CN104448127B - Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof - Google Patents
Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of polymer mobility control agent for being applied to special high salinity reservoirs and preparation method thereof, mainly solve polymer temperature-resistant anti-salt present in prior art and anti-shear performance is poor, it is impossible to the problem of meeting tertiary oil recovery requirement.The present invention in terms of polymer weight number, includes 5 ~ 99.9 parts of nonionic water-soluble monomers by using a kind of controlling agent of both sexes hydrophobic associated polymer；0 ~ 50 part of anionic monomer or/and cationic monomer；The technical scheme of 0.1 ~ 10 part of the hydrophobic monomer with surface-active, 0.1~5 part of inorganic matter and 1~20 part of surfactant, preferably resolves the problem, in the industrial production available for the polymer mobility control agent of special high salinity reservoirs.
Description
Technical field
The present invention relates to a kind of polymer mobility control agent for being applied to special high salinity reservoirs and preparation method thereof.
Background technology
Domestic each elephant passes through once, secondary oil recovery, and crude oil water content is continuously increased, and part elephant successively enters three
The secondary oil recovery stage.Polymer flooding is the main technique methods of tertiary oil recovery, and mechanism of oil displacement understands that technique is relatively easy, technology day
Become ripe, be an effective raising recovery efficiency technique measure.The mechanism of oil displacement of polymer mainly uses water-soluble polypropylene
The viscosity of amide molecule chain, improves the mobility ratio of displacing fluid, displacement efficiency and swept volume is improved, so as to reach raising recovery ratio
Purpose.Because the tertiary oil recovery cycle is long, deep layer oil temperature is high, and therefore, polymer used for tertiary oil recovery must have good increasing
Viscous, heatproof, salt resistance, shear resistant, and performance is steady in a long-term.
Early stage is usually used in enhanced oil recovery（EOR）The industrial products of polymer flooding only have partially hydrolyzed polyacrylamide (PHPA)
（PAM）, it reaches thickening dependent on the ion on HMW and polymer molecular chain and the repulsive interaction of highly polar side base
Effect.But, heavy polymer is when by larger stretching and shear stress, it is prone to mechanical degradation and lose viscous
Degree, it is particularly evident during injection of polymer in low-permeability rock stratum.Cation in the aqueous solution, especially divalent ion, can shield
The ionic group in polymer is covered, polymer molecular chain is crimped, hydrodynamic volume, which reduces, even to be precipitated, so that tackifying
Substantially reduce.When depth of stratum is up to 20000 feet, reservoir temperature is higher（About 100 DEG C）, the acyl in polyacrylamide (PAM)
Amido facile hydrolysis in the high temperature aqueous solution, makes the salt-resistance of polymer solution drastically decline.In recent years, relevant temperature-resistant and anti-salt type gathers
The research of acrylamide it is main by introduce big side base on main polymer chain or rigid side base improve polymer heat endurance,
Introduce the monomer for suppressing hydrolysis or the insensitive monomer of salt is carried out copolymerization to improve the hydrolysis and anti-salt property of polymer, or
Improve the temperature-resistant anti-salt performance of polymer by the heat resistance and salt tolerance of hydrophobic grouping.But due to the quality or valency of comonomer
Lattice make it that polymer is difficult to reach that HMW or product have higher cost, are answered in industrial production or tertiary oil recovery is actual
With can be somewhat limited.In current tertiary oil recovery, the polymer that can meet temperature-resistant anti-salt requirement is seldom, is not that price is too high
It is exactly unstable properties, particularly can not meets more than salinity 100000mg/L, the requirement of 85 DEG C of high temperature above.
Hydrophobic associated water-soluble polymer refers to carry the one of a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain
Class water-soluble polymer., should as novel polymeric oil-displacing agent due to the SOLUTION PROPERTIES such as its unique thickening, salt resistance, anti-shearing
Had a good application prospect for high salt, high shear oil reservoir development.Given birth to because of hydrophobic grouping is introduced in polymer molecule
Into hydrophobic association type copolymer, in aqueous medium its hydrophobic chain link to assemble and associate similar to surfactant mode,
Effective hydrodynamic volume increase of a macromolecular ball of string, aqueous medium viscosity is improved, and larger side base rises to polymer molecule backbone
To shielding action, weaken the p- COO of salt ion—The influence of group；And also there is larger side base certain steric hindrance to imitate
Should, strengthen chain rigidity.
