CN102304200B - Crosslinked polymer microspheres and preparation method thereof - Google Patents
Crosslinked polymer microspheres and preparation method thereof Download PDFInfo
- Publication number
- CN102304200B CN102304200B CN 201110140086 CN201110140086A CN102304200B CN 102304200 B CN102304200 B CN 102304200B CN 201110140086 CN201110140086 CN 201110140086 CN 201110140086 A CN201110140086 A CN 201110140086A CN 102304200 B CN102304200 B CN 102304200B
- Authority
- CN
- China
- Prior art keywords
- cross
- linked polymer
- preparation
- polymer microsphere
- oil
- 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
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides crosslinked polymer microspheres and a preparation method thereof. The preparation method comprises the following step of: in inert atmosphere, performing polymerization reaction on monomers in aqueous dispersion in which a polymer dispersant, inorganic salt and crosslinking monomers are dissolved to obtain the crosslinked polymer microspheres. When the crosslinked polymer microspheres are actually used, aqueous dispersion containing the crosslinked polymer microspheres or a concentrated solution prepared from crosslinked polymer microsphere powder can be directly adopted, is pumped into a water injection pipeline by a high pressure proportioning pump, and is mixed and diluted on line in field, and the mixed and diluted solution in predesigned mass percentage content is injected into an oil deposit through a water injection well to fulfill the aims of improving the nonhomogeneity of the oil deposit and improving the recovery ratio of crude oil of the oil deposit through water injection development.
Description
Technical field
The present invention relates to a kind of cross-linked polymer microsphere that can improve oil reservoir nonuniformity, raising waterflooding reservoir oil recovery factor and preparation method thereof, belong to the petroleum industry field.
Background technology
At present, the early development oil field progressively enters the water flood recovery intermediary and later stages, how further to improve volumetric conformance efficiency and ripples and the interior efficiency of displacement of volume of injecting water, economical, the existing oil field of exploitation is one of key subjects of needing to be resolved hurrily of petroleum industrial circle effectively, important effect has been brought into play in the development of wherein intensified oil reduction technology and application.
The intensified oil reduction technology relates to a lot of aspects, injects the volumetric conformance efficiency of liquid and displacement efficiency two classes in the raising swept volume and can be divided into raising based on the method for improving the displacement effect.
Along with going deep into of research, the nonuniformity of oil reservoir causes concern in the industry day by day to the influence of water drive, chemical flooding displacing fluid sweep efficiency, people recognize to have only the deep profile controlling of passing through, could be more economically, adjust, improve the nonuniformity of oil reservoir effectively, thereby improve the volumetric conformance efficiency that injects liquid, guarantee that chemical flooding realizes high efficiency of displacement, improve chemical flooding displacing fluid and the oil recovery factor in follow-up water drive stage.This wherein, be that the deep profile controlling technology of representative is to have superiority economically with cross-linked polymer flow-gel, cross-linked polymer solution, cross-linked polymer microsphere, effect is obvious, meet long-term injection, be beneficial to the technology of environmental protection, to research and the improvement of this method, the nonuniformity of adjusting, improve oil reservoir there is very important meaning on more profound.
At present, method for the preparation of the linked polymer coil of tertiary oil recovery, a kind of is to adopt linear partially hydrolyzed polyacrylamide (HPAM) dilute solution (massfraction at it below critical overlapping massfraction) and linking agent reaction, form the aqueous dispersion (that is cross-linked polymer solution) of linked polymer coil; Another method is to manage to form the water-dispersion phase of nanometer or micro-meter scale, in water-dispersion mutually, comprise cross-linking monomer at the copolymerization of interior multiple monomer, form the micro polymer micelle, these micelles swelling, dissolving back in water form the linked polymer coil of different scale.Theoretically, can form the linked polymer coil that particle diameter and earth bore road size are complementary after having only use to inject, could be detained effectively and the shutoff venturi, cause deep liquid stream changed course, the real nonuniformity that realizes adjusting and improving oil reservoir, the recovery ratio of raising waterflooding crude oil.
