CN104449617A - Anionic polyacrylamide water-in-water emulsion water shutoff profile control agent, and preparation method and using method thereof - Google Patents
Anionic polyacrylamide water-in-water emulsion water shutoff profile control agent, and preparation method and using method thereof Download PDFInfo
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Abstract
The invention discloses an anionic polyacrylamide water-in-water emulsion water shutoff profile control agent, and a preparation method and a using method thereof. The anionic polyacrylamide water-in-water emulsion water shutoff profile control agent consists of an anionic polyacrylamide water-in-water emulsion and a cross-linking agent. The preparation method comprises the following steps: adding deionized water, a stabilizing agent, part inorganic salts, nonionic monomers, anionic monomers, a chelating agent and (a chain transfer agent) into a reaction container, stirring uniformly, adjusting the pH value to a suitable range, introducing nitrogen to remove oxygen, adding an initiator to initiate a reaction, adding the remaining part inorganic salts in a reaction process, preserving heat, and discharging materials to obtain the anionic polyacrylamide water-in-water emulsion. The using method of the anionic polyacrylamide water-in-water emulsion serving as a water shutoff profile control agent comprises the following steps: diluting the water-in-water emulsion on situ or on line to prepare a uniform aqueous solution with a certain concentration, adding a certain amount of the cross-linking agent under the condition of stirring, stirring uniformly and injecting the aqueous solution into a stratum to realize the purpose of improving crude oil recovery rate.
Description
Technical field
The present invention relates to the profile control and water plugging technology field of oil production, particularly relate to a kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage.
Background technology
Water blockoff refers to and adopts machinery or chemical method, and the water-yielding capacity of restriction or reduction recovery well water-yielding stratum/section, to play the oil production potential of tryphine/section, thus reach reduction well water, improve the object of crude production rate, its target is oil well.Profile control refers to and adopts machinery or chemical method, and the water-retaining capacity of restriction or reduction water injection well most permeable zone/section, improves profile-log of water injection to reach, and then the effect of improving ecology swept volume, and its target is water injection well.The water-plugging technique of China's oil well is applied at the scene from the 1950's.Water plugging and profile controlling is divided into water pack off and chemical water plugging two class.Chemical water plugging is divided into again non-selective chemical plugging agent and selective chemical plugging agent.Anionic polyacrylamide belongs to selective chemical plugging agent.Common anionic polyacrylamide has multiple product form, such as dry powder, colloid, water-in-oil emulsion etc.The anionic polyacrylamide of dry powder has the advantage of being convenient to transport, but the steps such as drying, pulverizing, granulation are comprised in production process link, so energy consumption is high, larger dissolver is needed at the scene during application, and dissolution time is longer, this all constrains the application of dry powder product, especially the application of the specific area of some production operation narrow space, the water plugging and profile controlling of such as offshore oilfield, the area that production vessel is less does not hold comparatively large dissolver.There is the shortcoming that effect content is low, dissolution rate is slow in the anionic polyacrylamide of colloid form.Although water-in-oil emulsion dissolution rate is fast, make its price higher because add a large amount of oils in building-up process, again because adding of a large amount of oils makes it there is potential safety hazard when applying.Exactly because common anionic polyacrylamide product form exists shortcoming as above, therefore wish that a kind of more superior product form occurs, anionic polyacrylamide water-in-water emulsion water plugging profile control agent is exactly produce under this background.
Anionic polyacrylamide water-in-water emulsion is that water-soluble monomer, inorganic salt, stablizer, water and various auxiliary agent are dissolved in together, form homogeneous solution, then be polymerized under certain condition, polymer after polymerization is separated out from solution, and be evenly distributed in water medium because of the existence of stablizer, become uniform emulsion state.Anionic polyacrylamide water-in-water emulsion has the features such as dissolution rate is fast, easy to use, cheap, use safety.Anionic polyacrylamide water-in-water emulsion is used as water plugging profile control agent and is particularly suitable for using at the offshore production platform of narrow space.