But it is existing there are some researches show conflicting between the associative ability of such polymer and water solubility, good water solubility it is poly-
The carbochain of compound often hydrophobic monomer is shorter or content is relatively low, and associating effect is not obvious, need to be under higher polymer concentration
Show certain association effect and meet heat and salinity tolerance performance；And the polymer associate of the hydrophobic monomer containing long-chain or high content
Very capable, heat and salinity tolerance performance is good, but poorly water-soluble, and generally requiring long time can just be completely dissolved, and lose industry
Change the value of application.How preferable equalization point is found between, be that can such polymer be widely used in three times
The key of oil recovery process.
The country has carried out numerous studies in terms of hydrophobic associated polymer, wherein Southwest Petroleum Institute, Chengdu Univ. of Science ＆ Technology,
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-
The hydrophobic associated polymer of three kinds of construction units of alkyl phenyl ether, although have preferable Efficient Adhesive Promotion, but pi-allyl-alkyl phenyl
The synthesis of ether monomer is complex；Zhong Chuanrong etc.（CN101293944A、CN 101148582A）The virtue of condensed ring containing vinyl is synthesized
Hydrocarbon is as the hydrophobic associated polymer of hydrophobic monomer, and the polymerization process time is longer, only have rated at 45 DEG C polymer in fresh water and
Efficient Adhesive Promotion in salt solution, salt resistance effect assessment NaCl concentration<100000mg/L、CaC12Concentration<1000mg/L situation；
Ou Yangjian etc.（CN1317501）High-molecular hydrophobic associated polymer, in 75 DEG C of total salinity 12000mg/L, wherein Ca2+With
Mg2+For 300mg/L, sample concentration is 1500mg/L, using Brookfield viscometer, and shear rate is 36.7s-1Viscosity be 15.6 ~
12.4mPa.s；Hole beautiful jade etc.（CN1528734、CN1528797）The super high molecular weight water insoluble hydrophobic containing fluorocarbon group has been synthesized to form
Mould assembly polymer, have rated it in triumph salt solution（Total salinity 6000mg/L, calcium ions and magnesium ions 500mg/L）Increasing under the conditions of 70 DEG C
Viscosity, wherein fluorinated acrylate hydrophobic monomer is expensive；Jiang Liding（The synthesis of new family hydrophobic association polyacrylamide
And its rheological property of the aqueous solution, Master's thesis in 2007）Using surface active monomer NaAMC14S and the homogeneous copolymerization of the AM aqueous solution
The method of conjunction has been successfully prepared the copolymer NaAMC with hydrophobic block structure14S/AM, overcomes micellar co-polymerization using general
Some shortcomings that logical surfactant is brought, copolymer NaAMC14The length of S/AM hydrophobic micro- block can be outer by regulation
Plus the consumption of electrolyte is controlled, but research work biases toward theory, not 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, is adopted
Need to add substantial amounts of surfactant when with such a method being polymerize（Such as SDS）Make hydrophobic monomer solubilising in micella, but poly-
Substantial amounts of surfactant is added during conjunction has significant impact to the association behavior of polymer, and these surfactants are poly-
Close in product and interacted with hydrophobic segment, deteriorate the performance of hydrophobic associated water-soluble polymer.If removing these tables
Face activating agent, can increase the complexity of the last handling process such as separation and purifying.In order to simplify last handling process and strengthen polymer
Dissolubility, can using inherently have surface-active hydrophobic monomer.This kind of monomer contains hydrophobic grouping and hydrophilic simultaneously
Group, surfactant need not be it is possible to additionally incorporate in combined polymerization, can directly use traditional free yl solution polymerization, and
It can make that hydrophobic monomer is highly unordered to be irregularly introduced into copolymer.But there are research in foreign countries（Ezzell,S.A.,McCormick,
C.L., Macromolecules 1992,25(7), 1881~1886）It was found that, the copolymer of this kind of ionic hydrophobic monomer exists
Critical association concentration in the aqueous solution is more than 2 times of the identical Hydrophobic chain length of micella copolymer, and this point polymerize to hydrophobic association
The application of thing industrially is totally unfavorable.As can be seen here, domestic and international researcher to the structure of hydrophobic associated water-soluble polymer,
Property, viscosifying mechanisms and application have done the evaluation of numerous studies, exploration work, but polymer essentially according to grand celebration or Shengli Oil Field
Some mineral reserve conditions, temperature and salinity are all not belonging to high temperature and high salt type, for more than salinity 100000mg/L, more than 85 DEG C
The condition of high temperature almost without reference to.
