CN104449617B - A kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage - Google Patents
A kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage Download PDFInfo
- Publication number
- CN104449617B CN104449617B CN201410698126.0A CN201410698126A CN104449617B CN 104449617 B CN104449617 B CN 104449617B CN 201410698126 A CN201410698126 A CN 201410698126A CN 104449617 B CN104449617 B CN 104449617B
- Authority
- CN
- China
- Prior art keywords
- water
- emulsion
- anionic
- anionic polyacrylamide
- profile control
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
It is made of the invention discloses a kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and using usage, the anionic polyacrylamide water-in-water emulsion water plugging profile control agent anionic polyacrylamide water-in-water emulsion and crosslinking agent.Preparation method is：Deionized water, stabilizer, part inorganic salts, non-ionic monomer, anionic monomer, chelating agent, (chain-transferring agent) are added in reaction vessel and are stirred evenly, pH value is adjusted to suitable scope, logical nitrogen deoxygenation, add initiator initiation reaction, during the reaction and it is eventually adding the inorganic salts of remainder, blowing after insulation, up to anionic polyacrylamide " water-water " lotion.Application method as water plugging profile control agent is, " water-water " lotion on the spot or on-line dilution is made into certain density uniform aqueous solution, then under agitation, add a certain amount of crosslinking agent, after stirring evenly, stratum is injected, achievees the purpose that to improve oil recovery factor.
Description
Technical field
The present invention relates to the profile control and water plugging technology field of oil exploitation, more particularly to a kind of anionic polyacrylamide water bag
Aqueous emulsion water plugging profile control agent and preparation method thereof and use usage.
Background technology
Water blockoff refers to using method mechanically or chemically, limitation or the water-yielding capacity for reducing producing well water-yielding stratum/section, with hair
The oil production potential of oil-bearing layer/section is waved, so as to reach reduction well water, improves the purpose of crude output, its target is oil
Well.Profile control refers to using method mechanically or chemically, limitation or the water absorbing capacity for reducing water injection well high permeability zone/section, to reach
Improve profile-log of water injection, and then the effect of improving ecology swept volume, its target are water injection wells.China's oil well blocks up
Water technology is applied at the scene since the 1950s.Water plugging and profile controlling is divided into two class of water pack off and chemical water shutoff.Change
Learn water blockoff and be divided into non-selective chemical plugging agent and selective chemical water shutoff agent again.Anionic polyacrylamide belongs to selectiveization
Learn water shutoff agent.Common anionic polyacrylamide has multiple product form, such as dry powder, colloid, water-in-oil emulsion etc..Dry powder
The anionic polyacrylamide of form has the advantages that to be readily transported, but includes dry, crushing, granulation etc. in production process link
Step, so high energy consumption, needs larger dissolver when applying at the scene, and dissolution time is longer, this all constrains dry
The application of powder form product, the application of the specific area of especially some production operation narrow spaces, such as offshore oilfield block up
Water profile control, the less area of production platform do not accommodate larger dissolver.The anionic polyacrylamide of colloid form is deposited
Imitating the shortcomings that content is low, dissolution velocity is slow.Although water-in-oil emulsion dissolution velocity is fast, because adding in the synthesis process
Substantial amounts of oils makes its higher price, and in application, there are security risk since the addition of a large amount of oils makes it.Exactly because
Common anionic polyacrylamide product form there are it is as described above the shortcomings that, it is desirable to have a kind of more superior product
Form occurs, and anionic polyacrylamide water-in-water emulsion water plugging profile control agent is exactly to produce in this background.
Anionic polyacrylamide water-in-water emulsion is water-soluble monomer, inorganic salts, stabilizer, water and various auxiliary agents
Dissolving together, forms homogeneous solution, then polymerize under certain condition, and the macromolecule after polymerization is separated out from solution, and
It is evenly distributed on because of the presence of stabilizer in aqueous medium, becomes uniform emulsion state.Anionic polyacrylamide water bag
Aqueous emulsion has the characteristics that dissolution velocity is fast, easy to use, cheap, safe to use.Anionic polyacrylamide water-water
Lotion is used as water plugging profile control agent and is particularly suitable for using in the offshore production platform of narrow space.
