Liding
The synthesis of acrylamide and its rheological property of the aqueous solution, Master's thesis in 2007) use surface active monomer
NaAMC14S has been successfully prepared the copolymerization with hydrophobic block structure with the method for the homogeneous combined polymerization of the AM aqueous solution
Thing NaAMC14S/AM, overcomes some shortcomings that micellar co-polymerization is brought using conventional surfactants, altogether
Polymers NaAMC14The length of hydrophobic micro- block of S/AM can be controlled by adjusting the consumption of additional electrolyte,
But research work biases toward theory, the not no evaluation result under the conditions of actual oil field mineral reserve.
The studies above is made a general survey of, current synthetizing hydrophobic associated polymer most common method is micellar free radical copolymerization method,
Needing to add substantial amounts of surfactant (such as SDS) when adopting this method polymerization makes hydrophobic monomer solubilising in micella
It is interior, but add the substantial amounts of surfactant to have significant impact to the association behavior of polymer in the course of the polymerization process, this
A little surfactants interact in polymerizate with hydrophobic segment, deteriorate hydrophobic associated water-soluble polymer
Performance.If removing these surfactants, the complexity of the last handling process such as separation and purifying can be increased.For
Simplified last handling process simultaneously strengthens the dissolubility of polymer, can be using the inherently hydrophobicity list with surface-active
Body.This kind of monomer contains hydrophobic grouping and hydrophilic radical simultaneously, and surface-active need not be it is possible to additionally incorporate in combined polymerization
Agent, can directly use traditional free yl solution polymerization, and can make that hydrophobic monomer is highly unordered irregularly to be drawn
In entering copolymer.But foreign countries have research (Ezzell, S.A., McCormick, C.L., Macromolecules 1992,25 (7),
1881~1886) find, the copolymer of this kind of ionic hydrophobic monomer critical association concentration in aqueous is micella
More than 2 times of the identical Hydrophobic chain length of copolymer, this to hydrophobic associated polymer application industrially extremely not
Profit.As can be seen here, structure, property, viscosifying mechanisms of the domestic and international researcher to hydrophobic associated water-soluble polymer
And application has done numerous studies, has explored work, but polymer evaluation essentially according to grand celebration or Shengli Oil Field some ore deposits
Tibetan condition, temperature and salinity are all not belonging to high temperature and high salt type, for more than salinity 100000mg/L, temperature
More than 85 DEG C of condition almost without reference to.
The present invention is in the synthesis to each hydrophobically associating water soluble polymer and hydrophobically modified polyelectrolyte, structural characterization
And SOLUTION PROPERTIES aspect carry out extensively, on the basis of in-depth study, it is opposite to that using the monomer with surface-active
Interaction between the ionic comonomer of electric charge, one is that ionic comonomer has solubilization to surface active monomer,
It is not required to separately add surfactant in polymerization, two can be to form both sexes hydrophobic associated polymer, even if in hydrophobic list
Polymer also has high-effective viscosity and excellent heatproof, salt resistance and long-time stability under body lower content, and is not required to
Hydrolytic process, not only helps long-term ageing property afterwards, also reduces energy consumption, and does not influence the dissolving of product
Property；Add a certain amount of viscous steady agent to not only help the dissolving of polymer and play collaboration thickening in drying process to make
With yet further enhances ageing resistace.Found especially by substantial amounts of combine experiment, the hydrophobically associating
Polymer has special interaction with some surfactants, and the change according to both ratios can form difference
The polymer fluid or gel of associating intensity and viscosity, can simultaneously play the double effects not only adjusted but also drive, at three times
Serve as profile control agent in oil recovery.Polymer profile control agent suitable for high temperature and high salt harshness oil reservoir of the present invention is suitable for
The requirement of harsh oil reservoir of the total salinity more than 100,000 mg/L, temperature more than 85 DEG C, has in tertiary oil recovery engineering
There is good application prospect.