At present, main based on cationic polyacrylamide in the water-in-water emulsion patent of domestic application, this is because anionic polyacrylamide water-in-water emulsion is in building-up process, speed of response is fast, thermal discharge is large, and reaction is difficult to control, and the producer that can succeed is fewer.From the application situation of domestic patent, currently have three patents and relate to anionic polyacrylamide water-in-water emulsion.The patent of publication number CN1954021A has been reported for work a kind of method manufacturing anionic water-in-water polymer dispersion.A kind of anionic polymer A, continuous print aqueous phase, dispersant B is comprised in the dispersion of the method manufacture.With remaining dispersant B, reaction mixture is diluted after the completion of reaction according to described manufacture method.In the invention, dispersant B most preferably 100 % by weight anionic monomer unit form polymkeric substance.Polyacrylic acid potassium most preferably.Dispersion agent adds fashionable, and first add the 60-95 % by weight of dispersion agent total amount before reaction, remaining dispersion agent adds after end again.The reaction product of certain water-soluble polyfunctional alcohol and/or itself and aliphatic amide is also added as other dispersion components except dispersant B.The amount of dispersant B and other dispersion components is preferably 5-15 % by weight.Dispersant B and other ratios to be dispersed into point are preferably 1.00:0.30.The preferred acrylic acid water-soluble alkali metal salts of the anionic monomer that synthetic anionic polymer A uses, its sodium salt, sylvite and ammonium salt are particularly preferably.When selecting AMPS, its content is higher, dispersion pasty state.In the present invention, particularly preferred non-ionic monomer is acrylamide.The reaction product of preferred (methyl) vinylformic acid of amphiphilic monomer and polyoxyethylene glycol.The preferred dimethyl aminoethyl of cationic monomer (methyl) acrylate, dimethylaminopropyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate, dimethylaminomethyl (methyl) acrylate, dimethyl aminoethyl (methyl) acrylamide and/or dimethylaminopropyl (methyl) acrylamide by the quaternised quaternary ammonium salt of methyl chloride.That in polymer A, anionic monomer accounts for monomer total amount is preferably 5-40 % by weight.Monomer accounts for the 10-50 % by weight of the reaction liquid adding part dispersion agent.The polymericular weight that GPC method records this invention manufacture is greater than 1.0 × 10
8gram/mol.The molecular weight of dispersion agent is about 65,000 gram/mol.The salt preferably used in this invention is sodium-chlor, ammonium sulfate and/or sodium sulfate.Before salt adding can make reaction or after reaction, before preferred reaction.Add-on is with total water-water dispersion for benchmark, and its amount is preferably the 0.75-2.0 % by weight of dispersion.This invention preferably uses azo-initiator.Its add-on preferably accounts for the 0.01-0.1 % by weight of amount of monomer.Once can add and also can add in batches.Polymeric reaction temperature is preferably 30-90 DEG C.The amount of the dispersion agent that postorder adds is preferably 20-35 % by weight, and the temperature adding dispersion agent is preferably less than 35 DEG C, and it is necessary that this dispersion agent postorder adds step.This invention it is mentioned that the purposes in its auxiliary agent in aqueous system in solid/liquid separation, paper-making process and the preservative system in paper-making process.The synthetic method that patent reports one " water-water " type anionic polyacrylamide emulsion of publication number CN101649024A.Its synthetic method is by inorganic salt, non-ionic hydrophilic monomer, anionic monomer, hydrophobic monomer, has surface-active monomer, sequestrant, deionized water mixing, adjust ph to 6.5-7.5; even with emulsifier; logical nitrogen protection; 18-50 DEG C is added initiator at twice; a polyreaction 4-7 hour; after polymerization reaction times 1-3 hour, this product obtained.Inorganic salt are selected from ammonium sulfate, sodium sulfate, ammonium chloride, preferably sulfuric acid ammonium, and add-on is 20-30wt%.The preferred acrylamide add-on of non-ionic hydrophilic monomer accounts for the 75-85mol% of monomer total amount.The preferred 2-acrylamide-2-methyl propane sulfonic of anionic monomer, add-on accounts for the 4-8mol% of whole monomer system.Hydrophobic monomer preferable methyl ethyl propenoate accounts for the 5-9mol% of whole monomer system.Have the preferred Macrogol 200 mono acrylic ester of surface-active monomer, it accounts for the 6-8mol% of whole monomer system.Whole monomer system accounts for the 15-30wt% of whole