At present, in the water-in-water emulsion patent of domestic applications mainly based on cationic polyacrylamide, this is because cloudy
In the synthesis process, reaction speed is fast for cationic polyacrylamide water-in-water emulsion, and thermal discharge is big, and reaction is unmanageable, can do
Successful producer is fewer.From the point of view of the application situation of domestic patent, currently share three patents and be related to anion pp acyl
Amine water-in-water emulsion.The patent of publication number CN1954021A reported for work it is a kind of manufacture anionic water-in-water polymer dispersion side
Method.A kind of anionic polymer A, continuous water phase, dispersant B are included in the dispersion of this method manufacture.According to the manufacture
Method is after the completion of reaction diluted reaction mixture with remaining dispersant B.In the invention, dispersant B is most preferably
The polymer that the anionic monomer unit of 100 weight % is formed.Polyacrylic acid potassium is most preferably.It is first before reaction when dispersant adds
The 60-95 weight % of dispersant total amount is first added, remaining dispersant adds after.One is additionally added in addition to dispersant B
Fixed water-soluble polyfunctional alcohol and/or its reaction product with fatty amine are as other dispersion components.Dispersant B is scattered with other
The amount of component is preferably 5-15 weight %.The ratio between dispersant B and other dispersion components are preferably 1.00:0.30.Synthetic anionic
The water-soluble alkali metal salts of the preferred acrylic acid of anionic monomer used in polymer A, its sodium salt, sylvite and ammonium salt are especially excellent
Choosing.When selecting AMPS, its content is higher, dispersion paste.Particularly preferred non-ionic monomer is propylene in the present invention
Acid amides.The amphiphilic monomer preferably reaction product of (methyl) acrylic acid and polyethylene glycol.The preferred dimethylaminoethyl of cationic monomer
Base (methyl) acrylate, dimethylaminopropyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate, two
Methylaminomethyl (methyl) acrylate, dimethyl aminoethyl (methyl) acrylamide and/or dimethylaminopropyl (first
Base) acrylamide the quaternary ammonium salt quaternized by chloromethanes.That anionic monomer accounts for monomer total amount in polymer A is preferably 5-40
Weight %.Monomer accounts for the 10-50 weight % for the reaction liquid for adding part dispersant.GPC method measures the poly- of invention manufacture
Adduct molecule amount is more than 1.0 × 108Gram/mol.The molecular weight of dispersant is about 65,000 grams/mol.Preferably make in the invention
Salt is sodium chloride, ammonium sulfate and/or sodium sulphate.Salt is added to make before reaction or after reaction, before preferably reacting.Addition with
On the basis of total water-water dispersion, its amount is preferably the 0.75-2.0 weight % of dispersion.The invention is preferably using azo
Initiator.Its addition is preferably to account for the 0.01-0.1 weight % of amount of monomer.Can once add to be added portionwise.Polymerization
Reaction temperature is preferably 30-90 DEG C.The amount for the dispersant that postorder adds is preferably 20-35 weight %, adds the temperature of dispersant
Preferably smaller than 35 DEG C, it is necessary which, which adds step,.The invention is mentioned that its solid-liquid point in aqueous system
From the purposes in the preservative system in the auxiliary agent and paper-making process in, paper-making process.Publication number CN101649024A's is special
Profit reports a kind of synthetic method of " water-water " type anionic polyacrylamide emulsion.Its synthetic method is by inorganic salts, non-
Ionic hydrophilic monomer, anionic monomer, hydrophobic monomer, have the monomer of surface-active, chelating agent, deionized water mixing,
PH value is adjusted to 6.5-7.5, logical nitrogen protection uniform with emulsifier, 18-50 DEG C is added initiator at twice, is once polymerize
When reaction 4-7 is small, when after polymerization reaction time 1-3 is small, this product is made.Inorganic salts are selected from ammonium sulfate, sodium sulphate, chlorination
Ammonium, preferably sulfuric acid ammonium, addition 20-30wt%.The preferred acrylamide addition of non-ionic hydrophilic monomer accounts for monomer total amount
75-85mol%.The preferred 2- acrylamide-2-methyl propane sulfonics of anionic monomer, addition account for the 4- of whole monomer system
8mol%.The preferred ethyl methacrylate of hydrophobic monomer accounts for the 5-9mol% of whole monomer system.Monomer with surface-active
It is preferred that polyethylene glycol 200 mono acrylic ester, it accounts for the 6-8mol% of whole monomer system.Whole monomer system accounts for whole dispersion
The 15-30wt% of system.The copolymer of the preferred sodium acrylate of stabilizer and acrylamide, sodium chloride brine of the stabilizer in 1mol/L
In intrinsic viscosity be 100-300mL/g, stabilizing agent dosage accounts for the 15-20wt% of whole system.The preferred ethylenediamine tetraacetic of chelating agent
Acetic acid disodium, addition account for the 0.012-0.02wt% of whole dispersion.Initiator initiator system of ammonium persulfate/triethanolamine oxidation
Reduction system, 18-35 DEG C of initiation temperature, addition are the 0.010-0.024wt% of whole monomer system.Publication number
The patent of CN101735385A has been reported for work a kind of preparation method of anionic polyacrylamide by water dispersion, it includes brine, scattered
A few part compositions such as agent, dispensing and chelating agent, chain-transferring agent, initiator.Ammonium sulfate or sodium sulphate 30-40wt%, deionization
Water 55-69.9wt%, sodium chloride 0.1-5wt% are uniformly mixed to prepare brine；Dispersant is by 15-25wt%2- acrylamides -2-
Methyl propane sulfonic acid or acrylamide, 70-90wt% desalted waters, make initiator with the azo isobutyl amidine hydrochloride of 1-5ppm and exist
Trigger at 40-50 DEG C and be made.Dispensing by the acrylamide of 50-98wt%, the acrylic acid of 1-40wt%, 0.5-5wt% 2- third
Acrylamide -2- methyl propane sulfonic acids, the organic acid of 0.1-5wt% and brine composition, acrylamide, acrylic acid, 2- acrylamides -
2- methyl propane sulfonic acids, the total concentration of organic acid reach 15-30wt%, and pH value is adjusted to 5-9.Organic acid for itaconic acid or ethanedioic acid etc. no
Saturation monoacid or polyacid.Chelating agent is disodium ethylene diamine tetraacetate, and chain-transferring agent is sodium formate, its addition is respectively third
Acrylamide, acrylic acid, 2- acrylamide-2-methyl propane sulfonics, 10-100ppm, 10-500ppm of organic acid summation.Initiator
It is redox system, oxidant is potassium peroxydisulfate or ammonium persulfate, and reducing agent is sodium sulfite or sodium hydrogensulfite, addition
On the basis of acrylamide, acrylic acid, 2- acrylamide-2-methyl propane sulfonics, organic acid summation, oxidant 5-100ppm,
Reducing agent is 1-50ppm.
