CN105524215A - Heatproof salt-resistant acrylamide polymer microsphere dispersed system and preparation method and use thereof - Google Patents
Heatproof salt-resistant acrylamide polymer microsphere dispersed system and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a heatproof salt-resistant acrylamide polymer microsphere dispersed system and a preparation method and use thereof. The heatproof salt-resistant acrylamide polymer microsphere dispersed system mainly solves the problem that most of the acrylamide polymer microspheres in submicron to micron scale are prepared through an inverse emulsion polymerization method and contain a large amount of an oil phase and a certain amount of an emulsifier so that a cost is high, oil displacement effects do not exist and compatibility with the oil displacement surfactant is poor. Copolymerization ingredients undergo an alcohol-water dispersion polymerization reaction in the presence of an initiator to produce the heatproof salt-resistant acrylamide polymer microsphere dispersed system. The copolymerization ingredients comprise, by weight, 70-90 parts of an alcohol-water mixture, 1-10 parts of a stabilizing agent, 0.1-5 parts of a cross-linking agent and 10-30 parts of a copolymerization monomer. The heatproof salt-resistant acrylamide polymer microsphere dispersed system solves the above problem and can be used for fields of tertiary oil recovery depth profile control, water plugging and oil displacement for improving a yield.
Description
Technical field
The present invention relates to a kind of temperature resistant antisalt acrylamide copolymer microballoon dispersion system and its preparation method and application.
Background technology
Polyacrylamide microsphere is the polyacrylamide spheroidal particle containing linking agent, available homogeneous method and multi-phases process preparation.The former mainly comprises reversed emulsion polymerization, conversed phase micro emulsion copolymerization method, and product is generally latex or fine latex; Latter comprises dispersion copolymerization method, precipitation polymerization method, via Inverse-Phase Suspension Polymerization etc., and product is generally solia particle.Because polymerization process is different, the particle diameter of reaction product is also different.
Domestic each elephant through once, secondary oil recovery, crude oil water content constantly increases, and part elephant successively enters tertiary phase.Along with the raising of recovery percent, well water is the common problem existed in current oil-field development, particularly long-term injecting water exploitation maturing field due to oil reservoir nonuniformity and oil, water viscosity difference, cause injection water to advance by leaps and bounds and fingering along the most permeable zone between water injection well and recovery well or crack, cause the too early water logging of recovery well, oil offtake declines, moisture rising.Reduce well water, usually from water injection well shutoff most permeable zone or crack, the water-absorption surface of adjustment water injection well, reduce and inject water and charge into oil well along most permeable zone or crack, force and inject water change flow direction, enter middle low permeability layer thus improve the sweep efficiency injecting water, improving ecology development effectiveness.Polyacrylamide microsphere is as the one of the most frequently used organic water plugging profile control agent, have obvious selectivity to water, it is constant that it meets oil volume, meets water then volumetric expansion, therefore have good water plugging effect, there is validity period length simultaneously, do not pollute stratum, construction is simple, activity duration short holding point.Rate of permeation due to oil reservoir is different and nonuniformity is comparatively serious, needs the polymer microballoon of different size could meet the profile control shutoff requirement of Different Strata.Yardstick is shouted at micron-sized middle and high infiltration oil reservoir for hole, needs particle size range just can reach effective shutoff at submicron to micron-sized polymer microballoon.The polymer microballoon of this size can take reverse micro emulsion or dispersion copolymerization method to prepare, but containing a large amount of oil phases and a certain amount of emulsifying agent in inverse emulsion system, these components are invalid even can affect the compatibility with surfactant oil displacement for the displacement of reservoir oil, therefore, certain advantage is not just shown containing the dispersion polymerization systems of oil phase and emulsifying agent.