The present invention is to ionic, the synthesis of both sexes hydrophobic associated water-soluble polymer and hydrophobically modified polyelectrolyte, knot
Structure sign and SOLUTION PROPERTIES aspect are carried out on the basis of extensive, in-depth study, 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, is not required to
Separately add surfactant during polymerization, two be that can form both sexes hydrophobic associated polymer, under hydrophobic monomer lower content
Polymer also has high-effective viscosity and excellent heatproof, salt resistance and shear resistant；Except adding routine in rear hydrolytic process
Outside alkali, a certain amount of surfactant is additionally added, contributes to the dissolving of polymer and plays collaboration viscosifying action.Institute of the present invention
The polymer mobility control agent for being applied to special high salinity reservoirs stated has the quick property of high tackifying, normal salt（Meet salt retrogradation）, one
Determine the positive Thermo-sensitive of scope（Heat up retrogradation）With relatively low critical micelle concentration, and excellent anti-aging, anti-shear ability, fit
Requirement together in total salinity more than 100,000 oil reservoir oil displacements, has a good application prospect in tertiary oil recovery engineering.
The content of the invention
One of technical problems to be solved by the invention are the anti-high salinities of polymer high temperature resistant present in prior art
And there is provided a kind of polymer flow for being applied to special high salinity reservoirs the problem of can meet tertiary oil recovery requirement for shear resistant
Controlling agent is spent, the polymer has high-effective viscosity, temperature-resistant anti-salt（A range of chance salt retrogradation, heating retrogradation）, it is thermally-stabilised
And anti-shear performance it is excellent the characteristics of.
The two of the technical problems to be solved by the invention are to provide a kind of system for solving the polymer in one of technical problem
Preparation Method, this method has polymerisation process simple, without steps such as separation, purifying, reduces the advantage of cost.
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 extra-high ore deposit
The polymer mobility control agent of change degree oil reservoir, the molecular weight of the polymer is between 200-2000 ten thousand, by following monomer composition
Solution reacts in the presence of composite initiator to be made；The solution of described monomer composition is in terms of parts by weight, comprising with the following group
Point：
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 the hydrophobic monomer with surface-active；
D) 0.1~5 part of inorganic matter；
E) 1~20 part of surfactant
F) 200 ~ 2000 parts of water；
Wherein, the composite initiator, in terms of above-mentioned whole weight percent monomers, includes 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 amines of representative
Compound or by NH2R8R in the fat amine compound of representative, formula1~R7It is selected from C1~C14Straight or branched alkyl or alkyl derivative
Thing, R8Selected from C1~C18Straight or branched alkyl or alkyl derivative；
(d) 0.005~1% azo compound；
(e) 0.01~10% urea, thiocarbamide；
(f) 0.03~0.5% disodium ethylene diamine tetraacetate or diethylene triamine pentacetic acid (DTPA) sodium；
(g) 0.03~0.5% molecular weight regulator.
In above-mentioned technical proposal, the nonionic water-soluble monomers preferred scheme is selected from water-soluble vinyl monomer, institute
State vinyl monomer and be selected from acrylamide, Methacrylamide, NIPA, N-N- DMAAs, N-
N- acrylamides and N hydroxymethyl acrylamide, N- vinyl formamides, N- vinyl acetamides, N- vinylpyridines
And at least one in NVP.The anionic monomer preferred scheme is selected from 2- acrylamido -2- first
Base propane sulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylbenzenesulfonic acid, vinyl sulphur
In acid, vinyl phosphonate, allyl sulphonic acid, allyl phosphonic acid and/or its water-soluble alkali, alkaline-earth metal and ammonium salt at least
It is a kind of；Cationic monomer is selected from dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methacryloxypropyl
At least one in ethyl-trimethyl salmiac and 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides.
The hydrophobic monomer preferred scheme with surface-active is anionic surface activity monomer or cationic table
Face activated monomer.The hydrophobic monomer with surface-active more preferably scheme is the mono-vinyl class selected from 8-22 carbon atom
Compound.It is preferred that technical scheme, the anionic surface activity monomer be vinyl carbochain number be 8 ~ 18 acrylamide
Azanyl sodium sulfonate；Cationic surfactant monomer is the allyl alkyl ammonium chloride that vinyl carbochain number is 12 ~ 22.
The inorganic matter preferred scheme is acidic oxide such as boron oxide, silica etc., basic anhydride such as barium monoxide, oxygen
Change manganese, calcium oxide, magnesia etc. and amphoteric oxide aluminum oxide, zinc oxide etc..They or it is soluble in water generation great amount of hydroxy group,
Or two with hydrophobic associative behavior can be caused by the effect of hydrogen bond or other chemical bonds with anionic monomer reaction generation salt
Property polymer form variable network structure, under high salinity, high temperature or shear action have more preferable viscosity stability.