The size of a cross linked water soluble polymer ball of string that obtains among the preparation method of Chinese patent ZL 200410006334.6 open reports is generally the hundreds of nanometer, particle diameter is less, the size of a cross linked water soluble polymer ball of string that obtains among the preparation method that Chinese patent ZL 200710063645.X openly reports increases to several microns, adopt the cross linked water soluble polymer ball of string of above-mentioned two kinds of methods preparation can satisfy in, the service requirements of low-permeability oil pool, the test of ore deposit factory has obtained good raising recovery ratio effect.But in using, ore deposit factory also finds, for higher permeability oil reservoir (rate of permeation is greater than 1000 millidarcies), or exist the higher permeability band in, low-permeability oil pool, in order to obtain plugging effect preferably, test needs to increase the massfraction that injects a liquid cross linked water soluble polymer ball of string in early days, has reduced the economy of injection system.Therefore, study, seek the preparation method of a kind of large size cross linked water soluble polymer microballoon (ball of string), for improving and improve higher permeability oil reservoir (rate of permeation is greater than 1000 millidarcies), or exist the higher permeability band in, the displacement effect of low-permeability oil pool, will have very practical value.
Summary of the invention
The purpose of this invention is to provide a kind of cross-linked polymer microsphere and preparation method thereof.
The preparation method of cross-linked polymer microsphere provided by the invention comprises the steps: under inert atmosphere, and polymerization single polymerization monomer carries out polyreaction and obtains described cross-linked polymer microsphere in the aqueous dispersions that is dissolved with macromolecule dispersing agent, inorganic salt and cross-linking monomer.
Among the above-mentioned preparation method, the quality percentage composition of macromolecule dispersing agent, inorganic salt and cross-linking monomer described in the described aqueous dispersions is respectively 1.0%～10.0%, 10.0%～40.0% and 0.001%～3.0%; The quality percentage composition that described polymerization single polymerization monomer accounts for described aqueous dispersions is 1.0%～40.0%.
Among the above-mentioned preparation method, the quality percentage composition of macromolecule dispersing agent described in the described aqueous dispersions specifically can be 4.3%, 5.82% or 6.82%; The quality percentage composition of inorganic salt specifically can be 18% or 195 in the described aqueous dispersions; The quality percentage composition of cross-linking monomer specifically can be 0.45% or 0.46% in the described aqueous dispersions; The quality percentage composition that described polymerization single polymerization monomer accounts for described aqueous dispersions specifically can be 5.68% or 5.7%.
Among the above-mentioned preparation method, described polymerization single polymerization monomer can be the monomer molecule that only contains single pair of key and water soluble group in the molecular structure; Comprise non-ionic monomer, for example: acrylamide, Methacrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl pyrrolidone, N,N-DMAA, vinyl cyanide, diacetone acrylamide, (methyl) 2-hydroxyethyl acrylate acrylamide or vinylcarbinol etc.; Anionic monomer, for example: the corresponding salt of monomers such as (methyl) vinylformic acid, itaconicacid, toxilic acid, 2-acrylamide-2-methyl propane sulfonic acid or vinyl sulfonic acid; Cationic monomer, for example: (methyl) acrylyl oxy-ethyl-trimethyl salmiac, (methyl) acrylyl oxy-ethyl diethylmethyl ammonium chloride, (methyl) acrylyl oxy-ethyl dimethyl benzyl ammonium chloride, (methyl) acrylyl oxy-ethyl diethyl benzyl ammonium chloride or dimethyl diallyl ammonium chloride etc.
Among the above-mentioned preparation method, described inorganic salt can be in ammonium sulfate, sodium sulfate, vitriolate of tartar, ammonium chloride, Repone K and the sodium-chlor etc. at least a.
Among the above-mentioned preparation method, described cross-linking monomer can be the polyfunctional monomer that contains two or more pairs key in the molecular structure, and distance can be regulated by regulating the length that connects two key groups between two keys.For example: the bifunctional monomer can be N, N '-methylene-bisacrylamide, polyethyleneglycol diacrylate, polyoxyethylene glycol diallyl ether, N, N-diallyl dimethyl chlorination amine, N, N '-diallyl-N, N, N ', the own dichloride ammonium of N '-tetramethyl-or N, N '-two couple vinyl benzyl-N, N, N ', the own dichloride amine of N '-tetramethyl-etc.; The trifunctional monomer can be three vinylformic acid-(propyl group) trimethyl or pentaerythritol triallyl ether etc.