The content of the invention
One of technical problems to be solved by the invention be present in prior art high temperature and high salt harshness oil reservoir in coagulate
Glue class blocking agent is typically only used for improving the anisotropism of oil reservoir, and polymer is typically only used for improving oil and water mobility ratio, two
The problem that person can not unite two into one.By using a kind of polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir,
By special construction hydrophobic associated polymer, and compounded by a certain percentage by with some surfactants, according to
The field condition of reservoir formation, can adjust the association intensity and viscosity of polymer, played in injection process and both adjusted
The double effects for driving again.
The two of the technical problems to be solved by the invention be to provide it is a kind of solve in one of technical problem suitable for height
The preparation method of the polymer-type profile control agent of warm high salt harshness oil reservoir, the method has polymerisation process simple, nothing
Need to separate, purify and the step, the advantage of reduces cost such as hydrolysis afterwards.
One of in order to solve the above-mentioned technical problem, the present invention is as follows using following technical scheme：One kind is applied to high temperature
The polymer-type profile control agent of high salt harshness oil reservoir, by the hydrophobic associated polymer and surfactant compound of special construction
Composition, in terms of parts by weight, comprising following components：
A) 0.05~1.0 part of polymer；
B) 0.05~1.0 part of surfactant；
Wherein, the polymer is hydrophobic associated polymer, hydrophobic containing 0.5~2% 8~22 Long carbon chain ionics
Monomer；The surfactant is selected from nonionic, anion or the cation form that hydrophobic part carbon chain lengths are 8~18
Face activating agent.
In above-mentioned technical proposal, the hydrophobic associated polymer, by the solution including following monomer composition compound
Reacted in the presence of initiator and be obtained；Described monomer, in terms of parts by weight, comprising following components：
A) 5~99.9 parts of nonionic water-soluble monomers；
B) 0~50 part of anionic monomer or/and cationic monomer；
C) 0.1~10 part of structures alone
D) 0.1~5 part of hydrophobic monomer；
E) 200~2000 parts of water；
Wherein, the structures alone is the function monomer with cyclic structure or dendritic structure；
The composite initiator, in terms of above-mentioned whole weight percent monomers, comprising following components：
A) 0.003~0.5% persulfate；
B) 0.003~0.5% sulphite or acid sulphite；
C) 0.003~1% by NR1R2R3Tertiary amine compounds of representative or by N+R4R5R6R7The quaternary ammonium of representative
Class compound or by NH2R8The fat amine compound of representative, R in formula1~R7It is selected from C1~C14Straight or branched
Alkyl or alkyl derivative, R8Selected from C1~C18Straight or branched alkyl or alkyl derivative；
D) 0.005~2% azo compound；
E) 0.01~10% urea, thiocarbamide；
F) 0.03~1.0% disodium ethylene diamine tetraacetate or diethylene triamine pentacetic acid (DTPA) sodium；
G) 0.03~1.0% molecular weight regulator.
In above-mentioned technical proposal, the function monomer with cyclic structure preferably is selected from NVP, N- benzene
At least one in base maleimide；The function monomer of dendritic structure preferably is selected from N-tert-butyl acrylamide.
In above-mentioned technical proposal, the nonionic water-soluble monomers preferred scheme be selected from water-soluble vinyl monomer,
The vinyl monomer is selected from acrylamide, Methacrylamide, NIPA, N-N- dimethyl propylenes
Acrylamide, N-N- acrylamides and N hydroxymethyl acrylamide, N- vinyl formamides, N- vinyl second
At least one in acid amides.The anionic monomer preferred scheme be selected from 2- acrylamide-2-methylpro panesulfonic acids,
Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylbenzenesulfonic acid, vinyl
Sulfonic acid, vinyl phosphonate, allyl sulphonic acid, allyl phosphonic acid and/or its water-soluble alkali, alkaline-earth metal and ammonium
At least one in salt；Cationic monomer is selected from dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl chlorine
In change ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides
At least one.
In above-mentioned technical proposal, the hydrophobic monomer is preferably the hydrophobic monomer with surface-active, further preferably
Scheme is anionic surface activity monomer or cationic surfactant monomer.It is described with the hydrophobic of surface-active
Monomer more preferably scheme is selected from the 8-22 mono-vinyl class compound of carbon atom.Preferred technical scheme, it is described
Anionic surface activity monomer is the acrylamide azanyl sodium sulfonate that vinyl carbochain number is 8~18；Cationic
Surface active monomer is the allyl alkyl ammonium chloride that vinyl carbochain number is 12~22.