Persulfate preferred scheme is selected from potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate；Sulphite is selected from sulfurous acid
Sodium or potassium sulfite, acid sulphite are selected from sodium hydrogensulfite or potassium bisulfite；Tertiary amine compounds preferred scheme is choosing
From methacrylic acid N, N- dimethylaminoethyls, acrylic acid N, N- dimethylaminoethyl, β-dimethylaminopropionitrile, tetramethyl second two
Amine, hexa etc.；Quaternary ammonium compoundses are selected from N, N- dimethyl diallyl ammonium chlorides, N, N- diethyl diallyls
Ammonium chloride；Fat amine compound is selected from methylamine, ethylenediamine, 1,3- propane diamine, 1,4- butanediamine, N, N- dimethyl -1,3- third
Diamines etc.；Azo compound is selected from azo diisobutyl amidine hydrochloride, 2,2'- azos [2- (2- imidazoline -2- bases) propane]
Dihydrochloride etc.；Molecular weight regulator preferred scheme is selected from isopropanol, the tert-butyl alcohol, isobutanol, pentaerythrite or a contracting dipropyl
At least one in glycol.
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 extra-high ore deposit
The preparation method of the polymer mobility control agent of change degree oil reservoir, successively including following steps：
(a) water, nonionic water-soluble monomers, anionic monomer or/and cationic monomer are added in a kettle., had
The auxiliary agents such as the hydrophobic monomer and inorganic matter of surface-active；
(b) composite initiation system of part is added, is stirred, solution is formed；
(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, it is then added
Remaining composite initiator, continues to be passed through after nitrogen, sealing；
(d) reaction temperature is gradually increased to 40 ~ 60 DEG C after 0.5 ~ 1 hour, after reacting 2 ~ 8 hours, obtains gel polymerization
Product；
(e) cut and the composite hydrolysis agent containing surfactant is added after glue, in 80 ~ 90 oC hydrolysis 2 ~ 4 hours；So
It is dried in vacuo 3~6 hours at 60~90 DEG C afterwards, certain particle size is crushed to pulverizer or roller, is obtained suitable for extra-high
The polymer mobility control agent of salinity oil reservoir.
In above-mentioned technical proposal, technical scheme preferably, the composite hydrolysis agent, with the whole monomer weights of association polymer
Percentages, including following components：(a) at least one in 0~10% NaOH or sodium carbonate；(b) 0.5 ~ 50% table
Face activating agent.
The surfactant preferred scheme is selected from anionic surfactant such as C8-16Sodium alkyl sulfate, C8-16Alkane
Base benzene sulfonic acid sodium salt etc., cationic surface active agent such as C8-16Alkyl trimethyl bromine（Chlorine）Change ammonium etc., nonionic such as alkyl phenol
APEO（EO=4~30）Or their any mixture；
In above-mentioned technical proposal, polymer mobility control agent of special high salinity reservoirs and preparation method thereof, including it is following
Step：A certain amount of deionized water is first added in a kettle., then puts into acrylamide, surface active monomer and anion
And/or cationic monomer and other auxiliary agents are stirred to being completely dissolved.PH value is adjusted to 7 ~ 10 with NaOH solution, and starts to be passed through height
Temperature in the kettle is down to set point of temperature after pure nitrogen gas, 10 ~ 60min（10~30℃）, composite initiator is then sequentially added, is continued
Sealed after 10 ~ 60min of logical nitrogen.Reaction temperature is gradually increased to set point of temperature after 0.5 ~ 2 hour（40~60℃）, react 2 ~ 8 small
When after obtain gel polymerizate, the composite hydrolysis agent aqueous solution added after glue containing surfactant and alkali is cut, in 80 ~ 90 o
C hydrolysis 2 ~ 4 hours, is then dried in vacuo 3 ~ 6h at 60 ~ 90 DEG C, and sampling point after screening is smashed with pulverizer or roller
Analysis.
Polymer mobility control agent suitable for special high salinity reservoirs is by using 5 ~ 99.9 parts of non-ionic water-solubles
Monomer, 0 ~ 50 part of anion or/and cationic monomer, 0.1 ~ 10 part have surface-active hydrophobic monomer, 0.1~5 part it is inorganic
Thing；In the presence of composite initiation system, trigger the aqueous solution polymerization of comonomer, composite hydrolysis agent is then added as needed and is entered
Hydrolysis after row, last drying and crushing obtains solid content 90% or so, degree of hydrolysis 5~30%, molecular weight 200-2000 ten thousand
Polymer, has high-effective viscosity and the quick property of normal salt under the conditions of high temperature and high salt（Meet salt retrogradation）, a range of positive Thermo-sensitive
（Heat up retrogradation）With relatively low critical micelle concentration, and with preferable dissolubility, long-term thermal stability and anti-shear performance,
The requirement of more than 100,000 salinity high-temperature oil reservoir Polymer Used For Oil Displacements is met in tertiary oil recovery.The technique is simple to operation, is adapted to
Large-scale production.