Dispersion polymerization is a kind of new method for producing polymer, and first the beginning of the seventies is proposed by the investigators of ICI company of Britain.Strictly, dispersion polymerization is a kind of precipitation polymerization of specific type, and monomer, stablizer and initiator all dissolve in media as well, is homogeneous system before reaction starts.The polymkeric substance generated is not dissolved in medium, and after polymer chain reaches critical chain length, from medium, precipitating out.With-as the difference of precipitation polymerization be precipitating polymkeric substance be not out form Powdered or block polymkeric substance but be agglomerated into small-particle, suspend in media as well by means of stablizer, form the stable dispersion being similar to polymer emulsion.Dispersion polymerization process more complicated, each reaction parameter such as the selection, temperature of reaction etc. of stabilizer types and consumption, stablizer relative molecular mass, monomer concentration, initiator concentration, solvent all have very important impact to the size of final particle, distribution of sizes and product relative molecular mass.Dispersion polymerization is mainly used in oil-soluble monomer and non-polar monomer prepares mono-dispersion microballoon, water-soluble monomer particularly AM dispersion polymerization research relatively less.In recent years, utilize water as dispersion medium, the research of complex functionality PAM dispersion becomes focus gradually, this method not only increases polymer quality mark, and really achieve nontoxic, pollution-free, meet environmental requirement, also will become polyacrylamide microsphere and prepare one of developing direction.Dispersion polymerization can be divided into four large classes at present according to the kind of the stablizer added and dispersion system: alcohol-water, salt-water, polymkeric substance-water and mixed system, for the situation that domestic most oil fields salinity is higher, if adopt the salt-aqueous systems mostly being vitriol, meet causing the problem that divalent ion produces precipitation; Adopt polymkeric substance-aqueous systems, then will synthesize polymer stabilizer targetedly in advance, add the complicacy of preparation; Although mixed system combines the advantage of several system, because system is more complicated, more many compatibility issues can be run into when practical application; Therefore alcohol-water system is because its composition is simple, feature has comparatively outstanding advantage with surfactant oil displacement compatibleness is good etc.
There are some researchers to carry out at present and adopted alcohol-water system to carry out the research of polyacrylamide dispersion system, but few for the preparation of going back of acrylamide copolymer microballoon, only have some colleges and universities to have and study report on a small quantity.Tu Weixia (Tu Weixia, Wang Chonggang. novel pore throat nanoscale inorganic-organic polymer complex microsphere profile control reservoir oil displacing agent development [J]. Chinese offshore oil and gas, 2011,23 (4): 243-246) with SiO2 nano particle for inorganic component, with acrylamide, vinylformic acid and linking agent for organic constituent, dispersion polymerization processes is adopted to obtain a kind of inorganic-organic polymer complex microsphere profile adjustment and oil displacement material of novel pore scale.Research shows this complex microsphere structure, and microspherulite diameter is even, for submicron order is to micron order; Under the condition of high temperature, high salinity, having good swelling property and stability, inflatable more than 8 times of its particle diameter, is a kind of profile adjustment and oil displacement material with application potential; But viewed from the embodiment patent CN102485830A disclosed in it, solvent is the mixed solution of ethanol and ethyl acetate.Bu Daolu (Bu Daolu, Wan Tao, Song Maosheng, Deng. the research [J] of dispersion copolymerization method polyacrylamide microsphere amendment. New Chemical Materials, 2013, 41 (30): 42-44) etc. acrylamide and Sodium styrene sulfonate are carried out dispersion polymerization and prepare polyacrylamide microsphere amendment, investigate ethanol/deionized water volume ratio, acrylamide, initiator, dispersion agent, the consumption of linking agent and styrene sulfonic acid sodium content and the particle diameter of temperature of reaction on polyacrylamide microsphere amendment and the impact of gel-strength, result shows that synthesized polymer microballoon amendment particle diameter is adjustable, median size is 1.0 ~ 8.5 μm, there is dispersed and gel-strength preferably, but there is no the evaluation of sealing characteristics.Lei Guanglun etc. (CN1594493A) adopt dispersion polymerization synthetic method, by polyacrylamide amine monomers, linking agent, initiator and promoting agent etc. with high pressure spraying atomization and ultrasonic atomizatio by the mixing solutions such as polymerization single polymerization monomer and linking agent, be scattered in the oil-phase medium of suitable temp and carry out polymerization synthesis, wherein high pressure spraying atomization and ultrasonic atomization process implement and acquire a certain degree of difficulty, and use oil medium; Liu Shirong etc. (CN101735413A) invent a kind of functional polymer microsphere with multi-layer core-shell structure as profile-controlling and plugging agent, nucleation and the propagation process of dispersion polymerization process can be controlled by changing core/shell multipolymer ratio of components, linking agent and degree of crosslinking, ion monomer composition etc., obtain having different surfaces electrically, the functional microsphere of different-grain diameter and different mechanical property, to adapt to different reservoir conditions, but it is in a particular embodiment not about the performance evaluation of microballoon, unknown to its result of use; Wu Feipeng etc. (CN1940008A) first synthetic copolymer core, and then synthesis is coated on the outer field another kind of shell copolymers of core.By water-soluble neutral monomer acrylamide and ion monomer I and linking agent multipolymer group nucleation portion, form shell part by water-soluble neutral monomer acrylamide and ion monomer II and linking agent multipolymer; Ion monomer I and ion monomer II has opposite charges.This deep adjusting water blocking agent of self-crosslinked shell acrylamide multipolymer is a kind of white solid powder, and grain diameter is 500nm-100 μm.From the wide result to several order of magnitude of its size distribution, it should be the method that have employed precipitation polymerization.