In above-mentioned technical proposal, the persulfate preferred scheme is selected from potassium peroxydisulfate, sodium peroxydisulfate or persulfuric acid
Ammonium；Sulphite is selected from sodium sulfite or potassium sulfite, and acid sulphite is selected from sodium hydrogensulfite or bisulfite
Potassium；Tertiary amine compounds preferred scheme is selected from methacrylic acid N, N- dimethylaminoethyls, acrylic acid N, N- diformazan
Amino ethyl ester, β-dimethylaminopropionitrile, tetramethylethylenediamine, hexa etc.；Quaternary ammonium compoundses are selected from
N, N- dimethyl diallyl ammonium chloride, N, N- diethyl diallyl ammonium chlorides；Fat amine compound is selected from first
Amine, ethylenediamine, 1,3- propane diamine, 1,4- butanediamine, N, N- dimethyl -1,3- propane diamine etc.；Azo compound is selected
From azo diisobutyl amidine hydrochloride, 2,2'- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride etc.；Molecular weight is adjusted
Section agent preferred scheme be selected from isopropanol, the tert-butyl alcohol, isobutanol, pentaerythrite or dipropylene glycol at least
It is a kind of.
In order to solve the above-mentioned technical problem two, the present invention is as follows using following technical scheme：One kind is applied to high temperature
The preparation method of the polymer-type profile control agent of high salt harshness oil reservoir, comprises the following steps：
A) add in a kettle. water, nonionic water-soluble monomers, anionic monomer or/and cationic monomer,
Structures alone, hydrophobic monomer；
B) composite initiation system in addition to oxidation, reducing agent is added, is stirred, form solution；
C) pH value of regulation solution is to 7~10, and is passed through nitrogen, temperature in the kettle is down into 10~30 DEG C, then
Remaining composite initiator is added, after continuing to be passed through nitrogen, sealing；
D) polymerization is triggered to start after 0.1~1 hour, reaction temperature rises to 50~70 DEG C, and temperature-rise period continues 2~5
Hour, 1~3 hour is incubated after reaching the highest temperature, obtain gel polymerizate；
E) cut and add after glue drying aids, mediate it is uniform after at 85~95 DEG C forced air drying 1~3 hour, use
Pulverizer or roller are crushed to certain particle size, obtain hydrophobic associated polymer；
F) the desired amount of hydrophobic associated polymer and surfactant are well mixed, obtain described suitable for high temperature
The polymer-type profile control agent of high salt harshness oil reservoir.
In above-mentioned technical proposal, the drying aids, in terms of association polymer whole weight percent monomer, including
Following components：0.1~3% dispersant, 0.1~20% viscous steady agent.It is described to glue steady agent selected from free radical resistant type such as sulfurous
Sour sodium, phenol/quinones etc., reduced form such as sodium thiosulfate, thiocarbamide, sodium hydrogensulfite, tetraethyl amylamine, hydrazine etc.,
High-valency metal particle complexing agent such as arabo-ascorbic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid etc., alcohol, amine such as isopropanol, tertiary fourth
Alcohol, methenamine etc., one or more in polymer electrolyte such as PVA；Surfactant is selected from anionic table
Face activating agent such as C8-16Sodium alkyl sulfate, C8-16Sodium alkyl benzene sulfonate etc., cationic surface active agent such as C8-16
Alkyl trimethyl bromine (chlorine) changes ammonium etc., nonionic such as APES (EO=4~30) or they
Any mixture.
Polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir of the present invention and preparation method thereof, due to
Employ with the opposite ion monomer of surface active monomer ion characteristic, both interactions are to surface-active
Monomer has solubilization, is not required to separately add surfactant in polymerization；Even and if the hydrophobic associated polymer for obtaining
Polymer also has excellent temperature-resistant anti-salt, thermally-stabilised and anti-shear performance under hydrophobic monomer lower content；And
Composite initiation system is employed, and matched with preferred technique, therefore reacting balance, be conducive to chain to increase, produced
Thing molecular weight is controllable, and is not required to rear hydrolytic process, not only helps long-term ageing property, also reduces production energy
Consumption, and the dissolubility of product is not influenceed；A certain amount of viscous steady agent is added in drying process, polymerization is not only helped
The dissolving of thing simultaneously plays collaboration viscosifying action, yet further enhances ageing resistace.