The patent of CN1954021A controls reaction speed and stability of emulsion by adding dispersant and polyalcohol, and carries
And the application in terms of solid/liquid separation and papermaking.
The patent of CN101649024A controls reaction speed and polymer speed of separating out by adding hydrophobic monomer,
The patent of CN101735385A controls reaction speed by the way that initiator is added portionwise.
In oil exploitation, traditional water plugging and profiling technology has two kinds of water pack off and organic chemical water plugging and profile controlling.
Chemical method is used mostly when solving sand production, well water, the high liquid measure of oil well, low-producing technical problem.Anion
Polyacrylamide gel system is widely used in oil-water well water plugging and profile controlling as chemical water shutoff profile control agent.It is usually used in oil-water well water blockoff
The anionic polyacrylamide of profile control has two kinds of forms of dry powder and water-in-oil emulsion.But its respective jelly system is as water blockoff tune
Cuing open agent, also there are following defect：1. the anionic polyacrylamide of dry powder includes drying, crush, making in production process link
Grain and etc., so high energy consumption, needs larger dissolver when applying at the scene, and dissolution time is longer, this is all restricted
The application of dry powder product, the application of the specific area of especially some production operation narrow spaces, such as offshore oilfield
Water plugging and profile controlling, the less area of production platform do not accommodate larger dissolver；2. water-in-oil emulsion is in the synthesis process
Adding substantial amounts of oils makes its higher price, and water-in-oil emulsion is scarce there is also temperature-resistant anti-salt energy force difference, resistance to erosion energy force difference etc.
Fall into, and in application, there are security risk since the addition of a large amount of oils makes it；3. with polyvalent metal ion as crosslinking dosage form
Into polyacrylamide gel system there is also crosslinking time it is too fast, formed jelly system be easily dehydrated the defects of.Exactly because
Common polyacrylamide gel system water plugging profile control agent there are it is as described above the shortcomings that, it is a kind of more superior it is desirable to have
Polyacrylamide gel system occurs to solve the above problems, using anionic polyacrylamide water-in-water emulsion as host agent, phenol
Urea formaldehyde is exactly to produce in this background as the water plugging profile control agent of crosslinking agent.
At present, the water plugging profile control agent patent species of domestic applications is very much.The patent report of publication number CN00123964.3
A kind of production of inorganic water plugging profile control agent and application method.The water plugging profile control agent is made of first, second, the third three kinds of materials, and material is matched somebody with somebody
Than sulfoaluminate clinker fine powder 98.3% -98.9%, molasses 0.3%, sodium carbonate 0.8% -1.4%, second material proportioning：Anhydrite
76%th, quick lime 23.86%, sodium chloride 0.1%, lithium hydroxide 0.04%, the third material proportioning：Bentonite 50%, bauxite clay
46%th, molasses 3.0% -3.5%, calcium lignosulfonate 0.5% -1.0%.The first and second the third three kinds of materials are according to respective proportioning, by mixing
First, second, the third three kinds of materials are made in Moses, and fineness requirement specific surface area is more than 400m/kg, 3-4 times of water absorption rate, cubical expansivity
8-9 times, 50 DEG C-85 DEG C of oil temperature is adapted to, using Oil-well Reservior Water as mixed liquor, 6-10h of presetting period, final setting time 8-
12h, 3 days intensity is up to 3-6MPa, and water suction is more, and pump note diffusion length is remote, and water plugging and profile controlling scope is big, and the material is with " solid water is not
Gu the characteristics of oil ", can prevent crude oil pollution, Oil-well Reservior Water dilution mixing also can be used, it is easy to use.Publication number
Polymer water plugging profile control agent is reported in the patent of CN92112307.8.The polymer water plugging profile control agent is by organosilan and third
Acrylamide anionic monomer, cationic monomer, non-ionic monomer are formed a kind of vertical by free radical polymerization in aqueous
The high molecular polymer of body net structure, specific preparation method are prepared using aqueous solution suspension polymerisation mode, pass through addition
XL-23 dispersants, make polymerized monomer be uniformly dispersed in aqueous, and control the crosslinking degree of polymer water plugging profile control agent, system
Obtain a kind of elastomer of semi-transparent clear.The water plugging profile control agent has resistance to erosion, nontoxic and pollution-free, cost low and easy construction etc.
Advantage.
Anionic polyacrylamide water-in-water emulsion is used as water plugging profile control agent in other patents for oil-gas mining process
In have no report.In this patent, newborn speed and stability of emulsion are controlled into using the method for segmentation plus salt, to obtain stability
Good and larger molecular weight anionic polyacrylamide water-in-water emulsion, so that the lotion is suitable as Water in Water Shutoff in Oil Field tune
Cut open.In this patent, by adding suitable monomer, make anionic polyacrylamide water-in-water emulsion that there is salt tolerance, so that
The product is in offshore oil production platform in application, can be dissolved using seawater.