dispersion system.The multipolymer of the preferred sodium acrylate of stablizer and acrylamide, the intrinsic viscosity of stablizer in the sodium chloride brine of 1mol/L is 100-300mL/g, and stabilizing agent dosage accounts for the 15-20wt% of whole system.The preferred disodium ethylene diamine tetraacetate of sequestrant, add-on accounts for the 0.012-0.02wt% of whole dispersion system.Initiator initiator system of ammonium persulfate/trolamine redox system, kick off temperature 18-35 DEG C, add-on is the 0.010-0.024wt% of whole monomer system.The patent of publication number CN101735385A has been reported for work a kind of preparation method of anionic polyacrylamide by water dispersion, and it comprises a few part composition such as salt solution, dispersion agent, batching and sequestrant, chain-transfer agent, initiator.Ammonium sulfate or sodium sulfate 30-40wt%, deionized water 55-69.9wt%, sodium-chlor 0.1-5wt% Homogeneous phase mixing obtain salt solution; Dispersion agent is by 15-25wt%2-acrylamide-2-methyl propane sulfonic or acrylamide, and 70-90wt% de-salted water, makes initiator with the azo isobutyl amidine hydrochloride of 1-5ppm and cause obtained at 40-50 DEG C.Prepare burden and to be made up of the vinylformic acid of the acrylamide of 50-98wt%, 1-40wt%, the 2-acrylamide-2-methyl propane sulfonic of 0.5-5wt%, the organic acid of 0.1-5wt% and salt solution, acrylamide, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic, organic acid total concn reach 15-30wt%, and pH value is adjusted to 5-9.Organic acid is the unsaturated monoprotic acid such as methylene-succinic acid or oxalic acid or polyprotonic acid.Sequestrant is disodium ethylene diamine tetraacetate, and chain-transfer agent is sodium formiate, and its add-on is respectively 10-100ppm, 10-500ppm of acrylamide, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic, organic acid summation.Initiator is redox system, oxygenant is Potassium Persulphate or ammonium persulphate, and reductive agent is S-WAT or sodium bisulfite, add-on with acrylamide, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic, organic acid summation for benchmark, oxygenant is 5-100ppm, and reductive agent is 1-50ppm.
The patent of CN1954021A by adding dispersion agent and polyvalent alcohol controls speed of response and stability of emulsion, and mentions the application in solid/liquid separation and papermaking.
The patent of CN101649024A controls speed of response and polymkeric substance speed of separating out by adding hydrophobic monomer, and the patent of CN101735385A controls speed of response by adding initiator in batches.
In oil production, traditional water plugging and profiling technology has water pack off and organic chemical water plugging and profile controlling two kinds.Mostly chemical process is adopted when solving sand production, well water, oil well high liquid measure, low-producing technical problem.Anionic polyacrylamide jelly system is widely used in oil and water well water plugging and profile controlling as chemical water plugging amendment.The anionic polyacrylamide being usually used in oil and water well water plugging and profile controlling has dry powder and water-in-oil emulsion two kinds of forms.But also there is following defect as water plugging profile control agent in its respective jelly system: 1. the anionic polyacrylamide of dry powder comprises the steps such as drying, pulverizing, granulation in production process link, so energy consumption is high, larger dissolver is needed at the scene during application, and dissolution time is longer, this all constrains the application of dry powder product, especially the application of the specific area of some production operation narrow space, the water plugging and profile controlling of such as offshore oilfield, the area that production vessel is less does not hold comparatively large dissolver; 2. water-in-oil emulsion adds a large amount of oils and makes its price higher in building-up process, and water-in-oil emulsion also exists the defect such as temperature resistant antisalt ability, resistance to erosion ability, again because adding of a large amount of oils makes it there is potential safety hazard when applying; 3. also there is the defects such as crosslinking time jelly system that is too fast, that formed easily dewaters with polyvalent metal ion as the polyacrylamide gel system that linking agent is formed.Exactly because there is shortcoming as above in common polyacrylamide gel system water plugging profile control agent, therefore wish that a kind of more superior polyacrylamide gel system occurs to solve the problem, using anionic polyacrylamide water-in-water emulsion as host, resol is exactly produce under this background as the water plugging profile control agent of linking agent.