Use the polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir provided by the present invention and its preparation side
Method, shows excellent viscosifying action under high temperature and high salinity, and the viscous dense curve of polymer shows, the hydrophobic association
Polymer has stronger association, and viscosity amplification goes out up to two to three orders of magnitude, and critical micelle concentration
Present below 1000mg/L；There is polymer salt to viscosify effect more than 100,000 under salinity；Polymer it is long-term
Ageing-resistant and anti-shear performance is good.Compounded by a certain percentage with some surfactants with the hydrophobic associated polymer
Obtain being applied to the polymer-type profile control agent of high temperature and high salt harshness oil reservoir afterwards, viscosity can further improve, associate and make
With also can further strengthen, stronger sealing characteristics is shown, sealing ratiod can be used up to 93% as profile control agent,
Achieve preferable technique effect.
Below by specific embodiment, the present invention will be further elaborated.
Specific embodiment
【Embodiment 1】
First add in a kettle. in 2500g deionized waters, add 430g acrylamides (AM), 2- acrylamides
Base -2- methyl propane sulfonic acid (AMPS) 150g, 3.5g2- acrylamido myristyl sodium sulfonate (NaAMC14S)、
4.5g acrylyl oxy-ethyl-trimethyl salmiacs (DAC), neutrality is neutralized to NaOH, is subsequently added ethylenediamine
Tetraacethyl disodium 0.04g, urea 7g, isopropanol 0.07g, stirring is to being completely dissolved.PH value is adjusted with NaOH
To 8.9, and start to be passed through high pure nitrogen, temperature in the kettle is down to 15 DEG C after 30min, then sequentially add 0.2%
Aqueous solution of sodium bisulfite 10g, 0.5% methacrylic acid N, N- dimethylaminoethyl (DMAEMA) aqueous solution
10g, 0.5% azo diisobutyl amidine hydrochloride 10g, 0.3% persulfate aqueous solution 10g, continue logical nitrogen
Sealed after 30min.Reaction temperature is gradually increased to 52 DEG C after 1 hour, reaction obtains gel polymerization after 3.5 hours
Product, adds the drying aids of dispersant containing 5g and 30g thiocarbamides to mediate uniformly after cutting glue, and air blast is done at 90 DEG C
Dry 1.5h, sampling analysis after sieving is smashed with pulverizer.
It is 89.9% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test Rong solution Shi Jian≤90min, apparent viscosity
In 95 DEG C, salt solution total salinity 180000mg/L, Ca2++Mg2+：1000mg/L polymer is dense under 5000mg/L
Degree solution, using Haake torque rheometer, concentric drums shear rate 7.34s-1Under apparent viscosity be 76mPas.95℃
Viscosity retention ratio is respectively 102% after aging 30 days.
1000mg/L polymer concentrations solution is well mixed with 500mg/L sodium dodecyl sulfate solutions, viscosity
690mPa.s can be risen to, the core plugging of 1500mD shows, sealing ratiod is up to 82%.
【Embodiment 2】
First add in a kettle. in 2600g deionized waters, add 480g acrylamides (AM), 2- acrylamides
Base -2- methyl propane sulfonic acid (AMPS) 130g, 4.0g2- acrylamido dodecyl sodium sulfate (NaAMC12S)、
7.8g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides (DMC) and 5.0g nitrogen vinyl pyrrolidone (NVP),
Neutrality is neutralized to NaOH, disodium ethylene diamine tetraacetate 0.045g, urea 7.0g, isopropanol 0.06g is subsequently added,
Stirring is to being completely dissolved.PH value is adjusted to 9.0 with NaOH, and starts to be passed through high pure nitrogen, by kettle after 30min
Interior temperature is down to 16 DEG C, then sequentially adds 0.2% aqueous solution of sodium bisulfite 10.2g, 0.5% acrylic acid N, N-
Dimethylaminoethyl (DA) aqueous solution 11g, 0.5% azo diisobutyl amidine hydrochloride 11.9g, 0.3% mistake
Potassium sulfate solution 11.2g, seals after continuing logical nitrogen 30min.Reaction temperature is gradually increased to 58 DEG C after 1 hour,
Reaction obtains gel polymerizate after 3 hours, and 5g dispersants, 6g isopropanols and 45g sulfurous are added after cutting glue
Sour sodium mediates uniform, the forced air drying 1h at 95 DEG C, and sampling analysis after sieving is smashed with pulverizer.