Polymer mobility control agent of the present invention for being applied to special high salinity reservoirs and preparation method thereof, due to adopting
With with the opposite ion monomer of surface active monomer ion characteristic, both interaction has increasing to surface active monomer
Molten effect, is not required to separately add surfactant in polymerization；And obtain both sexes hydrophobic association polymerization even in hydrophobic monomer compared with
Polymer also has excellent temperature-resistant anti-salt, thermally-stabilised and anti-shear performance under low content；The inorganic matter of addition is in reaction system
In make it that the amphiphilic polymers with hydrophobic associative behavior form variable network knot by the effect of hydrogen bond or other chemical bonds
Structure, has more preferable viscosity stability under high salinity, high temperature or shear action；And composite initiation system is employed, and
It is matched with preferred technique, therefore reacting balance, be conducive to chain to increase, molecular weight of product is controllable, the rear hydrolysis process of use
Due to the addition of surfactant, contribute to the dissolving of polymer and play collaboration viscosifying action.Using provided by the present invention
Obtained polymer mobility control agent for being applied to special high salinity reservoirs of preparation technology and preparation method thereof, molecular weight 200 ~
It is adjustable between 20000000, excellent viscosifying action is shown under high temperature and high salinity, the viscous dense curve of polymer is shown, the both sexes
Hydrophobic associated polymer compound has stronger association, and viscosity amplification is up to two to three orders of magnitude, and critical glue
Beam concentration appears in below 2000mg/L；There is polymer salt to viscosify effect more than 100,000 under salinity, and viscosity-temperature curve shows,
Polymer viscosity at 60~80 DEG C substantially increases, though there is decline afterwards but still higher than the viscosity before 60 DEG C；Polymer
Ageing-resistant and anti-shear performance is good, in the tertiary oil recovery available for extra-high salinity high-temperature oil reservoir.
Below by specific embodiment, the present invention will be further elaborated.
Embodiment
【Embodiment 1】
First add in a kettle. in 2500g deionized waters, add 430g acrylamides（AM）, 2- acrylamidos -2-
Methyl propane sulfonic acid（AMPS）150g, 2.5g2- acrylamido myristyl sodium sulfonate（NaAMC14S）, 3.5g acrylyl oxy-ethyls
Trimethyl ammonium chloride（DAC）, neutrality is neutralized to NaOH, disodium ethylene diamine tetraacetate 0.04g, urea 7g, isopropyl is subsequently added
Alcohol 0.07g, stirring is to being completely dissolved.PH value is adjusted to 8.9 with NaOH, and start to be passed through after high pure nitrogen, 30min will be warm in kettle
Degree is down to 15 DEG C, then sequentially adds 0.2% aqueous solution of sodium bisulfite 10g, 0.5% methacrylic acid N, N- dimethylamino second
Ester（DMAEMA）The aqueous solution 10g, 0.5% azo diisobutyl amidine hydrochloride 10g, 0.3% persulfate aqueous solution 10g, after
Sealed after continuous logical nitrogen 30min.Reaction temperature is gradually increased to 48 DEG C after 1 hour, reaction obtains gel polymerization after 3.5 hours
Product, cuts the composite hydrolysis agent 500g aqueous solution that lauryl sodium sulfate containing 35g and 25gNaOH are added after glue, in 90 oC hydrolysis
Reaction 2 hours, is then dried in vacuo 5h at 75 DEG C, and sampling analysis after screening is smashed with pulverizer.
It is 89.5% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, by GB/
T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test Rong solution Shi Jian≤90min, by GB/T12005.6-89
Partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 11.6%, by GB/T12005.10-92 polyacrylamides
Amine molecule measures fixed（Viscosimetry）Intrinsic viscosity is determined, and by [η]=3.73 × 10-4Mw0.66It is 9,120,000 to calculate molecular weight.It is apparent
Viscosity is：
（1）In 95 DEG C, salt solution total salinity 157726 mg/L, Ca2++Mg2+：1500mg/L polymer under 6310 mg/L
Strength solution, using Brookfield viscometer, shear rate 7.34s-1Under apparent viscosity be 107mPas.After 95 DEG C of agings 30 days
Viscosity retention ratio is respectively 91%, and after high-speed shearing machine 5000rpm down cuts 30min, viscosity retention ratio is 86%.
（2）In 95 DEG C, salt solution total salinity 18000mg/L, Ca2++Mg2+：1500mg/L polymer is dense under 5700 mg/L
Solution is spent, using Brookfield viscometer, shear rate 7.34s-1Under apparent viscosity be 163mPas.95 DEG C of agings are glued after 30 days
It is respectively 92% to spend retention rate, and after high-speed shearing machine 5000rpm down cuts 30min, viscosity retention ratio is 89%.