The content of the invention
The present invention provides a kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and make
Usage.
The present invention adopts the following technical scheme that：
The anionic polyacrylamide water-in-water emulsion water plugging profile control agent of the present invention is by anionic polyacrylamide water bag
Aqueous emulsion and crosslinking agent composition, crosslinking agent account for the 30%-150wt% of anionic polyacrylamide water-in-water emulsion, described the moon
Cationic polyacrylamide water-in-water emulsion be water-soluble nonionic monomer, anionic monomer inorganic salts, stabilizer, chelating agent,
Triggered in the presence of deionized water by initiator and be polymerized, the crosslinking agent is phenolic resin, one kind in chromium cross linker
It is or several.
The inorganic salts are anhydrous sodium sulfate, ammonium sulfate, sodium chloride or sodium phosphate one or more therein, its content
Account for the 20%-30w% of anionic polyacrylamide water-in-water emulsion, preferably sulfuric acid ammonium and sodium sulphate.
The water-soluble nonionic monomer is acrylamide, its content accounts for water-soluble nonionic monomer and anionic monomer
The 80-99mol% of summation.
The anionic monomer be acrylic acid, sodium acrylate, 2- acrylamide-2-methyl propane sulfonics it is therein a kind of or
Several, its content accounts for water-soluble nonionic monomer and the 1-20mol% of anionic monomer summation.
The stabilizer is a kind of anionic polymer, which is polymerized by anionic monomer, the anion
Monomer is acrylic acid, sodium acrylate, 2- acrylamide-2-methyl propane sulfonics one or more therein, the quality of the stabilizer
The 4-7w% of anionic polyacrylamide water-water breast is accounted for, preferably the stabilizer is by sodium acrylate homopolymerization or by sodium acrylate and 2-
The copolymerization of acrylamide-2-methyl propane sulfonic sodium forms.
The chelating agent is selected from disodium ethylene diamine tetraacetate, preferably tetrasodium ethylenediamine tetraacetate, ethylenediamine tetra-acetic acid two
Sodium, its addition account for the 0.005-0.1w% of anionic polyacrylamide water-in-water emulsion.
The initiator is redox initiator or water-soluble azo class initiator or two kinds of initiation systems are compound makes
With oxidant is ammonium persulfate or potassium peroxydisulfate, and reducing agent is anhydrous sodium sulfite or sodium hydrogensulfite, and water-soluble azo class is drawn
Hair agent is V2, double (2- imidazolines) dihydrochlorides of 2'- azepines or 2,2'- azo diisobutyl amidine dihydrochloride, the use of initiator
The 0.006%-0.01% for water-soluble nonionic monomer and anionic monomer quality summation is measured, oxidation-reduction trigger system
Temperature in use is 20-30 DEG C；The temperature in use for the composite initiation system that oxidation-reduction initiator and thermal decomposition initiating are formed
For 20-30 DEG C；The temperature in use of water-soluble azo class thermal decomposition initiation system is 30-40 DEG C.The preferred redox of the invention is drawn
Send out agent ammonium persulfate and sodium hydrogensulfite.
The addition of the deionized water accounts for the 40-60wt% of anionic polyacrylamide water-in-water emulsion.
The preparation method of the anionic polyacrylamide water-in-water emulsion comprises the following steps that：
Deionized water, stabilizer, account for whole inorganic salts total amounts 70wt% inorganic salts (, non-ionic monomer, anion list
Body, chelating agent, be added in reaction vessel and stir evenly, and pH value is adjusted between 5-9, pH adjusting agent is selected from hydroxide
Sodium, potassium hydroxide, ammonium hydroxide, preferably sodium hydroxide, lead to nitrogen, initiator initiation reaction are added, during the reaction as lotion is glued
The increase of degree is slowly added to the inorganic salts of remaining 30wt%, when insulation 8-12 is small after blowing, up to anionic polyacrylamide
Water-in-water emulsion.
The application method of the anionic polyacrylamide water-in-water emulsion water plugging profile control agent of the present invention comprises the following steps that：
Anionic polyacrylamide water-in-water emulsion on the spot or on-line dilution to be configured to mass concentration be 0.6%-4wt% aqueous solutions,
Then crosslinking agent is added, is stirred evenly, squeezes into stratum.
The positive effect of the present invention is as follows：
Anionic polyacrylamide water-in-water emulsion dissolution velocity is fast, under the conditions of stirring sufficiently, dissolves a 10-15 minutes left sides
The right side can reach peak viscosity, and dissolve thorough.Injection device adjusts device plus mixed, it is possible to achieve on-line dilution, preparation,
Injection.It is opposite to need 1-2 hour with dry-type polyacrylamide amine solvent, and through being commonly present fish-eye shaped insoluble matter after dissolving
Situation, anionic polyacrylamide water-in-water emulsion water plugging profile control agent not only eliminate large-scale dissolver, save the electricity charge,
Shorten dissolution time, improve production efficiency, and be improved polyacrylamide utilization rate.
Embodiment
The following examples are that the present invention is described in further detail.