It is 88.7% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test Rong solution Shi Jian≤90min.Apparent viscosity
In 95 DEG C, salt solution total salinity 180000mg/L, Ca2++Mg2+：1000mg/L polymer is dense under 5000mg/L
Degree solution, using Haake torque rheometer, concentric drums shear rate 7.34s-1Under apparent viscosity be 69Pas.95℃
Viscosity retention ratio is respectively 117% after aging 30 days.
1000mg/L polymer concentrations solution is well mixed with 600mg/L neopelex solution, is glued
Degree can rise to 650mPa.s, and the core plugging of 1500mD shows, sealing ratiod is up to 84%.
【Embodiment 3】
First add in a kettle. in 2700g deionized waters, add 500g acrylamides (AM), 2- acrylamides
Base -2- methyl propane sulfonic acid (AMPS) 150g, 5.2g2- acrylamido sodium cetanesulfonate (NaAMC16S)
With 9.4g dimethyl diallyl ammonium chlorides (DMDAAC), neutrality is neutralized to NaOH, is subsequently added second
Edetate disodium 0.05g, urea 8.0g, isopropanol 0.07g, stirring is to being completely dissolved.Adjusted with NaOH
PH value starts to be passed through high pure nitrogen to 9.5, and temperature in the kettle is down into 20 DEG C after 30min, then sequentially adds
0.2% aqueous solution of sodium bisulfite 10.2g, 0.5% acrylic acid N, N- dimethylaminoethyl (DA) aqueous solution 12.1g,
0.5% 2,2'- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride 12g, 0.3% persulfate aqueous solution 11g,
Sealed after continuing logical nitrogen 30min.Reaction temperature is gradually increased to 55 DEG C after 1 hour, reaction is obtained after 2.5 hours
To gel polymerizate, 5g dispersants, 20g thiocarbamides and 5g 1-hydroxy ethylidene-1,1-diphosphonic acids is added to mediate after cutting glue
Even, the forced air drying 2h at 85 DEG C smashes sampling analysis after sieving with pulverizer.
It is 90.3% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test Rong solution Shi Jian≤90min.Apparent viscosity
In 95 DEG C, salt solution total salinity 180000mg/L, Ca2++Mg2+：1000mg/L polymer is dense under 5000mg/L
Degree solution, using Haake torque rheometer, concentric drums shear rate 7.34s-1Under apparent viscosity be 62Pas.95℃
Viscosity retention ratio is respectively 107% after aging 30 days.
1000mg/L polymer concentrations solution is well mixed with 400mg/LOP-10 solution, viscosity can rise to 480
The core plugging of mPa.s, 1200mD shows, sealing ratiod is up to 87%.
【Embodiment 4】
First add in a kettle. in 2600g deionized waters, add 510g acrylamides (AM), 2- acrylamides
Base -2- methyl propane sulfonic acid (AMPS) 170g, 5.0g hexadecyldimethyl benzyl ammonium allyl ammonium chloride (C16DMAAC)
With 7.8g methacrylic acids (MAA), neutrality is neutralized to NaOH, is subsequently added disodium ethylene diamine tetraacetate
0.048g, urea 7.5g, tert-butyl alcohol 0.08g, stirring is to being completely dissolved.PH value is adjusted to 8.7 with NaOH, and
Start to be passed through high pure nitrogen, temperature in the kettle is down to 12 DEG C after 30min, then sequentially add 0.2% bisulfite
Sodium water solution 11.2g, 0.5% methacrylic acid N, N- dimethylaminoethyl (DMAEMA) aqueous solution 12.6g,
0.5% azo diisobutyl amidine hydrochloride 12g, 0.3% persulfate aqueous solution 10.9g, continues logical nitrogen 30min
After seal.Reaction temperature is gradually increased to 52 DEG C after 1 hour, reaction obtains gel polymerizate after 3 hours,
5g dispersants, 20g thiocarbamides and 4g methenamines is added to mediate uniformly after cutting glue, the forced air drying 1.5h at 90 DEG C,
Sampling analysis after sieving is smashed with pulverizer.