【Embodiment 2】
First add in a kettle. in 2600g deionized waters, add 480g acrylamides（AM）, 2- acrylamidos -2-
Methyl propane sulfonic acid（AMPS）130g, 3.0g2- acrylamido dodecyl sodium sulfate（NaAMC12S）With 4.2g methacryls
Oxy-ethyl-trimethyl salmiac（DMC）, neutrality is neutralized to NaOH, disodium ethylene diamine tetraacetate 0.045g, urea is subsequently added
7.0g, isopropanol 0.06g, Alumina gel 15g, stirring is to being completely dissolved.PH value is adjusted to 9.0 with NaOH, and starts to be passed through high-purity
Temperature in the kettle is down to 16 DEG C after nitrogen, 30min, 0.2% aqueous solution of sodium bisulfite 10.2g is then sequentially added, 0.5% the third
Olefin(e) acid N, N- dimethylaminoethyl（DA）The aqueous solution 11g, 0.5% azo diisobutyl amidine hydrochloride 11.9g, 0.3% over cure
Sour aqueous solutions of potassium 11.2g, is sealed after continuing logical nitrogen 30min.Reaction temperature is gradually increased to 52 DEG C after 1 hour, reacted 3 hours
After obtain gel polymerizate, cut the 500g aqueous solution that neopelex containing 51g and 32gNaOH are added after glue,
90 oC hydrolysis 2 hours, are then dried in vacuo 5h at 75 DEG C, and sampling analysis after screening is smashed with pulverizer.Evaluation result
It is shown in Table 1.
【Embodiment 3】
First add in a kettle. in 2700g deionized waters, add 500g acrylamides（AM）, 2- acrylamidos -2-
Methyl propane sulfonic acid（AMPS）150g, acrylic acid 130g, 3.2g2- acrylamido sodium cetanesulfonate（NaAMC16S）And 5.2g
Dimethyl diallyl ammonium chloride（DMDAAC）, be neutralized to neutrality with NaOH, be subsequently added disodium ethylene diamine tetraacetate 0.05g,
Urea 8.0g, isopropanol 0.07g, calcium oxide 0.5g, stirring is to being completely dissolved.PH value is adjusted to 9.5 with NaOH, and starts to be passed through
Temperature in the kettle is down to 20 DEG C after high pure nitrogen, 30min, 0.2% aqueous solution of sodium bisulfite 10.2g is then sequentially added,
0.5% acrylic acid N, N- dimethylaminoethyl（DA）The aqueous solution 12.1g, 0.5% 2,2'- azos [2- (2- imidazoline -2- bases)
Propane] dihydrochloride 12g, 0.3% persulfate aqueous solution 11g, are sealed after continuing logical nitrogen 30min.Will reaction after 1 hour
Temperature is gradually increased to 55 DEG C, and reaction obtains gel polymerizate after 2.5 hours, cuts the 400g water added after glue containing 38gOP-20
Solution, in 90 oC hydrolysis 2 hours, is then dried in vacuo 5h at 75 DEG C, and sampling analysis after screening is smashed with pulverizer.
Evaluation result is shown in Table 1.
【Embodiment 4】
First add in a kettle. in 2600g deionized waters, add 510g acrylamides（AM）, 2- acrylamidos -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, disodium ethylene diamine tetraacetate 0.048g, urea 7.5g, tert-butyl alcohol 0.08g, silicon is subsequently added
Colloidal sol 12g, stirring is to being completely dissolved.PH value is adjusted to 8.7 with NaOH, and start to be passed through after high pure nitrogen, 30min will be warm in kettle
Degree is down to 12 DEG C, then sequentially adds 0.2% aqueous solution of sodium bisulfite 11.2g, 0.5% methacrylic acid N, N- dimethylamino
Ethyl ester（DMAEMA）The aqueous solution 12.6g, 0.5% azo diisobutyl amidine hydrochloride 12g, 0.3% persulfate aqueous solution
10.9g, is sealed after continuing logical nitrogen 30min.Reaction temperature is gradually increased to 52 DEG C after 1 hour, reaction obtains gel after 3 hours
Shape polymerizate, cut and the 500g aqueous solution containing 42gOP-10 and 30gNaOH is added after glue, in 85oC hydrolysis 2.5 hours, so
4h is dried in vacuo at 80 DEG C afterwards, sampling analysis after screening is smashed with pulverizer.Evaluation result is shown in Table 1.