Make a general survey of above-mentioned research, only have and adopt individually alcohol/water as dispersion system, although or introduce hydrophobic monomer but have employed organic solvent as dispersiveness to prepare the report of acrylamide copolymer microballoon dispersion system, but the alcohol-water system dispersion polymerization that high salinity reservoirs requires that can adapt to containing hydrophobic monomer has no open, also such microballoon is not used for the research report of oil field profile control and water plugging application.
The present invention carries out on extensive, deep Research foundation in the synthesis to acrylamide copolymer microballoon dispersion system, structural characterization and properties, adopt dispersion polymerization processes, in alcohol-water system, adopt commercial water-soluble polymers as stablizer, adopt the method for a step or polystep reaction, obtain the acrylamide copolymer dispersion system microballoon that solid content is higher, particle diameter is that submicron has monodispersity to micron order.Improve the rig-site utilization of recovery ratio for tertiary oil production in oil field depth profile control, water blockoff, the displacement of reservoir oil etc. after obtained acrylamide copolymer microballoon dispersion system is direct or composite with other oil field chemicals.
Summary of the invention
One of technical problem to be solved by this invention is that the submicron existed in prior art contains a large amount of oil phases and a certain amount of emulsifying agent to micron order acrylamide copolymer microballoon many employings inverse emulsion polymerization, these components add cost on the one hand, one side is the invalid problem with the compatibility of surfactant oil displacement that even can affect for the displacement of reservoir oil, a kind of temperature resistant antisalt acrylamide copolymer microballoon dispersion system is provided, adopt alcohol-water system dispersion polymerization, not containing oil phase and emulsifying agent, can solve the problem preferably.
Two of technical problem to be solved by this invention is to provide the preparation method of the temperature resistant antisalt acrylamide copolymer microballoon dispersion system in one of a kind of technical solution problem.
Three of technical problem to be solved by this invention is to provide the application of temperature resistant antisalt acrylamide copolymer microballoon dispersion system in tertiary oil production in oil field of one of a kind of technical solution problem.
In order to one of solve the problems of the technologies described above, the present invention is as follows by the following technical solutions: a kind of temperature resistant antisalt acrylamide copolymer microballoon dispersion system, and this dispersion system reacts obtained by copolymerization component under the existence of initiator; With weight parts, described copolymerization component comprises:
A) alcohol-water mixture of 70 ~ 90 parts;
B) 1 ~ 10 part of stablizer;
C) 0.1 ~ 5 part of linking agent;
D) comonomer of 10 ~ 30 parts.
In technique scheme, the mixture more than at least one or two of the alcohol in described alcohol-water mixture preferably in ethanol, propyl alcohol, (uncle) butanols, consumption accounts for 50 ~ 90w.t.% of alcohol-water system.
In technique scheme, described stablizer is preferably at least one in polyoxyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), hydroxypropylcellulose (HPC), polyacrylic acid (PAA) and dextrin, and consumption accounts for 1 ~ 10w.t.% of copolymerization component; Two or more mixture more preferably in polyoxyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), hydroxypropylcellulose (HPC), polyacrylic acid (PAA) and dextrin, consumption accounts for 1 ~ 10w.t.% of copolymerization component; Select the technical scheme better effects if of wherein two or more mixture.
In technique scheme, described linking agent is preferably from the mixture being more than at least one or two in methylene-bisacrylamide, Vinylstyrene, polyethyleneglycol diacrylate and pentaerythritol triacrylate, and consumption accounts for 0.1 ~ 5w.t.% of copolymerization component.
In technique scheme, described comonomer preferably comprises following component: nonionic water-soluble monomers, anionic monomer are or/and cationic monomer, hydrophobic monomer; Wherein nonionic water-soluble monomers is preferably from water-soluble vinyl monomer, at least one of described vinyl monomer preferably in the monomer shown in formula (1), formula (2), formula (3) or formula (4):
Wherein, R
1, R
4, R
5, R
6all independent preferred from hydrogen, C
1~ C
4alkyl; R
2, R
3all independent preferred from hydrogen, C
1~ C
4alkyl or hydroxyl substituted alkyl group.