Embodiment 1
To equipped with stirring, nitrogen tube, thermometer 250mL four-hole boiling flask in add 108.8g deionized waters, 32.4g third
Acrylamide, 44g ammonium sulfate, the acrylic acid of 5.58g, 10g stabilizers, 0.02gEDTA start stirring, 200 revs/min of mixing speed
Clock, adds 8g anhydrous sodium sulfates, the pH value of system is transferred to 7 with sodium hydroxide solution.30 DEG C are warming up to, leads to nitrogen 30 minutes, so
The sodium hydrogensulfite of 0.013g is added afterwards, adds the ammonium persulfate of 0.025g after five minutes, reaction in 15 minutes or so starts, with
Reaction carry out system viscosity increase, when viscosity increase to a certain extent, add the ammonium sulfate of 5g and the anhydrous sodium sulfate of 5g.It is viscous
Degree slowly reduces, and system is creamy white, and when 45 DEG C of insulations 12 are small, obtains the milky emulsion that rotary viscosity is 280mPas,
In the sodium-chloride water solution of 1mol/L, its inherent viscosity is 450mL/g.
Embodiment 2
To equipped with stirring, nitrogen tube, thermometer 250mL four-hole boiling flask in add 108.8g deionized waters, 32.4g first
Base acrylamide, 44g ammonium sulfate, the acrylic acid of 5.58g, 10g stabilizers, 0.02gEDTA start stirring, and 200 turns of mixing speed/
Minute, 8g anhydrous sodium sulfates are added, the pH value of system is transferred to 7 with sodium hydroxide solution.30 DEG C are warming up to, leads to nitrogen 30 minutes,
Then the sodium hydrogensulfite of 0.013g is added, adds the ammonium persulfate of 0.025g after five minutes, reaction in 15 minutes or so starts,
With reaction carry out system viscosity increase, when viscosity increase to a certain extent, add the ammonium sulfate of 5g and the anhydrous sodium sulfate of 5g.
Viscosity slowly reduces, and system is creamy white, and when 45 DEG C of insulations 12 are small, obtains the milky emulsion that rotary viscosity is 315mPas,
In the sodium-chloride water solution of 1mol/L, its inherent viscosity is 385mL/g.
Embodiment 3
To equipped with stirring, nitrogen tube, thermometer 250mL four-hole boiling flask in add 108.8g deionized waters, 32.4g third
Acrylamide, 44g ammonium sulfate, the acrylic acid of 2.88g, 2.7g2- acrylamide-2-methylpro panesulfonic acids, 10g stabilizers,
0.02gEDTA starts stirring, and 200 revs/min of mixing speed, adds 8g anhydrous sodium sulfates, with sodium hydroxide solution system
PH value is transferred to 7.30 DEG C are warming up to, leads to nitrogen 30 minutes, the sodium hydrogensulfite of 0.013g is then added, adds after five minutes
The ammonium persulfate of 0.025g, reaction in 15 minutes or so start, as reaction carries out system viscosity increase, when viscosity increases to necessarily
Degree, adds the ammonium sulfate of 5g and the anhydrous sodium sulfate of 5g.Viscosity slowly reduces, and system is creamy white, when 45 DEG C of insulations 12 are small,
The milky emulsion that rotary viscosity is 360mPas is obtained, in the sodium-chloride water solution of 1mol/L, its inherent viscosity is
377mL/g。
Embodiment 4
Into the reaction kettle of 50L, 26kg deionized waters are added, start stirring, 50 revs/min of mixing speed, then adds
10.5kg ammonium sulfate, 1.91kg anhydrous sodium sulfates, 7.75kg acrylamides, 1.33kg acrylic acid, 2.39kg stabilizers,
The pH value of system, 7 are adjusted to sodium hydroxide by 4.30gEDTA.30 DEG C are warming up to, leads to nitrogen and drives oxygen 60 minutes, then add 3.11g
Sodium hydrogensulfite, adds 5.98g ammonium persulfates, starts to react within 40 minutes or so after five minutes, and system viscosity carries out soon with reaction
Speed increase, when there is rod climbing phenomenon, adds the anhydrous sodium sulfate of 1.2kg and the ammonium sulfate of 1.2kg, then, under system viscosity
Breast is dropped into, when 45 DEG C of insulations 12 are small, the milky emulsion of rotary viscosity 259mPas is obtained, in the aqueous sodium chloride of 1mol/L
In liquid, its inherent viscosity is 470mL/g.
Embodiment 5
Into the reaction kettle of 500L, 156.17kg deionized waters are added, start stirring, 50 revs/min of mixing speed, then
63.16kg ammonium sulfate, 11.48kg anhydrous sodium sulfates, 46.61kg acrylamides, 8.01kg acrylic acid, 14.35kg is added to stablize
The pH value of system, 7 are adjusted to sodium hydroxide by agent, 25.77gEDTA.30 DEG C are warming up to, leads to nitrogen and drives oxygen 60 minutes, then add
18.66g sodium hydrogensulfites, add 35.89g ammonium persulfates, start to react within 40 minutes or so, system viscosity is with anti-after five minutes
It should quickly be increased, when there is rod climbing phenomenon, add the anhydrous sodium sulfate of 7.18kg and the ammonium sulfate of 7.18kg, then,
System viscosity is declined to become breast, when 45 DEG C of insulations 12 are small, the milky emulsion of rotary viscosity 265mPas is obtained, 1mol/L's
In sodium-chloride water solution, its inherent viscosity is 495mL/g.