【Comparative example 1】
By 650g acrylamide monomers, disodium ethylene diamine tetraacetate 0.04g, urea 7g, isopropanol 0.07g adds 2500g
In deionized water, after the dissolving completely that stirs, pH value is adjusted to 8.5 with NaOH solution.Then nitrogen 30min is led to, and by water
Bath temperature is adjusted to 15 DEG C, then sequentially adds 0.2% aqueous solution of sodium bisulfite 10g, 0.5% methacrylic acid N, N- diformazan ammonia
Base ethyl ester（DMAEMA）The aqueous solution 10g, 0.5% azo diisobutyl amidine hydrochloride 10g, 0.3% persulfate aqueous solution
10g, is sealed after continuing logical nitrogen 30min.Reaction temperature is gradually increased to 50 DEG C after 1 hour, reaction obtains gel after 3 hours
Polymerizate, cuts the hydrolytic reagent 730g aqueous solution added after glue containing 37gNaOH, in 90 oC hydrolysis 2 hours, then 75
5h is dried in vacuo at DEG C, sampling analysis after screening is smashed with pulverizer.
It is 88.92% by GBT12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GBT12005.6-89 partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 11.3%, is pressed
GBT12005.10-92 Molecular Weight for Polyacrylamide is determined（Viscosimetry）Intrinsic viscosity is determined, and by [η]=3.73 × 10-4Mw0.66
It is 19,630,000 to calculate molecular weight.Apparent viscosity is shown in Table 1.
【Comparative example 2】
By 450g acrylamides（AM）, 200g2- acrylamido -2- methyl propane sulfonic acids（AMPS）, ethylenediamine tetra-acetic acid two
Sodium 0.04g, urea 7g, isopropanol 0.07g are added in 2500g deionized waters, are stirred after dissolving completely, are adjusted with NaOH
PH value is to 9.0.Then lead to nitrogen 30min, and bath temperature is adjusted to 15 DEG C, then sequentially add 0.2% sodium hydrogensulfite water
Solution 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, are sealed after continuing logical nitrogen 30min.After 1 hour by reaction temperature gradually
50 DEG C are risen to, reaction obtains gel polymerizate after 3 hours, cuts the hydrolytic reagent 500g aqueous solution added after glue containing 25gNaOH,
In 90 oC hydrolysis 2 hours, 5h then is dried in vacuo at 75 DEG C, sampling analysis after screening is smashed with pulverizer.
It is 87.34% by GBT12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GBT12005.6-89 partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 12.6%, is pressed
GBT12005.10-92 Molecular Weight for Polyacrylamide is determined（Viscosimetry）Intrinsic viscosity is determined, and by [η]=3.73 × 10-4Mw0.66
It is 13,650,000 to calculate molecular weight.Apparent viscosity is shown in Table 1.
Table 1
* determined by GBT12005.10-92 Molecular Weight for Polyacrylamide（Viscosimetry）Determine intrinsic viscosity, and by [η]=
3.73×10-4Mw0.66Calculate molecular weight
* 1500mg/L polymer concentrations solution is in 95 DEG C, 7.34s-1Under apparent viscosity,
Salt solution 1：TDS157726mg/L Ca2++Mg2+6310mg/L,
Salt solution 2：TDS180000mg/L Ca2++Mg2+5700mg/L。
As can be seen that the polymer of the present invention has under the conditions of high temperature and high salt from the data in above-described embodiment table 1
Excellent high tackifying, the quick property of normal salt（Meet salt retrogradation）, a range of positive Thermo-sensitive（Heat up retrogradation）And it is anti-aging, anti-shearing
Ability.