In technique scheme, at least one of described anionic monomer preferably in 2-acrylamide-2-methylpro panesulfonic acid, vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-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 salt; At least one of cationic monomer preferably in dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride; Hydrophobic monomer be preferably Long carbon chain ionic surfactant monomer, esters of acrylic acid hydrophobic monomer, containing one or more mixtures in the hydrophobic monomer of polynary ring compound, wherein Long carbon chain ionic surfactant monomer be preferably alkyl carbon chain number be 8 ~ 18 acrylamide azanyl sodium sulfonate or alkyl carbon chain number be 12 ~ 22 allyl alkyl ammonium chloride; Esters of acrylic acid hydrophobic monomer is preferably (methyl) alkyl acrylate of 1 ~ 20 from alkyl carbon chain number, containing the hydrophobic monomer of polynary ring preferably from NVP, (tertiary butyl) vinylbenzene, N-phenylmaleimide.
In technique scheme, described initiator can be all kinds of initiator well-known to those skilled in the art, those skilled in the art can carry out routine and select, such as but do not limit the composition of one or more be selected from water-soluble oxide, water soluble oxidized-reduction system, azo compound etc.; Wherein water-soluble oxide is selected from the persulphates such as Potassium Persulphate, Sodium Persulfate, ammonium persulphate, water soluble oxidized-reduction system is selected from compound that above-mentioned water soluble persulfates and water-soluble reducing agent form as sulphite or bisul-phite etc., azo compound is selected from azo diisobutyl amidine hydrochloride, 2,2'-azos [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
In technique scheme, can add some auxiliary agents in copolymerization component, as complexing agent, such as disodium ethylene diamine tetraacetate or diethylene triamine pentacetic acid (DTPA) sodium etc. are to eliminate the impact of metal ion on reaction, and consumption accounts for 0.01 ~ 1w.t.% of whole system.
In order to solve the problems of the technologies described above two, the present invention adopts technical scheme as follows: a kind of preparation method of acrylamide copolymer microballoon dispersion system, comprises following step:
A linking agent, comonomer dissolves are obtained aqueous phase system by () in water;
B () adds alcohol in above-mentioned aqueous phase system, stablizer mixes, and pH value is adjusted to 4 ~ 8, obtains mixture;
C initiator solution that initiator is made into by ();
D described mixture drops in reactor by (), stir and pass into rare gas element, being controlled by reactor temperature, at 10 ~ 30 DEG C, about to add initiator after half an hour, continues logical nitrogen rare gas element and stops logical nitrogen after 5 ~ 10 minutes and seal;
E temperature of reaction is increased to 40 ~ 90 DEG C by (), until white fine particle appears in transparent system, continue reaction 1 ~ 2 hour, obtain the acrylamide copolymer microballoon dispersion system of White-opalescent;
In technique scheme, auxiliary agent can also be added in aqueous phase system in step (a), as complexing agent, such as disodium ethylene diamine tetraacetate or diethylene triamine pentacetic acid (DTPA) sodium etc. are to eliminate the impact of metal ion on reaction, and consumption accounts for 0.01 ~ 1% of copolymerization component.
In technique scheme, solid content or formation nucleocapsid structure needed for temperature resistant antisalt acrylamide copolymer microballoon dispersion system, also can carry out second and third time to feed in raw material, the temperature resistant antisalt acrylamide copolymer microballoon dispersion system finally obtained is the stabilising system of White-opalescent.
In order to solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the arbitrary described application of temperature resistant antisalt acrylamide copolymer microballoon dispersion system in tertiary oil production in oil field in a kind of technique scheme.
In technique scheme, described application can adopt routine techniques means well-known to those skilled in the art to be used in tertiary oil production in oil field by described acrylamide copolymer microballoon dispersion system, such as by temperature resistant antisalt acrylamide copolymer microballoon dispersion system directly or in temperature resistant antisalt acrylamide copolymer microballoon dispersion system, add tensio-active agent stir, this system just can be used for tertiary oil production in oil field depth profile control, water blockoff, the displacement of reservoir oil etc. and improves in the application at the scene of recovery ratio.