Embodiment 6
Into the reaction kettle of 2000L, 780.86kg deionized waters are added, start stirring, 50 revs/min of mixing speed, so
315.79kg ammonium sulfate, 57.42kg anhydrous sodium sulfates, 232.54kg acrylamides, 8.01kg acrylic acid, 40.05kg are added afterwards
The pH value of system, 7 are adjusted to sodium hydroxide by stabilizer, 128.86gEDTA.30 DEG C are warming up to, leads to nitrogen and drives oxygen 60 minutes, then
Add 93.3g sodium hydrogensulfites, after five minutes add 179.43g ammonium persulfates, start to react within 40 minutes or so, system viscosity with
Reaction quickly to be increased, when there is rod climbing phenomenon, add the anhydrous sodium sulfate of 35.89kg and the ammonium sulfate of 35.89kg,
Then, system viscosity is declined to become breast, when 45 DEG C of insulations 12 are small, obtains the milky emulsion of rotary viscosity 255mPas,
In the sodium-chloride water solution of 1mol/L, its inherent viscosity is 493mL/g.
Embodiment 7
CB1B-6 wells are under the jurisdiction of offshore oil production factory of sinopec Shengli Oil Field Co., Ltd, go into operation within 27th in August in 1999, and
Switch within 23rd water injection well in September in 2005, profile control horizon is in shop epimere, and water suction layer thickness is 36m, mean permeability 1108.1
×10-3μm2, average pore 36.98%, shale content 9.96%, belongs to three sections of water fillings of two level, mains pressure at present
8.4MPa, well head pressure 5.6MPa, day are 260m with fluence3, 20.29 ten thousand m of accumulation water filling3.The drop of pressure time is 95s, right
Oil well day oil-producing 143.6t is answered, average aqueous 42.6%.The well, to October 20, is gathered on October 15th, 2008 using anion
Acrylamide water-in-water emulsion carries out continuous profile control operation, and construction method is the water-soluble of anionic water-in-water lotion preparation 2%
Liquid, preparation method is, with water is filled in liquid pool, unlatching stirring, anionic polyacrylamide water-in-water emulsion is poured into pond, 10
Minute or so solution stirs evenly.Then the phenolic resin crosslinking agent of 50% lotion weight is poured into pond, stirs 10 minutes left sides
The right side, profile control agent, which is prepared, to be completed.First with 10m3The injection discharge capacity injection test of/h one hour, injection pressure are 2.6MPa, then with
12m3The discharge capacity of/h, point three slugs inject 990m altogether3Cross-linking system, the injection rate of three slugs is respectively 330m3、270m3、
270m3, it is subsequent to cross replacement 120m3High concentration polymer solution, finally replaces 8m3Seawater is real to ensure that medicament is fully injected into stratum
Border injection of polymer lotion 20.1t, crosslinking agent 6.84t, operation pressure have 2.6MPa slowly increase to 5.6MPa, until apply
Work terminates pressure and is held essentially constant, and site operation is very normal.Table one is the effect of increasing production that oil well is corresponded to after constructing.
One CB1B-6 well construction correspondence Anomalous character manufacturing parameters of table
Embodiment 8
It is 79.3t that GD2-21-15 wells, which are under the jurisdiction of daily fluid production rate before the sinopec Gudao area of Shengli Oilfield oil recovery factory well construction, day
Oil production 1.982t, aqueous 97.5%, construct on July 9th, 2010, construction method is the preparation of anionic water-in-water lotion
2% aqueous solution, preparation method are first a 10m3The pond of left and right fills water, stirring is opened, anion pp acyl
Amine water-in-water emulsion is slowly poured into pond, and solution stirs after ten minutes, then phenolic resin crosslinking agent is poured into pond, crosslinking agent
Dosage is the half of lotion, is stirred 10 minutes or so, and profile control agent, which is prepared, to be completed.Site operation discharge capacity 10-15m3/ h, is actually implanted into
Blocking agent 300m3, convert into anionic polyacrylamide water-in-water emulsion 6t.Construction pump pressure rises to 7MPa by 0.6MPa, and scene is applied
Work is smooth.Daily fluid production rate 80.4t after driving a well, daily oil production 3.816t, it is aqueous to be down to 95.3%, but due to daily fluid production rate compared with
Greatly, aqueous rising is caused, daily oil production declines, and to prevent from producing destruction to the frozen glue blocking layer just formed, Liquid output is made in time
Adjustment is gone out, daily fluid production rate slowly drops to 60.5t by 80.4t, and daily oil production increases to 5.203t, compared to being added before construction
3.2t, it is aqueous to drop to 91.4%, compared to have dropped 6.1% before construction, water-blocking operation from the point of view of current effect is achieved preferably
Effect.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of changes, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (9)
- A kind of 1. anionic polyacrylamide water-in-water emulsion water plugging profile control agent, it is characterised in that：The anion pp Acid amides water-in-water emulsion water plugging profile control agent is made of anionic polyacrylamide water-in-water emulsion and crosslinking agent, and crosslinking agent accounts for the moon The 30-150wt% of cationic polyacrylamide water-in-water emulsion, the anionic polyacrylamide water-in-water emulsion is water-soluble Property non-ionic monomer, anionic monomer triggered in the presence of inorganic salts, stabilizer, chelating agent, deionized water by initiator it is poly- Conjunction forms, and the crosslinking agent is phenolic resin, the one or more in chromium cross linker；The anionic polyacrylamide water bag The preparation method of aqueous emulsion comprises the following steps that：Deionized water, stabilizer, account for the 70wt% of whole inorganic salts total amounts without Machine salt, non-ionic monomer, anionic monomer, chelating agent are added in reaction vessel and stir evenly, and pH values are adjusted and arrive 5-9 Between, lead to nitrogen, add initiator initiation reaction, during the reaction with the increase of emulsion viscosity be slowly added to it is remaining The inorganic salts of 30wt%, insulation 8-12 it is small when after blowing, up to anionic polyacrylamide water-in-water emulsion.