It is 92.4% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test Rong solution Shi Jian≤90min.Apparent viscosity
In 95 DEG C, salt solution total salinity 180000mg/L, Ca2++Mg2+：1000mg/L polymer is dense under 5000mg/L
Degree solution, using Haake torque rheometer, concentric drums shear rate 7.34s-1Under apparent viscosity be 163Pas.95℃
Viscosity retention ratio is respectively 123% after aging 30 days.
The 1000mg/L polymer concentrations solution of above-mentioned salt solution is well mixed with 500mg/LOP-15 solution, equally
Under the conditions of apparent viscosity can rise to 920mPa.s, the core plugging of 2000mD shows that sealing ratiod reaches
93%.
【Comparative example 1】
1000mg/L polymer concentrations solution in embodiment 4 is individually carried out the core plugging table of 2000mD
Bright, sealing ratiod only has 35%.The apparent viscosity data of polymer solution, Yi Jishi before and after by being compounded in embodiment 4
Apply the sealing ratiod data in example 4 and comparative example 1 as can be seen that the compounding of polymer and surfactant achieve compared with
Good synergistic function.
Claims (10)
1. it is a kind of suitable for high temperature and high salt harshness oil reservoir polymer-type profile control agent, in terms of parts by weight, comprising with
Lower component：
A) 0.05~1.0 part of polymer；
B) 0.05~1.0 part of surfactant；
Wherein, the polymer is hydrophobic associated polymer, hydrophobic containing 0.5~2% 8~22 Long carbon chain ionics
Monomer；The surfactant is selected from nonionic, anion or the cation form that hydrophobic part carbon chain lengths are 8~18
Face activating agent.
2. the polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir according to claim 1, it is special
It is wherein described hydrophobic associated polymer to levy, by the depositing in composite initiator of the solution including following monomer composition
It is obtained in lower reaction；Described monomer, in terms of parts by weight, comprising following components：
A) 5~99.9 parts of nonionic water-soluble monomers；
B) 0~50 part of anionic monomer or/and cationic monomer；
C) 0.1~10 part of structures alone；
D) 0.1~5 part of hydrophobic monomer；
E) 200~2000 parts of water；
Wherein, the structures alone is the function monomer with cyclic structure or dendritic structure；
The composite initiator, in terms of above-mentioned whole weight percent monomers, comprising following components：
A) 0.003~0.5% persulfate；
B) 0.003~0.5% sulphite or acid sulphite；
C) 0.003~1% by NR1R2R3Tertiary amine compounds of representative or by N+R4R5R6R7The quaternary ammonium of representative
Class compound or by NH2R8The fat amine compound of representative, R in formula1~R7It is selected from C1~C14Straight or branched
Alkyl or alkyl derivative, R8Selected from C1~C18Straight or branched alkyl or alkyl derivative；
D) 0.005~2% azo compound；
E) 0.01~10% urea, thiocarbamide；
F) 0.03~1.0% disodium ethylene diamine tetraacetate or diethylene triamine pentacetic acid (DTPA) sodium；
G) 0.03~1.0% molecular weight regulator.
3. the hydrophobic associated polymer of special construction according to claim 2, it is characterised in that described non-
Water insoluble nonionic monomer is selected from water-soluble vinyl monomer, and the vinyl monomer is selected from acrylamide, metering system
Acid amides, NIPA, N-N- DMAAs, N-N- acrylamides and N- methylols
At least one in acrylamide, N- vinyl formamides, N- vinyl acetamides；The anionic monomer is selected from
2- acrylamide-2-methylpro panesulfonic acids, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, bar
Beans acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, vinyl phosphonate, allyl sulphonic acid, allyl phosphonic acid and/or its
At least one in water-soluble alkali, alkaline-earth metal and ammonium salt；Cationic monomer is selected from dimethyl diallyl chlorine
Change ammonium, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2- acrylamides
At least one in base -2- trimethoxysilyl propyl methacrylate ammonium chlorides.