Temperature resistant antisalt acrylamide copolymer microballoon dispersion system that the present invention relates to and preparation method thereof, owing to selecting alcohol-water system, adopts the method for a step or polystep reaction, obtains the temperature resistant antisalt acrylamide copolymer dispersion system microballoon that solid content is higher.The temperature resistant antisalt acrylamide copolymer microballoon dispersion system using preparation technology provided by the present invention to obtain, polymer microballoon initial particle is that submicron has monodispersity to micron order, the rig-site utilization of recovery ratio is improved for tertiary oil production in oil field depth profile control, water blockoff, the displacement of reservoir oil etc., not by the impact of on-the-spot water-mineralizing degree after obtained temperature resistant antisalt acrylamide copolymer microballoon dispersion system is direct or composite with other oil field chemicals.
Adopt technical scheme of the present invention, dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 5.2,9.4,12.8 times, carry out shutoff experiment at 0.2 mpa with the nucleopore filters of 10 microns and all obtain better effects, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the initial particle figure of embodiment 4 product;
Fig. 2 is the grain-size graph of the aging expansion of embodiment 4 product after 3 days;
Fig. 3 is the shutoff experimental data curve of the aging different number of days of embodiment 4.
Below by specific embodiment, the present invention will be further elaborated.
Embodiment
[embodiment 1]
First add 1000g deionized water in a reservoir, methylene-bisacrylamide (MBA) 2.5g, disodium ethylene diamine tetraacetate (EDTA) 0.3g, 2-acrylamide-2-methylpro panesulfonic acid (AMPS) 125g, acrylamide (AM) 375g, 2-acrylamido tetradecyl sodium sulfonate 5g, be stirred to and mix completely, carry out neutralizing and pH being adjusted to 7 with the equimolar sodium hydroxide of AMPS (NaOH), then polyoxyethylene glycol (PEG) 250g being stirred to adding the trimethyl carbinol (TBA) 1300g and molecular weight 20000 mixes completely.This solution is dropped in reactor, logical nitrogen 30min.At 15 DEG C, stirring is opened, keep rotating speed 300rpm, successively instill concentration be ammonium persulphate (APS) aqueous solution of 1.25%, sodium bisulfite (MBS) aqueous solution of 0.75% and 2.5% 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] each 10g of dihydrochloride (AIBA) aqueous solution, and maintenance leads to nitrogen and stirring, logical nitrogen is stopped after 30min, temperature is risen to 30 DEG C and keep 1h, rise to 50 DEG C again and keep 3h, period, visible reaction soln became translucent until final product White-opalescent emulsion form system gradually by transparent.
Can separate out solid content with reference to company standard " polymer microballoon in-depth profile control technical qualification " the measuring method test of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation is 21.5%; Dried powdered sample is carried out scanning electron microscopic observation, and obtaining initial mean particle size is 2.3 μm; Dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 5.2,7.8,9.6 times, carries out shutoff experiment at 0.2 mpa all obtain better effects with the nucleopore filters of 10 microns.
[embodiment 2]
First add 1000g deionized water in a reservoir, pentaerythritol triacrylate 2.2g, disodium ethylene diamine tetraacetate (EDTA) 0.22g, 2-acrylamide-2-methylpro panesulfonic acid (AMPS) 90g, acrylyl oxy-ethyl-trimethyl salmiac 30g, acrylamide (AM) 330g, Octyl acrylate 4g, be stirred to and mix completely, carry out neutralizing and pH being adjusted to 6.5 with the equimolar sodium hydroxide of AMPS (NaOH), add polyvinylpyrrolidone (PVP) 25g that the trimethyl carbinol (TBA) 775g and the trade mark are K30 again and be stirred to and mix completely.This solution is dropped in reactor, logical nitrogen 30min.At 15 DEG C, stirring is opened, keep rotating speed 280rpm, according to this instill concentration be ammonium persulphate (APS) aqueous solution of 5.5%, sodium bisulfite (MBS) aqueous solution of 3.3% and 11% 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] each 10g of dihydrochloride (AIBA) aqueous solution, and maintenance leads to nitrogen and stirring, logical nitrogen is stopped after 30min, temperature is risen to 30 DEG C and keep 1h, rise to 45 DEG C again and keep 2h, period, visible reaction soln became translucent until final product White-opalescent emulsion form system gradually by transparent.
Can separate out solid content with reference to company standard " polymer microballoon in-depth profile control technical qualification " the measuring method test of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation is 19.7%; Dried powdered sample is carried out scanning electron microscopic observation, and obtaining initial mean particle size is 1.8 μm; Dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 4.6,7.2,8.6 times, carries out shutoff experiment at 0.2 mpa all obtain better effects with the nucleopore filters of 10 microns.