- 2. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, it is characterised in that：It is described Inorganic salts be anhydrous sodium sulfate, ammonium sulfate, sodium chloride or sodium phosphate one or more therein, its content accounts for anion poly- third The 20-30wt% of acrylamide water-in-water emulsion.
- 3. the anionic polyacrylamide water-in-water emulsion water plugging profile control agent as described in claim 1, it is characterised in that：Institute The water-soluble nonionic monomer stated is acrylamide, its content accounts for water-soluble nonionic monomer and the 80- of anionic monomer summation 99mol%.
- 4. the anionic polyacrylamide water-in-water emulsion water plugging profile control agent as described in claim 1, it is characterised in that：Institute The anionic monomer stated is acrylic acid, sodium acrylate, 2- acrylamide -2- methyl propane sulfonic acids one or more therein, its Content accounts for water-soluble nonionic monomer and the 1-20mol% of anionic monomer summation.
- 5. the anionic polyacrylamide water-in-water emulsion water plugging profile control agent as described in claim 1, it is characterised in that：Institute The stabilizer stated is a kind of anionic polymer, which is polymerized by anionic monomer, which is propylene Acid, sodium acrylate, 2- acrylamide -2- methyl propane sulfonic acids one or more therein, the quality of the stabilizer account for it is cloudy from The 4-7wt% of sub- polyacrylamide water-in-water emulsion.
- 6. the anionic polyacrylamide water-in-water emulsion water plugging profile control agent as described in claim 1, it is characterised in that：Institute The chelating agent stated is disodium ethylene diamine tetraacetate, its addition accounts for the 0.005- of anionic polyacrylamide water-in-water emulsion 0.1wt%.
- 7. the anionic polyacrylamide water-in-water emulsion water plugging profile control agent as described in claim 1, it is characterised in that：Institute The initiator stated is used in combination for redox initiator or water-soluble azo class initiator or two kinds of initiation systems, and oxidant is Ammonium persulfate or potassium peroxydisulfate, reducing agent are anhydrous sodium sulfite or sodium hydrogensulfite, and water-soluble azo class initiator is 2,2'- Azo diisobutyl amidine dihydrochloride, the dosage of initiator is water-soluble nonionic monomer and anionic monomer quality summation 0.006% -0.01wt%.
- 8. the anionic polyacrylamide water-in-water emulsion water plugging profile control agent as described in claim 1, it is characterised in that：Go from The addition of sub- water accounts for the 40-60wt% of anionic polyacrylamide water-in-water emulsion.
- 9. such as the user of claim 1-8 any one of them anionic polyacrylamide water-in-water emulsion water plugging profile control agents Method, it is characterised in that：The application method comprises the following steps that：Anionic polyacrylamide water-in-water emulsion on the spot or It is 0.6% -4% aqueous solution that on-line dilution, which is configured to mass concentration, then adds crosslinking agent, stirs evenly, squeezes into stratum i.e. Can.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410698126.0A CN104449617B (en) | 2014-11-26 | 2014-11-26 | A kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410698126.0A CN104449617B (en) | 2014-11-26 | 2014-11-26 | A kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104449617A CN104449617A (en) | 2015-03-25 |
| CN104449617B true CN104449617B (en) | 2018-05-08 |
Family
ID=52896383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410698126.0A Active CN104449617B (en) | 2014-11-26 | 2014-11-26 | A kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104449617B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961863A (en) * | 2015-06-25 | 2015-10-07 | 武汉工程大学 | Method for preparing polysaccharide biogum polymer gel profile control agent |
| CN105418839A (en) * | 2015-11-17 | 2016-03-23 | 山东诺尔生物科技有限公司 | Preparation method of anion water-in-water type polyacrylamide |
| CN106749885A (en) * | 2015-11-19 | 2017-05-31 | 北京熠海能源科技有限公司 | A kind of preparation method and applications of nano-micro level water-in-water type microballoon profile control agent |
| CN106883357B (en) * | 2017-03-16 | 2019-01-18 | 东营方立化工有限公司 | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its preparation method and application |
| CN108329422B (en) * | 2018-02-07 | 2020-12-29 | 山东诺尔生物科技有限公司 | Water-in-water type microsphere profile control agent and preparation method thereof |
| CN108586671B (en) * | 2018-04-07 | 2019-06-04 | 四川大学 | A kind of hot increasing stick water-soluble polymer of anionic and its preparation method and application |
| CN109370552A (en) * | 2018-10-22 | 2019-02-22 | 中国海洋石油集团有限公司 | A method of delaying the uncrosslinked gel solution rate in the plugging agent of oil field |