Among the above-mentioned preparation method, described macromolecule dispersing agent can be selected commercially available macromolecule dispersing agent, for example adopt commercially available: relative molecular mass is the homopolymer of the polyvinyl alcohol of 4000-20000, polyvinylamine that relative molecular mass is 5000-30000, vinyl pyrrolidone or multipolymer etc., wherein adopts the homopolymer of vinyl pyrrolidone or multipolymer effect better; Or by the dilute solution polymerization of the described polymerization single polymerization monomer of ionic acquisition accordingly in the molecular structure of described cross-linked polymer microsphere, as comprising the negatively charged ion cross-linked polymer microsphere of acrylic amide-acrylic sodium-2-acrylamide-2-methyl propane sulfonic acid sodium structure in the synthetic molecules structure, described macromolecule dispersing agent can carry out dilute solution polymerization gained homopolymer by 2-acrylamide-2-methyl propane sulfonic acid sodium and serve as; Such as the cationic crosslinked polymer microballoon that comprises nitrile-acrylamide-acrylic acid acyl-oxygen ethyl-trimethyl salmiac structure in the zwitter-ion cross-linked polymer microsphere that comprises nitrile-acrylamide-acrylic acid acyl-oxygen ethyl-trimethyl salmiac-2-acrylamide-2-methyl propane sulfonic acid sodium structure in the synthetic molecules structure or the molecular structure, described macromolecule dispersing agent can carry out dilute solution polymerization gained homopolymer by acrylyl oxy-ethyl-trimethyl salmiac and serve as again.
Among the above-mentioned preparation method, also can comprise in oxidative initiator, water-soluble thermal decomposition initiating, sequestrant, pH value conditioning agent and the solubility promoter at least a in the described dispersion liquid.
Among the above-mentioned preparation method, described oxidative initiator can be ammonium persulphate, described oxidative initiator can separately or be carried out oxidation-reduction reaction with reducing gas and be formed free radical, initiated polymerization, described reducing gas is preferably sulfurous gas, the quality percentage composition that the add-on of described oxidative initiator can account for described aqueous dispersions is 0.0001%-0.0005%, as 0.00025% or 0.0003%; Described water-soluble thermal decomposition initiating can be 2,2 '-azo two 2-[1-(2-hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] and propane } dihydrochloride, 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane) dihydrochloride or 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane) dihydrochloride, described water-soluble thermal decomposition initiating is used for the described polymerization single polymerization monomer of polymerization later stage initiation residue, reduce polymerization single polymerization monomer content remaining in the aqueous dispersions of described cross-linked polymer microsphere, the quality percentage composition that the add-on of described water-soluble thermal decomposition initiating can account for described aqueous dispersions is 0.0001%-0.0008%, as 0.0005% or 0.00075%; Described sequestrant is disodium ethylene diamine tetraacetate, be used for slowing down, eliminate the polymer monomer heavy metal ion to the influence of polyreaction, the quality percentage composition that the add-on of described sequestrant can account for described aqueous dispersions is 0.0001%-0.0005%, as 0.0005%; Described pH value conditioning agent is sodium hydroxide, yellow soda ash or sodium bicarbonate, is used for regulating the pH value of aqueous dispersions, guarantees the acid-basicity that aqueous dispersions is suitable; Described solubility promoter can be urea, can make each composition of aqueous phase can fully be dissolved in water, and the quality percentage composition that the add-on of described solubility promoter can account for described aqueous dispersions is 0.001%-0.005%, as 0.001%.
Among the above-mentioned preparation method, described method also comprise with described cross-linked polymer microsphere precipitate, refining and dry step.
Among the above-mentioned preparation method, the temperature of described polyreaction can be 5 ℃-85 ℃, as 35 ℃ or 50 ℃; The time of described polyreaction can be 4 hours-12 hours, as 10 hours.
The particle diameter of the cross-linked polymer microsphere of method for preparing of the present invention is 3 μ m-50 μ m, as 9.6 μ m, 14.5 μ m or 15.6 μ m.