[embodiment 3]
First add 880g deionized water in a reservoir, Vinylstyrene 3.2g, disodium ethylene diamine tetraacetate (EDTA) 0.28g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 80g, acrylamide (AM) 480g, t-butyl styrene 6g, be stirred to and mix completely, with sodium hydroxide (NaOH) aqueous solution, pH is adjusted to 5.5, then adds polyvinyl alcohol (PVA) 25g that the trimethyl carbinol (TBA) 1590g and the trade mark are 17-88 and be stirred to and mix completely.This solution is dropped in reactor, logical nitrogen 30min.At 30 DEG C, stirring is opened, keep rotating speed 280rpm, instillation concentration is Diisopropyl azodicarboxylate (AIBN) the ethanolic soln 10g of 4%, and maintenance leads to nitrogen and stirring, logical nitrogen is stopped after 30min, temperature is risen to 55 DEG C and keep 3h, period, visible reaction soln became translucent until final product White-opalescent emulsion form system gradually by transparent.
Can separate out solid content with reference to company standard " polymer microballoon in-depth profile control technical qualification " the measuring method test of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation is 24.9%; Dried powdered sample is carried out scanning electron microscopic observation, and obtaining initial mean particle size is 3.2 μm; Dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 3.9,8.5,10.8 times, carries out shutoff experiment at 0.2 mpa all obtain better effects with the nucleopore filters of 10 microns.
[embodiment 4]
First add 600g deionized water in a reservoir, polyethyleneglycol diacrylate 2.8g, disodium ethylene diamine tetraacetate (EDTA) 0.26g, 2-acrylamide-2-methylpro panesulfonic acid (AMPS) 70g, dimethyl diallyl ammonium chloride 50g, acrylamide (AM) 330g, NVP 8.5g, be stirred to and mix completely, carry out neutralizing and pH being adjusted to 6.5 with the equimolar sodium hydroxide of AMPS (NaOH), add polyvinylpyrrolidone (PVP) 4g that the trimethyl carbinol (TBA) 1880g and the trade mark are K90 again and be stirred to and mix completely.This solution is dropped in reactor, logical nitrogen 30min.At 30 DEG C, stirring is opened, keep rotating speed 280rpm, instillation concentration is ammonium persulphate (APS) aqueous solution 10g of 3.2%, and maintenance leads to nitrogen and stirring, logical nitrogen is stopped after 30min, temperature risen to 55 DEG C of maintenance 2h, rise to 65 DEG C of maintenance 1h again, period, visible reaction soln became translucent until final product White-opalescent emulsion form system gradually by transparent.
Can separate out solid content with reference to company standard " polymer microballoon in-depth profile control technical qualification " the measuring method test of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation is 21.4%; Dried powdered sample is carried out scanning electron microscopic observation, and obtaining initial mean particle size is 1.2 μm; Dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 3.2,7.4,9.1 times, carries out shutoff experiment at 0.2 mpa all obtain better effects with the nucleopore filters of 10 microns.
[embodiment 5]
First add 550g deionized water in a reservoir, methylene-bisacrylamide (MBA) 2.2g, disodium ethylene diamine tetraacetate (EDTA) 0.2g, 2-acrylamide-2-methylpro panesulfonic acid (AMPS) 90g, acrylamide (AM) 310g, solution property (C18DMAAC) 8g, be stirred to and mix completely, carry out neutralizing and pH being adjusted to 5 with the equimolar sodium hydroxide of AMPS (NaOH), then add polyvinylpyrrolidone (PVP) 12g that ethanol 1700g and the trade mark are K60 and be stirred to and mix completely.This solution is dropped in reactor, logical nitrogen 30min.At 25 DEG C, stirring is opened, keep rotating speed 230rpm, instillation concentration is Potassium Persulphate (KPS) aqueous solution 10g of 4%, and maintenance leads to nitrogen and stirring, logical nitrogen is stopped after 30min, temperature risen to 45 DEG C of maintenance 2h, rise to 70 DEG C of maintenance 4h again, period, visible reaction soln became translucent until final product White-opalescent emulsion form system gradually by transparent.
Can separate out solid content with reference to company standard " polymer microballoon in-depth profile control technical qualification " the measuring method test of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation is 16.4%; Dried powdered sample is carried out scanning electron microscopic observation, and obtaining initial mean particle size is 2.5 μm; Dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 5.2,9.4,12.3 times, carries out shutoff experiment at 0.2 mpa all obtain better effects with the nucleopore filters of 10 microns.
[embodiment 6]
First add 1000g deionized water in a reservoir, methylene-bisacrylamide (MBA) 2.5g, disodium ethylene diamine tetraacetate (EDTA) 0.3g, 2-acrylamide-2-methylpro panesulfonic acid (AMPS) 100g, acrylamide (AM) 400g, 2-acrylamido sodium laurylsulfonate 10g, be stirred to and mix completely, carry out neutralizing and pH being adjusted to 7 with the equimolar sodium hydroxide of AMPS (NaOH), add polyvinylpyrrolidone (PVP) 25g and hydroxypropylcellulose (HPC) 50g that ethanol 1300g and the trade mark are K30 again and be stirred to and mix completely.This solution is dropped in reactor, logical nitrogen 30min.At 15 DEG C, stirring is opened, keep rotating speed 300rpm, successively instill concentration be ammonium persulphate (APS) aqueous solution of 1.25%, sodium bisulfite (MBS) aqueous solution of 0.75% and 2.5% 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] each 10g of dihydrochloride (AIBA) aqueous solution, and maintenance leads to nitrogen and stirring, logical nitrogen is stopped after 30min, temperature is risen to 30 DEG C and keep 1h, rise to 60 DEG C again and keep 3h, period, visible reaction soln became translucent until final product White-opalescent emulsion form system gradually by transparent.
Can separate out solid content with reference to company standard " polymer microballoon in-depth profile control technical qualification " the measuring method test of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation is 19.8%; Dried powdered sample is carried out scanning electron microscopic observation, and obtaining initial mean particle size is 5.8 μm; Dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 4.2,7.1,10.2 times, carries out shutoff experiment at 0.2 mpa all obtain better effects with the nucleopore filters of 10 microns.
[embodiment 7]
First add 550g deionized water in a reservoir, polyethyleneglycol diacrylate 2.8g, disodium ethylene diamine tetraacetate (EDTA) 0.26g, 2-acrylamide-2-methylpro panesulfonic acid (AMPS) 80g, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride 40g, acrylamide (AM) 330g, N-phenylmaleimide 7.8g, be stirred to and mix completely, carry out neutralizing and pH being adjusted to 6.5 with the equimolar sodium hydroxide of AMPS (NaOH), add polyvinylpyrrolidone (PVP) 3g and dextrin 5g that the trimethyl carbinol (TBA) 1880g and the trade mark are K90 again and be stirred to and mix completely.This solution is dropped in reactor, logical nitrogen 30min.At 30 DEG C, stirring is opened, keep rotating speed 280rpm, instillation concentration is ammonium persulphate (APS) aqueous solution 12g of 2.2%, and maintenance leads to nitrogen and stirring, logical nitrogen is stopped after 30min, temperature risen to 55 DEG C of maintenance 2h, rise to 70 DEG C of maintenance 1h again, period, visible reaction soln became translucent until final product White-opalescent emulsion form system gradually by transparent.
Can separate out solid content with reference to company standard " polymer microballoon in-depth profile control technical qualification " the measuring method test of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation is 20.6%; Dried powdered sample is carried out scanning electron microscopic observation, and obtaining initial mean particle size is 8.9 μm; Dispersion system is directly used total mineralization 165000mg/L (wherein Ca
2++ Mg
2+salt solution 7000mg/L) is made into the solution of 0.15%, at 90 DEG C aging 1 day, 3 days, 7 days, solution is observed under an optical microscope, with the particle diameter after expansion compared with initial particle, expansion multiple is respectively 5.2,9.4,12.8 times, carries out shutoff experiment at 0.2 mpa all obtain better effects with the nucleopore filters of 10 microns.
[embodiment 8]
With embodiment 6, just replace polyvinylpyrrolidone (PVP) 25g and hydroxypropylcellulose (HPC) 50g with polyvinylpyrrolidone (PVP) 75g, the corresponding expansion multiple of product is respectively 3.4,5.6,7.3 times, carries out shutoff experiment effect be at 0.2 mpa worse than embodiment 6 with the nucleopore filters of 10 microns.
[embodiment 9]
With embodiment 6, just replace polyvinylpyrrolidone (PVP) 25g and hydroxypropylcellulose (HPC) 50g with hydroxypropylcellulose (HPC) 75g, the corresponding expansion multiple of product is respectively 3.6,6.5,8.9 times, carries out shutoff experiment effect be at 0.2 mpa worse than embodiment 6 with the nucleopore filters of 10 microns.