At present, the water plugging profile control agent patent kind of domestic application is a lot.The production that patent reports a kind of inorganic water plugging profile control agent of publication number CN00123964.3 and using method.This water plugging profile control agent is made up of first, second, the third three kinds of materials, first material proportioning sulfoaluminate clinker fine powder 98.3%-98.9%, molasses 0.3%, sodium carbonate 0.8%-1.4%, second material proportioning: anhydrite 76%, unslaked lime 23.86%, sodium-chlor 0.1%, lithium hydroxide 0.04%, third material proportioning: wilkinite 50%, bauxite clay 46%, molasses 3.0%-3.5%, wooden calcium 0.5%-1.0%.The first and second the third three kinds of materials are according to respective proportioning, first, second, the third three kinds of materials are made through mixing Moses, fineness requirement specific surface area is greater than 400m/kg, water-intake rate 3-4 times, cubical expansivity 8-9 times, adapting to oil temperature 50 DEG C-85 DEG C, take Oil-well Reservior Water as mixed solution, presetting period 6-10h, final setting time 8-12h, within 3 days, intensity can reach 3-6MPa, and water suction is many, infusion diffusion length is far away, water plugging and profile controlling scope is large, and this material has the feature of " solid water not solidify the oil ", can prevent crude oil pollution, also can use Oil-well Reservior Water dilution mixture, easy to use.Polymer water plugging amendment is reported in the patent of publication number CN92112307.8.This polymer water plugging amendment is the high molecular polymer being formed a kind of tridimensional network by organosilane and acrylamide anionic monomer, cationic monomer, non-ionic monomer in aqueous by free radical polymerization, concrete preparation method is, aqueous solution suspension polymerization mode is adopted to prepare, by adding XL-23 dispersion agent, polymerization single polymerization monomer is uniformly dispersed in aqueous, and control the crosslinking degree of polymer water plugging amendment, the elastomerics of obtained a kind of semi-transparent clear.This water plugging profile control agent has the advantages such as the low and easy construction of resistance to erosion, nontoxic pollution-free, cost.
For oil-gas mining process, anionic polyacrylamide water-in-water emulsion is used as water plugging profile control agent and has no report in other patent.In this patent, adopt the method for segmentation salt adding to be controlled to newborn speed and stability of emulsion, obtain the anionic polyacrylamide water-in-water emulsion larger with molecular weight that have good stability, thus make this emulsion be suitable as Water in Water Shutoff in Oil Field profile control.In this patent, by adding suitable monomer, make anionic polyacrylamide water-in-water emulsion have salt tolerance, thus make this product when offshore oil production platform is applied, seawater can be adopted to dissolve.
Summary of the invention
The invention provides a kind of anionic polyacrylamide water-in-water emulsion water plugging profile control agent and preparation method thereof and use usage.
The present invention adopts following technical scheme:
Anionic polyacrylamide water-in-water emulsion water plugging profile control agent of the present invention is made up of anionic polyacrylamide water-in-water emulsion and linking agent, linking agent accounts for the 30%-150wt% of anionic polyacrylamide water-in-water emulsion, described anionic polyacrylamide water-in-water emulsion is water-soluble nonionic monomer, anionic monomer is formed by initiator initiated polymerization under the existence of inorganic salt, stablizer, sequestrant, deionized water, and described linking agent is one or more in resol, chromium cross linker.
Described inorganic salt are anhydrous sodium sulphate, ammonium sulfate, sodium-chlor or sodium phosphate wherein one or more, and its content accounts for the 20%-30w% of anionic polyacrylamide water-in-water emulsion, preferably sulfuric acid ammonium and sodium sulfate.
Described water-soluble nonionic monomer is acrylamide, and its content accounts for the 80-99mol% of water-soluble nonionic monomer and anionic monomer summation.
Described anionic monomer is vinylformic acid, sodium acrylate, 2-acrylamide-2-methyl propane sulfonic wherein one or more, and its content accounts for the 1-20mol% of water-soluble nonionic monomer and anionic monomer summation.
Described stablizer is a kind of anionic polymer, this polymkeric substance is polymerized by anionic monomer, this anionic monomer is vinylformic acid, sodium acrylate, 2-acrylamide-2-methyl propane sulfonic wherein one or more, the quality of this stablizer accounts for the 4-7w% of anionic polyacrylamide water-water breast, and preferably this stablizer forms by sodium acrylate homopolymerization or by sodium acrylate and the copolymerization of 2-acrylamide-2-methyl propane sulfonic sodium.
Described sequestrant is selected from disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, preferred disodium ethylene diamine tetraacetate, and its add-on accounts for the 0.005-0.1w% of anionic polyacrylamide water-in-water emulsion.
Described initiator is redox initiator or water-soluble azo class initiator or two kinds of initiator system compound uses, oxygenant is ammonium persulphate or Potassium Persulphate, reductive agent is sodium sulphite anhydrous 99.3 or sodium bisulfite, water-soluble azo class initiator is V2, two (2-tetrahydroglyoxaline) dihydrochloride or 2 of 2'-azepine, 2'-azo diisobutyl amidine dihydrochloride, the consumption of initiator is the 0.006%-0.01% of water-soluble nonionic monomer and anionic monomer quality summation, and the use temperature of oxidation-reduction trigger system is 20-30 DEG C; The use temperature of the composite initiation system that oxidation-reduction initiator and thermal decomposition initiating are formed is 20-30 DEG C; The use temperature of water-soluble azo class thermolysis initiator system is 30-40 DEG C.This invention preferential oxidation reduction initiator ammonium persulfate and sodium bisulfite.