| CN111909306B (en) * | 2020-08-14 | 2022-05-31 | 西安石油大学 | Double-aqueous-phase PAM/AMPS nano microsphere latex as well as preparation method and application thereof |
| CN116715807A (en) * | 2023-08-11 | 2023-09-08 | 江苏富淼科技股份有限公司 | Anionic aquatic product in water and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1479762A (en) * | 2000-12-08 | 2004-03-03 | ʩ�п˺�ɭ��˾ | Method for producing water-in-water polymer displersions |
| CN101735385A (en) * | 2009-12-13 | 2010-06-16 | 安徽省天润功能高分子工程研究有限公司 | Method for preparing anionic polyacrylamide by water dispersion |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004013750A1 (en) * | 2004-03-18 | 2005-11-03 | Stockhausen Gmbh | Anionic water-in-water polymer dispersions, process for their preparation and their use |
| CN101649024B (en) * | 2009-08-19 | 2011-04-27 | 中国海洋石油总公司 | Preparation method of water-in-water cationic polyacylamide emulsion |
| CN102286128A (en) * | 2009-12-31 | 2011-12-21 | 中国科学院成都有机化学有限公司 | Cationic hydrophobically associated polyacrylamide water-in-water emulsion |
| CN102532375B (en) * | 2011-12-29 | 2014-07-09 | 浙江传化股份有限公司 | Polyacrylamide microsphere |
-
2014
- 2014-11-26 CN CN201410698126.0A patent/CN104449617B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1479762A (en) * | 2000-12-08 | 2004-03-03 | ʩ�п˺�ɭ��˾ | Method for producing water-in-water polymer displersions |
| CN101735385A (en) * | 2009-12-13 | 2010-06-16 | 安徽省天润功能高分子工程研究有限公司 | Method for preparing anionic polyacrylamide by water dispersion |
Non-Patent Citations (1)
| Title |
|---|
| 新型聚丙烯酰胺乳液合成及在油田中应用;刘志良等;《钻采工艺》;20090731;第32卷(第4期);第89页摘要，91页左栏倒数第2段至右栏第2段，表3-4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104449617A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104449617B (en) | A kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage | |
| US4702319A (en) | Enhanced oil recovery with hydrophobically associating polymers containing sulfonate functionality | |
| CN112375185B (en) | Small-molecule thick oil viscosity reduction polymer and preparation method thereof | |
| CN102433108B (en) | Temperature-resistance salt-resistance filtrate reducer for drilling fluid and preparation method thereof | |
| US20200199442A1 (en) | Heavy oil activator and preparation method and use thereof | |
| CN110358008A (en) | A kind of 100 nanospheres and preparation method of temperature-tolerant anti-salt polyacrylamide class | |
| CN107337762A (en) | A kind of hydrophobic association cross-linked polymer microsphere, preparation method and application | |
| CN105462568A (en) | Resin type nanoparticle latex blocking agent for drilling fluids and preparation method of blocking agent | |
| CN104232040B (en) | Plugging agent for postponing colloid foam and method thereof for oilfield high-water-content aquifer profile modification water plugging | |
| CN104861953A (en) | Oil field fracture temporary plugging agent and preparation method thereof | |
| CN105505364A (en) | Oil displacing agent for increasing oil recovery in high temperature high salt mid-low permeability oil reservoir, preparation method and applications thereof | |
| CN105399897B (en) | Temperature-tolerant anti-salt polyacrylamide is birdsed of the same feather flock together compound and preparation method thereof | |
| CN107793529A (en) | A kind of high temperature resistant acid fracturing polymer and preparation method | |
| CN102352232A (en) | Temperature-resistant and salt-resistant polymer clean fracturing fluid thickening agent and preparation method thereof | |
| CN105567208A (en) | Oil-displacement composition with improved injectivity, and preparation method and application thereof | |
| CN104531104A (en) | High-temperature-resistant and salt-bearing filtrate loss reducer and preparation method thereof | |
| CN102093880A (en) | Water control agent for oil well and preparation method thereof | |
| CN108587580A (en) | Drilling fluid high-temperature salt-resistant fluid loss additive modified gum resin and preparation method thereof | |
| CN105176499A (en) | Filtrate reducer capable of resisting high temperature and high-concentration salt and preparation method thereof | |
| CN106939158A (en) | A kind of heat and salinity tolerance polymer oil-displacing agent and preparation method thereof | |
| CN112851856A (en) | Salt-tolerant polymer microsphere plugging agent and preparation method thereof | |
| CN105860951A (en) | Acidic polymer fracturing fluid and preparation method thereof | |
| CN106279526B (en) | A kind of gel micro-sphere system and preparation method thereof, gel micro-sphere dispersion, gel micro-sphere strengthen Polymer Flooding | |
| CN103788295B (en) | A kind of two-step method prepares the method for acrylamide based copolymer | |
| CN105175628A (en) | Oil well cement water-loss control agent compatible with AMPS (2-acrylamido-methylpropanesulfonic acid)-IA retarder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |