CN105524215B - Temperature-resistant anti-salt acrylamide copolymer microballoon dispersion and its preparation method and application - Google Patents
Temperature-resistant anti-salt acrylamide copolymer microballoon dispersion and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of temperature-resistant anti-salt acrylamide copolymer microballoon dispersion and its preparation method and application, mainly solves to exist in the prior art sub-micron to micron order acrylamide copolymer microballoon and mostly use that inverse emulsion polymerization contains a large amount of oil mutually and a certain amount of emulsifier causes the problems such as at high cost, the displacement of reservoir oil is invalid, poor with the compatibility of surfactant oil displacement.Using a kind of temperature-resistant anti-salt acrylamide copolymer microballoon dispersion, which is made in the presence of initiator by the reaction of alcohol aqueous dispersion polymerization by copolymerization component；Based on parts by weight, the copolymerization component includes: 70~90 parts of alcohol-water mixture；1~10 part of stabilizer；0.1~5 part of crosslinking agent；The technical solution of 10~30 parts of comonomer preferably resolves the problem, can be used for the field application that depth profile control used for tertiary oil recovery, water blockoff, displacement of reservoir oil etc. improve recovery ratio.
Description
Technical field
The present invention relates to a kind of temperature-resistant anti-salt acrylamide copolymer microballoon dispersions and its preparation method and application.
Background technique
Polyacrylamide microsphere is the polyacrylamide spheroidal particle containing crosslinking agent, can use homogeneous method and heterogeneous legal system
It is standby.The former mainly includes reversed emulsion polymerization, conversed phase micro emulsion copolymerization method, and product is generally latex or fine latex；The latter is then
Including dispersion copolymerization method, precipitation polymerization method, via Inverse-Phase Suspension Polymerization etc., product is generally solia particle.Not due to polymerization
Together, the partial size of reaction product is also different.
Domestic each elephant is by primary, secondary oil recovery, and crude oil water content is continuously increased, and part elephant successively enters three
The secondary oil recovery stage.With the raising of recovery percent, well water is a common problem present in current oil field development, especially
It is heterogeneity and oily, water viscosity difference of the old filed due to oil reservoir of long-term injecting water exploitation, causes injection water along water injection well
High permeability zone or crack between producing well are advanced by leaps and bounds and fingering, causes the too early water logging of producing well, oil production decline, aqueous rising.
Well water is reduced, usually blocks high permeability zone or crack, the water-absorption surface for adjusting water injection well, reduction injection water edge from water injection well
Oil well is charged into high permeability zone or crack, and injection water is forced to change flow direction, and less permeable layer is in improve injection water
Sweep efficiency, improving ecology development effectiveness.The one kind of polyacrylamide microsphere as most common organic water plugging profile control agent, to water
There is apparent selectivity, its chance oil volume is constant, meets water then volume expansion, therefore has good water plugging effect, while having effectively
Phase is long, does not pollute stratum, construction is simple, activity duration short holding point.Due to the permeability of oil reservoir is different and heterogeneity compared with
Seriously, the profile control for needing various sizes of polymer microballoon to be just able to satisfy Different Strata blocks requirement.Scale is shouted micro- for hole
The middle and high infiltration oil reservoir of meter level needs particle size range to can be only achieved effective closure in sub-micron to micron-sized polymer microballoon.
The polymer microballoon of the size can take reverse micro emulsion or dispersion copolymerization method to prepare, but contain in inverse emulsion system
Mutually and a certain amount of emulsifier, these components are invalid even will affect and Surfactant for EOR for the displacement of reservoir oil to a large amount of oil
The compatibility of agent, therefore, not showing certain advantage the dispersion polymerization systems of oil-containing phase and emulsifier.