The add-on of described deionized water accounts for the 40-60wt% of anionic polyacrylamide water-in-water emulsion.
The concrete steps of the preparation method of described anionic polyacrylamide water-in-water emulsion are as follows:
Deionized water, stablizer, account for whole inorganic salt total amount 70wt% inorganic salt (, non-ionic monomer, anionic monomer, sequestrant, join in reaction vessel and stir, pH value is adjusted between 5-9, pH value regulator is selected from sodium hydroxide, potassium hydroxide, ammoniacal liquor, preferred sodium hydroxide, logical nitrogen, add initiator initiation reaction, along with the increase of emulsion viscosity slowly adds the inorganic salt of remaining 30wt% in reaction process, be incubated blowing after 8-12 hour, obtain anionic polyacrylamide water-in-water emulsion.
The concrete steps of the using method of anionic polyacrylamide water-in-water emulsion water plugging profile control agent of the present invention are as follows: anionic polyacrylamide water-in-water emulsion on the spot or on-line dilution to be mixed with mass concentration be the 0.6%-4wt% aqueous solution, then linking agent is added, stir, squeeze into stratum.
Positively effect of the present invention is as follows:
Anionic polyacrylamide water-in-water emulsion dissolution rate is fast, under stirring sufficient condition, dissolves and just can reach peak viscosity in about 10-15 minute, and dissolves thoroughly.Injection device adds mixed tune device, can be implemented in line dilution, preparation, injects.Relative and dry powder type polyacrylamide amine solvent needs 1-2 hour, and through often there is the situation of fish-eye shaped insolubles after dissolving, anionic polyacrylamide water-in-water emulsion water plugging profile control agent not only eliminates large-scale dissolver, saves the electricity charge, shortens dissolution time, improves production efficiency, and polyacrylamide utilization ratio is improved.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1
To be equipped with stirring, nitrogen tube, thermometer 250mL four-hole boiling flask in add 108.8g deionized water, 32.4g acrylamide, 44g ammonium sulfate, 5.58g vinylformic acid, 10g stablizer, 0.02gEDTA starts stirring, stirring velocity 200 revs/min, adds 8g anhydrous sodium sulphate, with sodium hydroxide solution, the pH value of system is transferred to 7.Be warming up to 30 DEG C, logical nitrogen 30 minutes, then adds the sodium bisulfite of 0.013g, add the ammonium persulphate of 0.025g after 5 minutes again, reaction in about 15 minutes starts, along with system viscosity increase is carried out in reaction, when viscosity increases to a certain degree, add the ammonium sulfate of 5g and the anhydrous sodium sulphate of 5g.Viscosity slowly reduces, and system is creamy white, and 45 DEG C are incubated 12 hours, and obtain the milky emulsion that rotary viscosity is 280mPas, in the sodium chloride aqueous solution of 1mol/L, its limiting viscosity is 450mL/g.
Embodiment 2
To be equipped with stirring, nitrogen tube, thermometer 250mL four-hole boiling flask in add 108.8g deionized water, 32.4g Methacrylamide, 44g ammonium sulfate, 5.58g vinylformic acid, 10g stablizer, 0.02gEDTA starts stirring, stirring velocity 200 revs/min, adds 8g anhydrous sodium sulphate, with sodium hydroxide solution, the pH value of system is transferred to 7.Be warming up to 30 DEG C, logical nitrogen 30 minutes, then adds the sodium bisulfite of 0.013g, add the ammonium persulphate of 0.025g after 5 minutes again, reaction in about 15 minutes starts, along with system viscosity increase is carried out in reaction, when viscosity increases to a certain degree, add the ammonium sulfate of 5g and the anhydrous sodium sulphate of 5g.Viscosity slowly reduces, and system is creamy white, and 45 DEG C are incubated 12 hours, and obtain the milky emulsion that rotary viscosity is 315mPas, in the sodium chloride aqueous solution of 1mol/L, its limiting viscosity is 385mL/g.
Embodiment 3
To be equipped with stirring, nitrogen tube, thermometer 250mL four-hole boiling flask in add 108.8g deionized water, 32.4g acrylamide, 44g ammonium sulfate, the vinylformic acid of 2.88g, 2.7g2-acrylamide-2-methylpro panesulfonic acid, 10g stablizer, 0.02gEDTA starts stirring, stirring velocity 200 revs/min, adds 8g anhydrous sodium sulphate, with sodium hydroxide solution, the pH value of system is transferred to 7.Be warming up to 30 DEG C, logical nitrogen 30 minutes, then adds the sodium bisulfite of 0.013g, add the ammonium persulphate of 0.025g after 5 minutes again, reaction in about 15 minutes starts, along with system viscosity increase is carried out in reaction, when viscosity increases to a certain degree, add the ammonium sulfate of 5g and the anhydrous sodium sulphate of 5g.Viscosity slowly reduces, and system is creamy white, and 45 DEG C are incubated 12 hours, and obtain the milky emulsion that rotary viscosity is 360mPas, in the sodium chloride aqueous solution of 1mol/L, its limiting viscosity is 377mL/g.
Embodiment 4
To in the reactor of 50L, add 26kg deionized water, start stirring, stirring velocity 50 revs/min, then add 10.5kg ammonium sulfate, 1.91kg anhydrous sodium sulphate, 7.75kg acrylamide, 1.33kg vinylformic acid, 2.39kg stablizer, 4.30gEDTA, with sodium hydroxide, the pH value of system is adjusted to 7.Be warming up to 30 DEG C, logical nitrogen drives oxygen 60 minutes, then adds 3.11g sodium bisulfite, add 5.98g ammonium persulphate after 5 minutes, within about 40 minutes, start reaction, system viscosity increases fast along with reaction, when there is rod climbing phenomenon, add the anhydrous sodium sulphate of 1.2kg and the ammonium sulfate of 1.2kg, subsequently, system viscosity is declined to become breast, 45 DEG C are incubated 12 hours, obtain the milky emulsion of rotary viscosity 259mPas, in the sodium chloride aqueous solution of 1mol/L, its limiting viscosity is 470mL/g.
Embodiment 5
To in the reactor of 500L, add 156.17kg deionized water, start stirring, stirring velocity 50 revs/min, then add 63.16kg ammonium sulfate, 11.48kg anhydrous sodium sulphate, 46.61kg acrylamide, 8.01kg vinylformic acid, 14.35kg stablizer, 25.77gEDTA, with sodium hydroxide, the pH value of system is adjusted to 7.Be warming up to 30 DEG C, logical nitrogen drives oxygen 60 minutes, then adds 18.66g sodium bisulfite, add 35.89g ammonium persulphate after 5 minutes, within about 40 minutes, start reaction, system viscosity increases fast along with reaction, when there is rod climbing phenomenon, add the anhydrous sodium sulphate of 7.18kg and the ammonium sulfate of 7.18kg, subsequently, system viscosity is declined to become breast, 45 DEG C are incubated 12 hours, obtain the milky emulsion of rotary viscosity 265mPas, in the sodium chloride aqueous solution of 1mol/L, its limiting viscosity is 495mL/g.
Embodiment 6
To in the reactor of 2000L, add 780.86kg deionized water, start stirring, stirring velocity 50 revs/min, then add 315.79kg ammonium sulfate, 57.42kg anhydrous sodium sulphate, 232.54kg acrylamide, 8.01kg vinylformic acid, 40.05kg stablizer, 128.86gEDTA, with sodium hydroxide, the pH value of system is adjusted to 7.Be warming up to 30 DEG C, logical nitrogen drives oxygen 60 minutes, then adds 93.3g sodium bisulfite, add 179.43g ammonium persulphate after 5 minutes, within about 40 minutes, start reaction, system viscosity increases fast along with reaction, when there is rod climbing phenomenon, add the anhydrous sodium sulphate of 35.89kg and the ammonium sulfate of 35.89kg, subsequently, system viscosity is declined to become breast, 45 DEG C are incubated 12 hours, obtain the milky emulsion of rotary viscosity 255mPas, in the sodium chloride aqueous solution of 1mol/L, its limiting viscosity is 493mL/g.