Claims (6)
1. a kind of polymer mobility control agent for being applied to special high salinity reservoirs, the molecular weight of described polymer is in 200-
Between 20000000, reacted and be made in the presence of composite initiator by the solution of following monomer composition；Described monomer composition
Solution includes following components in terms of parts by weight：
A) 5~99.9 parts of nonionic water-soluble monomers；
B) 0~50 and more than 0 part of anionic monomer or/and cationic monomer；
C) 0.1~10 part of the hydrophobic monomer with surface-active；
D) 0.1~5 part of inorganic matter；
E) 200~2000 parts of water；
Wherein, the composite initiator, in terms of above-mentioned whole weight percent monomers, includes 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 compoundses of representative or
By NH2R8R in the fat amine compound of representative, formula1~R7It is selected from C1~C14Straight or branched alkyl or alkyl derivative, R8
Selected from C1~C18Straight or branched alkyl or alkyl derivative；
(d) 0.005~1% azo compound；
(e) 0.01~10% urea, thiocarbamide；
(f) 0.03~0.5% disodium ethylene diamine tetraacetate or diethylene triamine pentacetic acid (DTPA) sodium；
(g) 0.03~0.5% molecular weight regulator；
The nonionic water-soluble monomers are selected from water-soluble vinyl monomer, and the vinyl monomer is selected from acrylamide, methyl
Acrylamide, NIPA, N, N- DMAAs, N, N- acrylamides and N- methylol propylene
At least one in acid amides, N- vinyl formamides, N- vinyl acetamides, N- vinylpyridines and NVP
Kind；Anionic monomer is selected from 2- acrylamide-2-methylpro panesulfonic acids, acrylic acid, methacrylic acid, itaconic acid, maleic acid, richness
Horse acid, crotonic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, vinyl phosphonate, allyl sulphonic acid, allyl phosphonic acid and/or its water
At least one in insoluble alkali metal, alkaline-earth metal and ammonium salt；Cationic monomer is selected from dimethyl diallyl ammonium chloride, propylene
Acyloxyethyl trimethyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2- acrylamido -2- methyl-propyls three
At least one in ammonio methacrylate；The inorganic matter is acidic oxide, basic anhydride or amphoteric oxide；
The preparation method of the polymer mobility control agent, successively including following steps：
(a) water, nonionic water-soluble monomers, anionic monomer or/and cationic monomer are added in a kettle., lived with surface
The hydrophobic monomer and auxiliary agent inorganic matter of property；
(b) composite initiator of part is added, is stirred, solution is formed；
(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, remaining is then added
Composite initiator, continues to be passed through after nitrogen, sealing；
(d) reaction temperature is gradually increased to 40~60 DEG C after 0.5~1 hour, after reacting 2~8 hours, obtains gel polymerization production
Thing；
(e) cut and the composite hydrolysis agent containing surfactant is added after glue, in 80~90 DEG C of hydrolysis 2~4 hours；Then exist
It is dried in vacuo 3~6 hours at 60~90 DEG C, certain particle size is crushed to pulverizer or roller, obtains being applied to extra-high mineralising
Spend the polymer mobility control agent of oil reservoir；
The composite hydrolysis agent, in terms of the whole weight percent monomers of association polymer, including following components：
(a) at least one in 0~20% NaOH or sodium carbonate；
(b) 0.5~50% surfactant；
The surfactant is selected from C8-C16Sodium alkyl sulfate or C8-C16The anionic surfactant of sodium alkyl benzene sulfonate,
C8-C16Alkyl trimethyl bromine (chlorine) change the cationic surface active agent of ammonium, the APES of EO=4~30 it is non-
At least one in ionic surfactant.
2. the polymer mobility control agent according to claim 1 for being applied to special high salinity reservoirs, it is characterised in that institute
The hydrophobic monomer with surface-active is stated for anionic surface activity monomer or cationic surfactant monomer.
3. the polymer mobility control agent according to claim 1 for being applied to special high salinity reservoirs, it is characterised in that institute
The acidic oxide stated is boron oxide, silica, and described basic anhydride are barium monoxide, manganese oxide, calcium oxide, magnesia,
Described amphoteric oxide is aluminum oxide, zinc oxide.
4. the polymer mobility control agent according to claim 2 for being applied to special high salinity reservoirs, it is characterised in that institute
The hydrophobic monomer with surface-active is stated for the mono-vinyl class compound selected from 8-22 carbon atom.
5. the polymer mobility control agent according to claim 2 for being applied to special high salinity reservoirs, it is characterised in that institute
It is the acrylamide azanyl sodium sulfonate that vinyl carbochain number is 8~18 to state anionic surface activity monomer；Cationic table
Face activated monomer is the allyl alkyl ammonium chloride that vinyl carbochain number is 12~22.
6. the polymer mobility control agent according to claim 1 for being applied to special high salinity reservoirs, it is characterised in that mistake
Sulfate is selected from potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate；Sulphite is selected from sodium sulfite or potassium sulfite, acid sulfurous
Hydrochlorate is selected from sodium hydrogensulfite or potassium bisulfite；Tertiary amine compounds are selected from methacrylic acid N, N- dimethylaminoethyl, third
Olefin(e) acid N, N- dimethylaminoethyl, β-dimethylaminopropionitrile, tetramethylethylenediamine, hexa；Quaternary ammonium compoundses are selected
From N, N- dimethyl diallyl ammonium chlorides, N, N- diethyl diallyl ammonium chlorides；Fat amine compound is selected from methylamine, second
Diamines, 1,3- propane diamine, 1,4- butanediamine, N, N- dimethyl -1,3- propane diamine；Azo compound is selected from azo diisobutyl
Amidine hydrochloride, 2,2'- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride；Molecular weight regulator is selected from isopropanol, tertiary fourth
At least one in alcohol, isobutanol, pentaerythrite or dipropylene glycol.
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