Dispersin polymerization is a kind of new method for producing polymer, the beginning of the seventies by Britain's ICI Company researchers first
It proposes.Strictly, dispersin polymerization is a kind of precipitation polymerization of specific type, and monomer, stabilizer and initiator are all dissolved in Jie
In matter, reaction starts preceding for homogeneous system.Polymer generated is insoluble in the medium, and polymer chain reaches critical chain length
Afterwards, it separates out and from medium.With-as precipitation polymerization difference be separate out come polymer be not to form powdered or block
The polymer of shape but be agglomerated into little particle, by means of stabilizer suspend in the medium, formed be similar to polymer emulsion it is steady
Determine dispersion.Dispersion polymerization process is more complicated, opposite point of each response parameter such as stabilizer types and dosage, stabilizer
Protonatomic mass, monomer concentration, initiator concentration, the selection of solvent, reaction temperature etc. all to the size of final particle, size distribution with
And product relative molecular mass has critically important influence.Dispersin polymerization is mainly used for oil-soluble monomer and non-polar monomer preparation is single
The dispersin polymerization research of dispersion microsphere, water-soluble monomer especially AM is relatively fewer.In recent years, decentralized medium is used water as,
The research of synthesis functionalization PAM dispersion is increasingly becoming hot spot, and this method not only increases polymer quality score, Er Qiezhen
It is just realizing nontoxic, pollution-free, is meeting environmental requirement, will also become one of polyacrylamide microsphere preparation developing direction.According to
Dispersin polymerization can be divided into four major class at present by the stabilizer of addition and the type of dispersion: alcohol-water, salt-water, polymer-water
And mixed system, for the higher situation of domestic most oil field salinities, if using the salt-aqueous systems for being mostly sulfate, it will
Chance divalent ion is caused to lead to the problem of precipitating；Using polymer-aqueous systems, then it is steady that targeted polymer is synthesized in advance
Determine agent, increases the complexity of preparation；Although mixed system combines the advantages of several systems, but since system is increasingly complex,
Many compatibility issues but will be encountered in practical application；Therefore alcohol-water system is because its composition is simple and Surfactant for EOR
The features such as agent compatibility is good has the advantages that more prominent.
There are some researchers to carry out the research for carrying out polyacrylamide dispersion system using alcohol-water system at present, but
It is used to prepare being not much for acrylamide copolymer microballoon, there are a small amount of research report in only some colleges and universities.Tu Weixia (Tu Wei
Rosy clouds, the novel pore throat nanoscale inorganic of Wang Chonggang-organic polymer complex microsphere profile control reservoir oil displacing agent development [J] China offshore oil and gas,
2011,23 (4): 243-246) using SiO2 nano particle as inorganic component, it is to have unit with acrylamide, acrylic acid and crosslinking agent
Point, a kind of inorganic-organic polymer complex microsphere profile adjustment and oil displacement material of novel pore scale has been made using dispersion polymerization processes
Material.Research shows that the complex microsphere structure, microspherulite diameter is uniform, for submicron order to micron order；In high temperature, the item of high salinity
There is good dilatancy and stability, it is a kind of profile adjustment and oil displacement with application potential that partial size is 8 times or more inflatable under part
Material；But in terms of the embodiment in patent CN102485830A disclosed in it, solvent is the mixed liquor of ethyl alcohol and ethyl acetate.Foretell
(Bu Daolu, Wan Tao, Song Maosheng wait research [J] chemical industry novel-section of dispersion copolymerization method polyacrylamide microsphere profile control agent to road dew
Material, 2013,41 (30): 42-44) etc. acrylamide and sodium styrene sulfonate are subjected to dispersin polymerization are prepared for pam microemulsion
Ball profile control agent has investigated ethyl alcohol/deionized water volume ratio, acrylamide, initiator, dispersing agent, the dosage of crosslinking agent and benzene second
Alkene sulfonic acid sodium content and reaction temperature are to the partial size of polyacrylamide microsphere profile control agent and the influence of gel strength, the results showed that institute
The polymer microballoon profile control agent partial size of synthesis is adjustable, and average grain diameter is 1.0~8.5 μm, has preferable dispersibility and gel strong
Degree, but the not evaluation of sealing characteristics.Lei Guanglun etc. (CN 1594493A) uses dispersin polymerization synthetic method, i.e., by polypropylene
Amide monomer, crosslinking agent, initiator and activating agent etc. are with high-pressure injection atomization and ultrasonic atomizatio by polymerized monomer and crosslinking agent etc.
Mixed solution is scattered in the oil-phase medium of suitable temperature and carries out polymerization synthesis, wherein high-pressure injection atomization and ultrasonic atomizatio work
Skill, which implements, to acquire a certain degree of difficulty, and uses oil medium；Liu Shirong etc. (CN101735413A) has invented a kind of tool
There is the functional polymer microsphere of multi-layer core-shell structure as profile-controlling and plugging agent, it can be by changing core shell copolymer ratio of components, handing over
The nucleation and propagation process for joining the control dispersion polymerization process such as agent and the degree of cross linking, ion monomer composition, obtain with different surfaces
Electrically, the functional microsphere of different-grain diameter and different mechanical properties, to adapt to different reservoir conditions, but in a particular embodiment simultaneously
There is no the performance evaluation in relation to microballoon, it is unknown to be used for effect；Wu Feipeng etc. (CN 1940008A) synthesizes copolymerization first
Then object core synthesizes another shell copolymers for being coated on core outer layer again.By water-soluble neutral monomer acrylamide and ion list
Body I and crosslinking agent copolymer group nucleation portion are copolymerized by water-soluble neutral monomer acrylamide and ion monomer II and crosslinking agent
Object constitutes shell parts；Ion monomer I and ion monomer II has opposite charges.The nucleocapsid is from knot acrylamide copolymer deep
Profile-controlling and plugging agent is a kind of white solid powder, and grain diameter is 500nm-100 μm.From wide to the several order of magnitude of its particle diameter distribution
Result see, it should be the method using precipitation polymerization.
The studies above is made a general survey of, only individually using alcohol/water as dispersion, although or introducing hydrophobic monomer use
Organic solvent prepares the report of acrylamide copolymer microballoon dispersion as dispersibility, but contains hydrophobic monomer
The alcohol-water system dispersin polymerization for adapting to high salinity reservoirs requirement is not disclosed, such microballoon is not used for oil field profile control yet
The research report of water blockoff application.
The present invention carries out wide in synthesis, structural characterization and the properties to acrylamide copolymer microballoon dispersion
On the basis of general, in-depth study, using dispersion polymerization processes, made in alcohol-water system using the water-soluble polymer of commercialization
For stabilizer, it is micro- to obtain the higher acrylamide copolymer dispersion of solid content for the method reacted using one or more steps
Ball, partial size are sub-micron to micron order and have monodispersity.Acrylamide copolymer microballoon dispersion obtained is direct
Or showing for recovery ratio is improved for tertiary oil production in oil field depth profile control, water blockoff, displacement of reservoir oil etc. after compounding with other oil field chemicals
Field application.
Summary of the invention
The first technical problem to be solved by the present invention is sub-micron existing in the prior art to micron order acrylamide
Quasi polymer microballoon mostly uses inverse emulsion polymerization to contain a large amount of oil phase and a certain amount of emulsifier, on the one hand these components increase
Cost is added, has been on the one hand invalid the problem of even will affect the compatibility with surfactant oil displacement for the displacement of reservoir oil, mentions
For a kind of temperature-resistant anti-salt acrylamide copolymer microballoon dispersion, using alcohol-water system dispersin polymerization, not oil-containing phase and cream
Agent can preferably solve the above problems.
The second technical problem to be solved by the present invention is to provide a kind of temperature-resistant anti-salt third solved in one of technical problem
The preparation method of acrylamide polymer microballoon dispersion.
The third technical problem to be solved by the present invention is to provide a kind of temperature-resistant anti-salt propylene for solving one of technical problem
Application of the acylamide polymer microballoon dispersion in tertiary oil production in oil field.
One of in order to solve the above-mentioned technical problem, the present invention is as follows using following technical scheme: a kind of temperature-resistant anti-salt propylene
Acylamide polymer microballoon dispersion, which is reacted in the presence of initiator by copolymerization component is made；With weight
Number meter, the copolymerization component includes:
A) 70~90 parts of alcohol-water mixture；
B) 1~10 part of stabilizer；
C) 0.1~5 part of crosslinking agent；
D) 10~30 parts of comonomer.
In above-mentioned technical proposal, the alcohol in the alcohol-water mixture preferably is selected from ethyl alcohol, propyl alcohol, at least one in (uncle) butanol
Kind or two or more mixtures, dosage account for 50~90w.t.% of alcohol-water system.
In above-mentioned technical proposal, the stabilizer is preferably polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyethylene pyrrole
At least one of pyrrolidone (PVP), hydroxypropyl cellulose (HPC), polyacrylic acid (PAA) and dextrin, dosage accounts for copolymerization component
1~10w.t.%；Further preferably polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), hydroxyl
Two or more mixtures in propyl cellulose (HPC), polyacrylic acid (PAA) and dextrin, dosage account for copolymerization component 1~
10w.t.%；Select the technical solution effect of the above mixture of two of them more preferable.
In above-mentioned technical proposal, the crosslinking agent preferably is selected from as methylene-bisacrylamide, divinylbenzene, polyethylene glycol
At least one of diacrylate and pentaerythritol triacrylate or two or more mixtures, dosage account for copolymerization component
0.1~5w.t.%.
In above-mentioned technical proposal, the comonomer preferably comprises following components: nonionic water-soluble monomers, anion
Monomer or/and cationic monomer, hydrophobic monomer；Wherein nonionic water-soluble monomers preferably are selected from water-soluble vinyl monomer, described
Vinyl monomer preferably is selected from least one of formula (1), formula (2), monomer shown in formula (3) or formula (4):
Wherein, R1、R4、R5、R6Independently it preferably is selected from hydrogen, C1~C4Alkyl；R2、R3Independently it preferably is selected from hydrogen, C1~C4's
Alkyl or hydroxyl substituted alkyl group.
In above-mentioned technical proposal, the anionic monomer preferably be selected from 2- acrylamide-2-methylpro panesulfonic acid, acrylic acid,
Methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, alkene
At least one of propyl sulfonic acid, allyl phosphonic acid and/or its water-soluble alkali, alkaline-earth metal and ammonium salt；Cationic monomer
It preferably is selected from dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl trimethyl chlorine
Change at least one of ammonium and 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chloride；Hydrophobic monomer be preferably Long carbon chain from
One or more of subtype surface active monomer, esters of acrylic acid hydrophobic monomer, hydrophobic monomer containing polynary cyclic compound
Mixture, wherein Long carbon chain ionic surfactant monomer is preferably the acrylamide azanyl sulphur that alkyl carbon chain number is 8~18
The allyl alkyl ammonium chloride that sour sodium or alkyl carbon chain number are 12~22；Esters of acrylic acid hydrophobic monomer preferably is selected from alkyl carbon chain number
For 1~20 (methyl) alkyl acrylate, the hydrophobic monomer containing polynary ring preferably is selected from n-vinyl pyrrolidone, (tert-butyl)
Styrene, N-phenylmaleimide.
In above-mentioned technical proposal, the initiator can be all kinds of initiators well-known to those skilled in the art, ability
Field technique personnel can carry out conventional selection, such as but do not limit selected from water-soluble oxide, water soluble oxidized-reduction system,
The composition of one or more of azo compound etc.；Wherein water-soluble oxide is selected from potassium peroxydisulfate, sodium peroxydisulfate, mistake
The persulfates such as ammonium sulfate, water soluble oxidized-reduction system is selected from above-mentioned water soluble persulfates and water-soluble reducing agent is such as sub-
Compound, the azo compound of the compositions such as sulfate or acid sulphite are selected from azo diisobutyl amidine hydrochloride, 2,2'-
Azo [2- (2- imidazoline -2- base) propane] dihydrochloride, azodiisobutyronitrile, azobisisoheptonitrile etc..
In above-mentioned technical proposal, some auxiliary agents, such as complexing agent, such as disodium ethylene diamine tetraacetate can be added in copolymerization component
Or diethylene triamine pentacetic acid (DTPA) sodium etc. to be to eliminate influence of the metal ion to reaction, dosage account for whole system 0.01~
1w.t.%.
In order to solve the above-mentioned technical problem two, the present invention is as follows using technical solution: a kind of acrylamide copolymer
The preparation method of microballoon dispersion, including the following steps:
(a) it is dissolved in the water crosslinking agent, comonomer to obtain aqueous phase system；
(b) it is uniformly mixed that alcohol, stabilizer are added in above-mentioned aqueous phase system, and pH value is adjusted to 4~8, obtains mixture
Material；
(c) initiator solution for being made into initiator；
(d) mixed material is put into reaction kettle, stirs and be passed through inert gas, reactor temperature control is existed
10~30 DEG C, initiator about is added after half an hour, continues logical nitrogen inert gas 5~stop logical nitrogen after ten minutes and seal；
(e) reaction temperature is increased to 40~90 DEG C, until white fine particle occurs in transparent system, the reaction was continued 1~2
Hour, obtain the acrylamide copolymer microballoon dispersion of White-opalescent；
In above-mentioned technical proposal, auxiliary agent, such as complexing agent, such as second two can also be added in the aqueous phase system in step (a)
To eliminate influence of the metal ion to reaction, dosage accounts for copolymerization component for amine tetraacethyl disodium or diethylene triamine pentacetic acid (DTPA) sodium etc.
0.01~1%.
In above-mentioned technical proposal, according to solid content needed for temperature-resistant anti-salt acrylamide copolymer microballoon dispersion
Or core-shell structure is formed, second and third secondary charging can be also carried out, the temperature-resistant anti-salt acrylamide copolymer microballoon finally obtained point
Granular media system is the stabilising system of White-opalescent.
In order to solve the above-mentioned technical problem three, The technical solution adopted by the invention is as follows: in a kind of above-mentioned technical proposal
Application of any temperature-resistant anti-salt acrylamide copolymer microballoon dispersion in tertiary oil production in oil field.
In above-mentioned technical proposal, the application can use conventional technical means well-known to those skilled in the art by institute
The acrylamide copolymer microballoon dispersion stated is in tertiary oil production in oil field, such as by temperature-resistant anti-salt acrylamide polymer
It closes object microballoon dispersion directly or surfactant is added in temperature-resistant anti-salt acrylamide copolymer microballoon dispersion
It stirs evenly, which can be used for answering for the scene of the raising recovery ratio such as tertiary oil production in oil field depth profile control, water blockoff, displacement of reservoir oil
In.
Temperature-resistant anti-salt acrylamide copolymer microballoon dispersion of the present invention and preparation method thereof, due to selecting
Alcohol-water system, the method reacted using one or more steps obtain the higher temperature-resistant anti-salt acrylamide copolymer of solid content point
Granular media system microballoon.Use temperature-resistant anti-salt acrylamide copolymer microballoon dispersion made from preparation process provided by the present invention
System, polymer microballoon initial particle are sub-micron to micron order and have monodispersity, temperature-resistant anti-salt acrylic amide obtained
Polymer microballoon dispersion directly or after compounding with other oil field chemicals is used for tertiary oil production in oil field depth profile control, blocks up
Water, displacement of reservoir oil etc. improve the field application of recovery ratio, are not influenced by live water-mineralizing degree.
Using technical solution of the present invention, dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 5.2,9.4,12.8 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa, achieves preferable technical effect.
Detailed description of the invention
Fig. 1 is the initial particle figure of 4 product of embodiment；
Fig. 2 is the grain-size graph after 4 product aging of embodiment expands 3 days；
Fig. 3 is the closure experimental data curve of 4 aging different number of days of embodiment.
Below by specific embodiment, the present invention will be further elaborated.
Specific embodiment
[embodiment 1]
1000g deionized water, methylene-bisacrylamide (MBA) 2.5g, ethylenediamine tetra-acetic acid two are first added in a reservoir
Sodium (EDTA) 0.3g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS) 125g, acrylamide (AM) 375g, 2- acrylamide
Base myristyl sodium sulfonate 5g is stirred to being mixed thoroughly, is neutralized with the equimolar sodium hydroxide of AMPS (NaOH)
And pH is adjusted to 7, add polyethylene glycol (PEG) 250g of the tert-butyl alcohol (TBA) 1300g and molecular weight 20000 and is stirred to complete
It is complete to be uniformly mixed.This solution is put into reaction kettle, nitrogen 30min is led to.Stirring is opened at 15 DEG C, keeps revolving speed
It is water-soluble for 1.25% ammonium persulfate (APS) aqueous solution, 0.75% sodium hydrogensulfite (MBS) successively to instill concentration by 300rpm
Liquid and 2.5% 2,2'- azo [2- (2- imidazoline -2- base) propane] dihydrochloride (AIBA) each 10g of aqueous solution, and keep after
Continuous logical nitrogen and stirring stop logical nitrogen after 30min, temperature are risen to 30 DEG C of holdings 1h, then rise to 50 DEG C of holding 3h, it is during which visible instead
Solution is answered gradually to become translucent until end product White-opalescent emulsion form system by transparent.
Referring to Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control skill
Art condition " measuring method test can be precipitated solid content be 21.5%；Powder sample after drying is scanned Electronic Speculum to see
It examines, obtaining initial mean particle size is 2.3 μm；Dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 5.2,7.8,9.6 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa.
[embodiment 2]
1000g deionized water, pentaerythritol triacrylate 2.2g, disodium ethylene diamine tetraacetate are first added in a reservoir
(EDTA) 0.22g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS) 90g, acrylyl oxy-ethyl-trimethyl salmiac 30g, third
Acrylamide (AM) 330g, 2-ethyl hexyl acrylate 4g, stirring to being mixed thoroughly, with the equimolar sodium hydroxide of AMPS (NaOH)
Neutralize and pH is adjusted to 6.5, adds the tert-butyl alcohol (TBA) 775g and the trade mark as the polyvinylpyrrolidone (PVP) of K30
25g is simultaneously stirred to being mixed thoroughly.This solution is put into reaction kettle, nitrogen 30min is led to.Stirring is opened at 15 DEG C,
Revolving speed 280rpm is kept, instilling concentration according to this is 5.5% ammonium persulfate (APS) aqueous solution, 3.3% sodium hydrogensulfite
(MBS) aqueous solution and 11% 2,2'- azo [2- (2- imidazoline -2- base) propane] dihydrochloride (AIBA) each 10g of aqueous solution,
And maintenance leads to nitrogen and stirring, stops logical nitrogen after 30min, temperature is risen to 30 DEG C of holding 1h, then rise to 45 DEG C of holding 2h, phase
Between visible reaction solution by transparent gradually become translucent until end product White-opalescent emulsion form system.
Referring to Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control skill
Art condition " measuring method test can be precipitated solid content be 19.7%；Powder sample after drying is scanned Electronic Speculum to see
It examines, obtaining initial mean particle size is 1.8 μm；Dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 4.6,7.2,8.6 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa.
[embodiment 3]
880g deionized water, divinylbenzene 3.2g, disodium ethylene diamine tetraacetate (EDTA) are first added in a reservoir
0.28g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 80g, acrylamide (AM) 480g, t-butyl styrene 6g, stirring
To being mixed thoroughly, pH is adjusted to 5.5 with sodium hydroxide (NaOH) aqueous solution, adds the tert-butyl alcohol (TBA) 1590g and the trade mark
For 17-88 polyvinyl alcohol (PVA) 25g and stir to being mixed thoroughly.This solution is put into reaction kettle, nitrogen is led to
30min.Stirring is opened at 30 DEG C, keeps revolving speed 280rpm, instills azodiisobutyronitrile (AIBN) ethyl alcohol that concentration is 4%
Solution 10g, and maintenance leads to nitrogen and stirring, stops logical nitrogen after 30min, temperature is risen to 55 DEG C of holding 3h, during which may be used
See that reaction solution gradually becomes translucent until end product White-opalescent emulsion form system by transparent.
Referring to Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control skill
Art condition " measuring method test can be precipitated solid content be 24.9%；Powder sample after drying is scanned Electronic Speculum to see
It examines, obtaining initial mean particle size is 3.2 μm；Dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 3.9,8.5,10.8 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa.
[embodiment 4]
600g deionized water, polyethyleneglycol diacrylate 2.8g, disodium ethylene diamine tetraacetate are first added in a reservoir
(EDTA) 0.26g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS) 70g, dimethyl diallyl ammonium chloride 50g, acryloyl
Amine (AM) 330g, n-vinyl pyrrolidone 8.5g, stirring to being mixed thoroughly, with the equimolar sodium hydroxide of AMPS
(NaOH) it carries out neutralizing and pH is adjusted to 6.5, add the tert-butyl alcohol (TBA) 1880g and the trade mark as the polyvinylpyrrolidone of K90
(PVP) it 4g and stirs to being mixed thoroughly.This solution is put into reaction kettle, nitrogen 30min is led to.Stirring is opened at 30 DEG C
It opens, keeps revolving speed 280rpm, instill ammonium persulfate (APS) aqueous solution 10g that concentration is 3.2%, and maintenance leads to nitrogen and stirs
It mixes, stops logical nitrogen after 30min, temperature is risen into 55 DEG C of holding 2h, rises to 65 DEG C of holding 1h again, during which visible reaction solution
Gradually become translucent until end product White-opalescent emulsion form system by transparent.
Referring to Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control skill
Art condition " measuring method test can be precipitated solid content be 21.4%；Powder sample after drying is scanned Electronic Speculum to see
It examines, obtaining initial mean particle size is 1.2 μm；Dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 3.2,7.4,9.1 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa.
[embodiment 5]
550g deionized water, methylene-bisacrylamide (MBA) 2.2g, disodium ethylene diamine tetraacetate are first added in a reservoir
(EDTA) 0.2g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS) 90g, acrylamide (AM) 310g, octadecyldimethyl
Allyl ammonium chloride (C18DMAAC) 8g, stirring to being mixed thoroughly, with the equimolar sodium hydroxide of AMPS (NaOH) into
Row neutralizes and pH is adjusted to 5, adds ethyl alcohol 1700g and the trade mark as polyvinylpyrrolidone (PVP) 12g of K60 and stirs extremely
It is mixed thoroughly.This solution is put into reaction kettle, nitrogen 30min is led to.Stirring is opened at 25 DEG C, keeps revolving speed
230rpm instills potassium peroxydisulfate (KPS) aqueous solution 10g that concentration is 4%, and maintenance leads to nitrogen and stirring, stops after 30min
Logical nitrogen, rises to 45 DEG C of holding 2h for temperature, rises to 70 DEG C of holding 4h again, and during which visible reaction solution gradually becomes half by transparent
It is transparent until end product White-opalescent emulsion form system.
Referring to Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control skill
Art condition " measuring method test can be precipitated solid content be 16.4%；Powder sample after drying is scanned Electronic Speculum to see
It examines, obtaining initial mean particle size is 2.5 μm；Dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 5.2,9.4,12.3 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa.
[embodiment 6]
1000g deionized water, methylene-bisacrylamide (MBA) 2.5g, ethylenediamine tetra-acetic acid two are first added in a reservoir
Sodium (EDTA) 0.3g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS) 100g, acrylamide (AM) 400g, 2- acrylamide
Base dodecyl sodium sulfate 10g is stirred to being mixed thoroughly, is neutralized with the equimolar sodium hydroxide of AMPS (NaOH)
And pH is adjusted to 7, ethyl alcohol 1300g and the trade mark are added as polyvinylpyrrolidone (PVP) 25g and hydroxypropyl cellulose of K30
(HPC) it 50g and stirs to being mixed thoroughly.This solution is put into reaction kettle, nitrogen 30min is led to.It will stirring at 15 DEG C
It opens, keeps revolving speed 300rpm, successively instilling concentration is 1.25% ammonium persulfate (APS) aqueous solution, 0.75% sulfurous acid
Hydrogen sodium (MBS) aqueous solution and 2.5% 2,2'- azo [2- (2- imidazoline -2- base) propane] dihydrochloride (AIBA) aqueous solution
Each 10g, and maintenance leads to nitrogen and stirring, stops logical nitrogen after 30min, temperature is risen to 30 DEG C of holding 1h, then rise to 60 DEG C of guarantors
3h is held, during which visible reaction solution gradually becomes translucent until end product White-opalescent emulsion form system by transparent.
Referring to Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control skill
Art condition " measuring method test can be precipitated solid content be 19.8%；Powder sample after drying is scanned Electronic Speculum to see
It examines, obtaining initial mean particle size is 5.8 μm；Dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 4.2,7.1,10.2 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa.
[embodiment 7]
550g deionized water, polyethyleneglycol diacrylate 2.8g, disodium ethylene diamine tetraacetate are first added in a reservoir
(EDTA) 0.26g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS) 80g, 2- acrylamido -2- trimethoxysilyl propyl methacrylate base
Ammonium chloride 40g, acrylamide (AM) 330g, N-phenylmaleimide 7.8g, stirring is to being mixed thoroughly, with AMPS etc.
Mole sodium hydroxide (NaOH) neutralize and pH be adjusted to 6.5, adding the tert-butyl alcohol (TBA) 1880g and the trade mark is K90's
Polyvinylpyrrolidone (PVP) 3g and dextrin 5g is simultaneously stirred to being mixed thoroughly.This solution is put into reaction kettle, nitrogen is led to
30min.Stirring is opened at 30 DEG C, keeps revolving speed 280rpm, instills ammonium persulfate (APS) aqueous solution that concentration is 2.2%
12g, and maintenance leads to nitrogen and stirring, stops logical nitrogen after 30min, temperature is risen to 55 DEG C of holding 2h, rises to 70 DEG C again
1h is kept, during which visible reaction solution gradually becomes translucent until end product White-opalescent emulsion form system by transparent.
Referring to Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control skill
Art condition " measuring method test can be precipitated solid content be 20.6%；Powder sample after drying is scanned Electronic Speculum to see
It examines, obtaining initial mean particle size is 8.9 μm；Dispersion is directly used to total salinity 165000mg/L (wherein Ca2++Mg2+
Salt water 7000mg/L) is made into 0.15% solution, aging 1 day, 3 days, 7 days at 90 DEG C, under an optical microscope by solution
Observation, with the partial size after expansion compared with initial particle, expansion multiple is respectively 5.2,9.4,12.8 times, with 10 microns of nucleopore
Filter membrane carries out blocking experiment acquirement better effects at 0.2 mpa.
[embodiment 8]
With embodiment 6, polyvinylpyrrolidone (PVP) 25g and hydroxyl only are replaced with polyvinylpyrrolidone (PVP) 75g
Propyl cellulose (HPC) 50g, the corresponding expansion multiple of product are respectively 3.4,5.6,7.3 times, and the nuclear pore filter film with 10 microns exists
Closure experiment effect is carried out under 0.2MPa is worse than embodiment 6.
[embodiment 9]
With embodiment 6, polyvinylpyrrolidone (PVP) 25g and hydroxypropyl only are replaced with hydroxypropyl cellulose (HPC) 75g
Base cellulose (HPC) 50g, the corresponding expansion multiple of product are respectively 3.6,6.5,8.9 times, and the nuclear pore filter film with 10 microns exists
Closure experiment effect is carried out under 0.2MPa is worse than embodiment 6.
By the comparison of embodiment 6 and embodiment 8,9, it is surprisingly found by the inventors that, select two kinds of stabilizer mixing to achieve
The effect of synergistic effect is superior to a kind of implementation result.
Claims (6)
1. a kind of temperature-resistant anti-salt acrylamide copolymer microballoon dispersion, the dispersion is by copolymerization component in initiator
In the presence of react be made；Based on parts by weight, the copolymerization component includes:
A) 70~90 parts of alcohol-water mixture；
B) 1~10 part of stabilizer；
C) 0.1~5 part of crosslinking agent；
D) 10~30 parts of comonomer；
Wherein, the stabilizer be polyvinylpyrrolidone, hydroxypropyl cellulose mixture, dosage account for copolymerization component 1~
10w.t.%；The comonomer includes following components:
A) nonionic water-soluble monomers of 5~99.9w.t.%；
B) 0~50w.t.% and be greater than 0 anionic monomer or/and cationic monomer；
C) hydrophobic monomer of 0.1~10w.t.%；
The nonionic water-soluble monomers be selected from water-soluble vinyl monomer, the water-soluble vinyl monomer be selected from formula (1),
At least one of monomer shown in formula (2), formula (3) or formula (4):
Wherein, R1、R4、R5、R6It is independently chosen from hydrogen, C1~C4Alkyl；R2、R3It is independently chosen from hydrogen, C1~C4Alkyl or hydroxyl
Base replaces alkyl；
The hydrophobic monomer is Long carbon chain ionic surfactant monomer, esters of acrylic acid hydrophobic monomer, containing polynary cyclic annular chemical combination
One or more of hydrophobic monomer of object mixture, it is 8 that wherein Long carbon chain ionic surfactant monomer, which is alkyl carbon chain number,
The allyl alkyl ammonium chloride that~18 acrylamide azanyl sodium sulfonate or alkyl carbon chain number is 12~22；Esters of acrylic acid is dredged
Aqueous monomer is selected from the alkyl acrylate or alkyl methacrylate that alkyl carbon chain number is 1~20, the hydrophobic list containing polynary ring
Body is selected from n-vinyl pyrrolidone, styrene or t-butyl styrene, N-phenylmaleimide.
2. temperature-resistant anti-salt acrylamide copolymer microballoon dispersion according to claim 1, it is characterised in that described
Alcohol in alcohol-water mixture is selected from least one of ethyl alcohol, propyl alcohol, butanol or tert-butyl alcohol, dosage account for alcohol-water system 50~
90w.t.%.
3. temperature-resistant anti-salt acrylamide copolymer microballoon dispersion according to claim 1, it is characterised in that described
It is methylene-bisacrylamide, three acrylic acid of divinylbenzene, polyethyleneglycol diacrylate and pentaerythrite that crosslinking agent, which is selected from,
At least one of ester etc., dosage account for 0.1~5w.t.% of whole system.
4. temperature-resistant anti-salt acrylamide copolymer microballoon dispersion according to claim 1, it is characterised in that described
Anionic monomer be selected from 2- acrylamide-2-methylpro panesulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, richness
Horse acid, crotonic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, allyl sulphonic acid, allyl phosphonic acid and/or its water
At least one of insoluble alkali metal, alkaline-earth metal and ammonium salt；The cationic monomer is selected from dimethyl diallyl chlorination
Ammonium, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2- acrylamido -2- methyl
At least one of hydroxypropyltrimonium chloride.
5. any temperature-resistant anti-salt acrylamide copolymer microballoon dispersion preparation method of Claims 1 to 4, including
Following steps:
(a) it is dissolved in the water crosslinking agent, comonomer to obtain aqueous phase system；
(b) it is uniformly mixed that alcohol, stabilizer are added in above-mentioned aqueous phase system, and pH value is adjusted to 4~8, obtains mixed material；
(c) by water soluble starter with a certain concentration wiring solution-forming soluble in water, by oil-soluble initiator with a small amount of ethyl alcohol or second
Acetoacetic ester dissolution is made into certain density solution；
(d) mixed material is put into reaction kettle, stirs and be passed through inert gas, by reactor temperature control 10~
30 DEG C, initiator about is added after half an hour, continues logical nitrogen inert gas 5~stop logical nitrogen after ten minutes and seal；
(e) reaction temperature is increased to 40~90 DEG C, until white fine particle occurs in transparent system, it is 1~2 small that the reaction was continued
When, obtain the acrylamide copolymer microballoon dispersion of White-opalescent；
(f) according to required solid content or formation core-shell structure, second and third secondary charging, the propylene finally obtained can also be carried out
Acylamide polymer microballoon dispersion is the stabilising system of White-opalescent.
6. any temperature-resistant anti-salt acrylamide copolymer microballoon dispersion of Claims 1 to 4 is adopted three times in oil field
Application in oil.
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