Embodiment 7
CB1B-6 well is under the jurisdiction of offshore oil production factory of Shengli Oil Field company limited of China Petrochemical Industry, and go into operation on August 27th, 1999, and transfer water injection well on September 23rd, 2005, profile control horizon is in shop epimere, and water accepting layer thickness is 36m, and mean permeability is 1108.1 × 10-3 μm
2, average pore is 36.98%, and shale index is 9.96%, and belong to secondary three sections of water fillings at present, mains pressure 8.4MPa, wellhead pressure is 5.6MPa, and day injection allocation amount is 260m
3, accumulation water filling 20.29 ten thousand m
3.The pressure breakdown time is 95s, corresponding oil well day produce oil 143.6t, on average moisture 42.6%.This well is on October 15th, 2008 to October 20, anionic polyacrylamide water-in-water emulsion is adopted to carry out continuous profile control operation, constructional method is the aqueous solution anionic water-in-water emulsion preparation 2%, compound method is fill water in dosing pond, open and stir, anionic polyacrylamide water-in-water emulsion is poured in pond, and within about 10 minutes, solution stirring is even.Then the phenolic resin crosslinking agent of 50% emulsion weight is poured in pond, stir about 10 minutes, amendment has been prepared.First with 10m
3the injection discharge capacity injection test of/h one hour, injection pressure is 2.6MPa, subsequently with 12m
3the discharge capacity of/h, point three slugs inject 990m altogether
3cross-linking system, the injection rate of three slugs is respectively 330m
3, 270m
3, 270m
3, cross replacement 120m subsequently
3high concentration polymer solution, finally replaces 8m
3seawater to guarantee that medicament injects stratum completely, actual injection of polymer emulsion 20.1t, linking agent 6.84t, operation pressure have 2.6MPa slowly be increased to 5.6MPa, until construction terminate pressure substantially remain unchanged, site operation is very normal.Table one is the effect of increasing production of corresponding oil well after construction.
Corresponding Anomalous character manufacturing parameter before and after table one CB1B-6 well construction
Embodiment 8
It is 79.3t that GD2-21-15 well is under the jurisdiction of daily fluid production rate before China Petrochemical Industry's this well construction of Gudao area of Shengli Oilfield oil recovery factory, daily oil production 1.982t, moisture 97.5%, construct on July 9th, 2010, constructional method is the aqueous solution anionic water-in-water emulsion preparation 2%, and compound method is first a 10m
3the pond of left and right fills water, opens and stirs, anionic polyacrylamide water-in-water emulsion is slowly poured in pond, solution stirring after 10 minutes, then is poured into phenolic resin crosslinking agent in pond, and the dosage of linking agent is the half of emulsion, stir about 10 minutes, amendment has been prepared.Site operation discharge capacity 10-15m
3/ h, actual injection blocking agent 300m
3, amount to anionic polyacrylamide water-in-water emulsion 6t.Construction pump pressure rises to 7MPa by 0.6MPa, and site operation is smooth.Daily fluid production rate 80.4t after driving a well, daily oil production 3.816t, moisturely be down to 95.3%, but because daily fluid production rate is larger, cause moisture rising, daily oil production declines, destroy for preventing from producing the frozen glue blocking layer just formed, Liquid output has made adjustment in time, and daily fluid production rate slowly drops to 60.5t by 80.4t, and daily oil production is increased to 5.203t, 3.2t is added before comparing construction, moisturely drop to 91.4%, have dropped 6.1% before comparing construction, just current effect water-blocking operation achieves good effect.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (10)
1. an anionic polyacrylamide water-in-water emulsion water plugging profile control agent, it is characterized in that: described anionic polyacrylamide water-in-water emulsion water plugging profile control agent is made up of anionic polyacrylamide water-in-water emulsion and linking agent, linking agent accounts for the 30-150wt% of anionic polyacrylamide water-in-water emulsion, described anionic polyacrylamide water-in-water emulsion is water-soluble nonionic monomer, anionic monomer is at inorganic salt, stablizer, sequestrant, formed by initiator initiated polymerization under the existence of deionized water, described linking agent is resol, one or more in chromium cross linker.
2. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, it is characterized in that: described inorganic salt are anhydrous sodium sulphate, ammonium sulfate, sodium-chlor or sodium phosphate wherein one or more, and its content accounts for the 20-30wt% of anionic polyacrylamide water-in-water emulsion.
3. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, is characterized in that: described water-soluble nonionic monomer is acrylamide, and its content accounts for the 80-99mol% of water-soluble nonionic monomer and anionic monomer summation.
4. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, it is characterized in that: described anionic monomer is vinylformic acid, sodium acrylate, 2-acrylamide-2-methyl propane sulfonic wherein one or more, and its content accounts for the 1-20mol% of water-soluble nonionic monomer and anionic monomer summation.
5. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, it is characterized in that: described stablizer is a kind of anionic polymer, this polymkeric substance is polymerized by anionic monomer, this anionic monomer is vinylformic acid, sodium acrylate, 2-acrylamide-2-methyl propane sulfonic wherein one or more, and the quality of this stablizer accounts for the 4-7wt% of anionic polyacrylamide water-in-water emulsion.
6. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, it is characterized in that: described sequestrant is disodium ethylene diamine tetraacetate, its add-on accounts for the 0.005-0.1wt% of anionic polyacrylamide water-in-water emulsion.
7. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, it is characterized in that: described initiator is redox initiator or water-soluble azo class initiator or two kinds of initiator system compound uses, oxygenant is ammonium persulphate or Potassium Persulphate, reductive agent is sodium sulphite anhydrous 99.3 or sodium bisulfite, water-soluble azo class initiator is V2, two (2-tetrahydroglyoxaline) dihydrochloride or 2 of 2'-azepine, 2'-azo diisobutyl amidine dihydrochloride, the consumption of initiator is the 0.006%-0.01wt% of water-soluble nonionic monomer and anionic monomer quality summation.
8. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, is characterized in that: the add-on of deionized water accounts for the 40-60wt% of anionic polyacrylamide water-in-water emulsion.
9. anionic polyacrylamide water-in-water emulsion water plugging profile control agent as claimed in claim 1, is characterized in that: the concrete steps of the preparation method of described anionic polyacrylamide water-in-water emulsion are as follows:
Deionized water, stablizer, the 70wt% inorganic salt accounting for whole inorganic salt total amount, non-ionic monomer, anionic monomer, sequestrant, join in reaction vessel and stir, pH value is adjusted between 5-9, logical nitrogen, add initiator initiation reaction, along with the increase of emulsion viscosity slowly adds the inorganic salt of remaining 30wt% in reaction process, be incubated blowing after 8-12 hour, obtain anionic polyacrylamide water-in-water emulsion.
10. the using method of the anionic polyacrylamide water-in-water emulsion water plugging profile control agent as described in any one of claim 1-9, it is characterized in that: the concrete steps of described using method are as follows: anionic polyacrylamide water-in-water emulsion on the spot or on-line dilution to be mixed with mass concentration be the 0.6%-4% aqueous solution, then linking agent is added, stir, squeeze into stratum.
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Cited By (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 |
| CN106883357A (en) * | 2017-03-16 | 2017-06-23 | 东营方立化工有限公司 | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its production and use |
| CN108329422A (en) * | 2018-02-07 | 2018-07-27 | 山东诺尔生物科技有限公司 | A kind of water-in-water type microballoon profile control agent and preparation method thereof |
| CN108586671A (en) * | 2018-04-07 | 2018-09-28 | 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 |
| CN111909306A (en) * | 2020-08-14 | 2020-11-10 | 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 (6)
| 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 |
| US20070203290A1 (en) * | 2004-03-18 | 2007-08-30 | Ashland Licensing And Intellectual Property Llc | Anionic Water-In-Water Polymer Dispersion, Method For The Production Thereof And Its Use |
| CN101649024A (en) * | 2009-08-19 | 2010-02-17 | 中国海洋石油总公司 | Preparation method of water-in-water cationic polyacylamide emulsion |
| 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 |
| 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 |
| CN102532375A (en) * | 2011-12-29 | 2012-07-04 | 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 (6)
| 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 |
| US20070203290A1 (en) * | 2004-03-18 | 2007-08-30 | Ashland Licensing And Intellectual Property Llc | Anionic Water-In-Water Polymer Dispersion, Method For The Production Thereof And Its Use |
| CN101649024A (en) * | 2009-08-19 | 2010-02-17 | 中国海洋石油总公司 | Preparation method of water-in-water cationic polyacylamide emulsion |
| 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 |
| 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 |
| CN102532375A (en) * | 2011-12-29 | 2012-07-04 | 浙江传化股份有限公司 | Polyacrylamide microsphere |
Non-Patent Citations (3)
| Title |
|---|
| 刘军等: "多种形态聚丙烯酰胺在胜利油田开发中的应用", 《精细石油化工进展》 * |
| 刘志良等: "新型聚丙烯酰胺乳液合成及在油田中应用", 《钻采工艺》 * |
| 方明: "《中国石油学会第八届青年学术年会优秀论文集：2013》", 31 May 2014, 石油工业出版社 * |
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| CN106883357A (en) * | 2017-03-16 | 2017-06-23 | 东营方立化工有限公司 | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its production and use |
| CN108329422A (en) * | 2018-02-07 | 2018-07-27 | 山东诺尔生物科技有限公司 | A kind of water-in-water type microballoon profile control agent and preparation method thereof |
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| 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 |
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