By the contrast of embodiment 6 and embodiment 8,9, contriver is surprised to find, and selects two kinds of stablizers mixing to achieve synergistic effect, is all better than a kind of implementation result.
Claims (10)
1. a temperature resistant antisalt acrylamide copolymer microballoon dispersion system, this dispersion system reacts obtained by copolymerization component under the existence of initiator; With weight parts, described copolymerization component comprises:
A) alcohol-water mixture of 70 ~ 90 parts;
B) 1 ~ 10 part of stablizer;
C) 0.1 ~ 5 part of linking agent;
D) comonomer of 10 ~ 30 parts.
2. temperature resistant antisalt acrylamide copolymer microballoon dispersion system according to claim 1, the alcohol that it is characterized in that in described alcohol-water mixture is selected from least one in ethanol, propyl alcohol, (uncle) butanols, and consumption accounts for 50 ~ 90w.t.% of alcohol-water system.
3. temperature resistant antisalt acrylamide copolymer microballoon dispersion system according to claim 1, it is characterized in that described stablizer is at least one in polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropylcellulose, polyacrylic acid and dextrin, consumption accounts for 1 ~ 10w.t.% of copolymerization component.
4. temperature resistant antisalt acrylamide copolymer microballoon dispersion system according to claim 1, it is characterized in that described linking agent is selected from as at least one in methylene-bisacrylamide, Vinylstyrene, polyethyleneglycol diacrylate and pentaerythritol triacrylate etc., consumption accounts for 0.1 ~ 5w.t.% of whole system.
5. temperature resistant antisalt acrylamide copolymer microballoon dispersion system according to claim 1, is characterized in that described comonomer comprises following component:
A) nonionic water-soluble monomers of 5 ~ 99.9w.t.%;
B) 0 ~ 50w.t.% anionic monomer is or/and cationic monomer;
C) hydrophobic monomer of 0.1 ~ 10w.t.%.
6. temperature resistant antisalt acrylamide copolymer microballoon dispersion system according to claim 5, it is characterized in that described nonionic water-soluble monomers is selected from water-soluble vinyl monomer, described vinyl monomer is selected from least one in formula (1), formula (2), formula (3) or the monomer shown in formula (4):
Wherein, R
1, R
4, R
5, R
6all independently be selected from hydrogen, C
1~ C
4alkyl; R
2, R
3all independently be selected from hydrogen, C
1~ C
4alkyl or hydroxyl substituted alkyl group.
7. temperature resistant antisalt acrylamide copolymer microballoon dispersion system according to claim 5, is characterized in that described anionic monomer is selected from least one in 2-acrylamide-2-methylpro panesulfonic acid, vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-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 salt; Described cationic monomer is selected from least one in dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride.
8. temperature resistant antisalt acrylamide copolymer microballoon dispersion system according to claim 5, it is characterized in that described hydrophobic monomer be Long carbon chain ionic surfactant monomer, esters of acrylic acid hydrophobic monomer, containing one or more mixtures in the hydrophobic monomer of polynary ring compound.
9. the arbitrary described temperature resistant antisalt acrylamide copolymer microballoon dispersion system preparation method of claim 1 ~ 8, comprises following step:
A linking agent, comonomer dissolves are obtained aqueous phase system by () in water;
B () adds alcohol in above-mentioned aqueous phase system, stablizer mixes, and pH value is adjusted to 4 ~ 8, obtains mixture;
C oil-soluble initiator with finite concentration wiring solution-forming soluble in water, dissolves with a small amount of ethanol or ethyl acetate etc. and is made into certain density solution by () by water soluble starter;
D described mixture drops in reactor by (), stir and pass into rare gas element, reactor temperature is controlled at 10 ~ 30 DEG C, about (be greater than or less than and all cannot half an hour half an hour?) after add initiator, continue logical nitrogen rare gas element after 5 ~ 10 minutes (unclear, a scope please be provide.) stop logical nitrogen and seal;
E temperature of reaction is increased to 40 ~ 90 DEG C by (), until white fine particle appears in transparent system, continue reaction 1 ~ 2 hour, obtain the acrylamide copolymer microballoon dispersion system of White-opalescent;
F () is according to required solid content or form nucleocapsid structure, and also can carry out second and third time and feed in raw material, the acrylamide copolymer microballoon dispersion system finally obtained is the stabilising system of White-opalescent.
10. the arbitrary described application of temperature resistant antisalt acrylamide copolymer microballoon dispersion system in tertiary oil production in oil field of claim 1 ~ 8.
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