4. the hydrophobic associated polymer of special construction according to claim 2, it is characterised in that the band
The function monomer of cyclic structure is selected from least one in NVP, N-phenylmaleimide；Tree
The function monomer of dendritic morphology is selected from N-tert-butyl acrylamide.
5. the hydrophobic associated polymer of special construction according to claim 2, it is characterised in that described to dredge
Aqueous monomer is anionic surface activity monomer or cationic surfactant monomer.
6. the hydrophobic associated polymer of special construction according to claim 2, it is characterised in that described
Hydrophobic monomer is selected from the 8-22 mono-vinyl class compound of carbon atom.
7. the hydrophobic associated polymer of special construction according to claim 5, it is characterised in that described the moon
Ionic surfactant monomer is the acrylamide azanyl sodium sulfonate that vinyl carbochain number is 8~18；Cationic table
Face activated monomer is the allyl alkyl ammonium chloride that vinyl carbochain number is 12~22.
8. the hydrophobic associated polymer of special construction according to claim 2, it is characterised in that persulfuric acid
Salt is selected from potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate；Sulphite is selected from sodium sulfite or potassium sulfite, acid
Sulphite is selected from sodium hydrogensulfite or potassium bisulfite；Tertiary amine compounds are selected from methacrylic acid N, N- diformazan ammonia
Base ethyl ester, acrylic acid N, N- dimethylaminoethyl, β-dimethylaminopropionitrile, tetramethylethylenediamine, hexa-methylene four
Amine etc.；Quaternary ammonium compoundses are selected from N, N- dimethyl diallyl ammonium chlorides, N, N- diethyl diallyl ammonium chlorides
Deng；Fat amine compound is selected from methylamine, ethylenediamine, 1,3- propane diamine, 1,4- butanediamine, N, N- dimethyl -1,3-
Propane diamine etc.；Azo compound is selected from azo diisobutyl amidine hydrochloride, 2,2'- azos [2- (2- imidazoline -2- bases)
Propane] dihydrochloride etc.；Molecular weight regulator is selected from isopropanol, the tert-butyl alcohol, isobutanol, pentaerythrite or a contracting two
At least one in propane diols.
9. the preparation of the polymer-type profile control agent suitable for high temperature and high salt harshness oil reservoir according to claim 1
Method, comprises the following steps：
A) water, nonionic water-soluble monomers, anionic monomer or/and cationic monomer, knot are added in a kettle.
Structure monomer, hydrophobic monomer；
B) composite initiation system in addition to oxidation, reducing agent is added, is stirred, form solution；
C) pH value of regulation solution is to 7~10, and is passed through nitrogen, and temperature in the kettle is down into 10~30 DEG C, Ran Houfen
Not Jia Ru oxidant and reducing agent, after continuing to be passed through nitrogen, sealing；
D) polymerization is triggered to start after 0.1~1 hour, reaction temperature rises to 50~70 DEG C, and it is small that temperature-rise period continues 2~5
When, 1~3 hour is incubated after reaching the highest temperature, obtain gel polymerizate；
E) cut and add after glue drying aids, mediate it is uniform after at 85~95 DEG C forced air drying 1~3 hour, use powder
Broken machine or roller are crushed to certain particle size, obtain hydrophobic associated polymer；
F) the desired amount of hydrophobic associated polymer and surfactant are well mixed, obtain described suitable for height
The polymer-type profile control agent of warm high salt harshness oil reservoir.
10. it is according to claim 9 suitable for high temperature and high salt harshness oil reservoir polymer-type profile control agent system
Preparation Method, it is characterised in that the drying aids, in terms of hydrophobic associated polymer whole weight percent monomer,
Including following components：
A) 0.1~3% dispersant；
B) 0.1~20% viscous steady agent；
Wherein, the dispersant is the mineral oil containing lipophilic surfactant；Glue steady agent be selected from free radical resistant type,
One or more in reduced form, high volence metal ion complexing agent, alcohol or amine, polymer-type.
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