During the actual use of cross-linked polymer microsphere provided by the invention, can directly adopt the strong solution of the aqueous dispersions that contains described cross-linked polymer microsphere or described cross-linked polymer microsphere powder preparation, pump into waterflood-transmission line through the high pressure proportioning pump, on-the-spot on-line mixing, dilution back are injected into oil reservoir inside with the quality percentage composition of design in advance by water injection well, reach the purpose of improving the oil reservoir nonuniformity, improving the waterflooding reservoir oil recovery factor.When cross-linked polymer microsphere of the present invention is used as the amendment that is fit to improve the oil reservoir nonuniformity, improve the waterflooding reservoir oil recovery factor, usually the quality percentage composition for 0.1～3.0 ‰ scope of injecting quality in effectively, when its quality percentage composition for inject quality 0.2～1.5 ‰ the time effect better, and when its quality percentage composition for the injection quality 0.4～0.8 ‰ the time best results.Certainly, for the oil reservoir of different geologic conditions, different development phases, also should specifically determine functional quality mark and the injection mode that it is actual by early stage laboratory experiment, numerical simulation.
In the profile control of oil reservoir is handled, by cross-linked polymer microsphere provided by the invention at higher permeability (rate of permeation is greater than 1000 millidarcies), or exist the higher permeability band in, the machinery in the low-permeability oil pool is detained, shutoff large-size venturi, cause deep liquid stream changed course, can adjust and improve the heterogeneous body influence of oil reservoir, the formed advantage aquaporin of shutoff oil deposit deep part long-term injecting water.The water solution system of cross-linked polymer microsphere provided by the invention is particularly suitable for higher permeability oil reservoir (rate of permeation is greater than 1000 millidarcies), or exist the higher permeability band in, low-permeability oil pool uses, improves the recovery ratio of waterflooding intermediary and later stages oil reservoir crude oil.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Adopting the cross-linked polymer microsphere aqueous solution of determining volume is 2.0 μ m to perm-plug method
2Shutoff profile control performance and the oil displacement efficiency of synthetic core, the simulation cross-linked polymer microsphere aqueous solution is estimated the shutoff profile control performance of the cross-linked polymer microsphere aqueous solution to the shutoff in reservoir formation duct.
The preparation of embodiment 1, cross-linked polymer microsphere
Gas gas ingress pipe is being housed, thermometer, add polyvinylpyrrolidone (K-60) 1.50 grams in the jacketed reactor of constant speed stirrer, ammonium sulfate 16.50 grams, sodium-chlor 1.50 grams, acrylamide (AM) 5.68 grams, sodium acrylate 1.02 grams, 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 3.30 grams, N, N '-diallyl-N, N, N ', own dichloride ammonium 0.45 gram of N '-tetramethyl-, 0.50 milligram of sequestrant disodium ethylene diamine tetraacetate, 1.0 milligrams of solubility promoter ureas, more than various compositions be dissolved in 68.00 grams ultrapure waters (specific conductivity≤4 μ S/cm), and be 7.5-8.5 with 35% sodium hydrate regulator solution pH value; In the above-mentioned aqueous dispersions, the quality percentage composition of ammonium sulfate and sodium-chlor is 18.0%; The quality percentage composition of acrylamide is 5.68%; The quality percentage composition of polyvinylpyrrolidone, sodium acrylate and 2-acrylamide-2-methyl propane sulfonic acid is 5.82%; N, N '-diallyl-N, N, N ', the quality percentage composition of the own dichloride ammonium of N '-tetramethyl-is 0.45%; The quality percentage composition of disodium ethylene diamine tetraacetate is 0.0005%; The quality percentage composition of urea is 0.001%.
Setting 35 ℃ is kick off temperature, at first feed the rare gas element high pure nitrogen in the above-mentioned saline aqueous dispersions and drive oxygen, oxygen level in the reduction system (≤0.3 μ g/g) is convenient to polyreaction and is initiated, add 0.30 milligram of ammonium persulphate (the quality percentage composition that accounts for aqueous dispersions is 0.0003%), 2,0.50 milligram of 2 '-azo two (2-amidine propane) dihydrochloride (the quality percentage composition that accounts for aqueous dispersions is 0.0005%), feed the compound formation oxidation-reduction trigger system of reducing gas sulfurous gas and aqueous phase ammonium persulphate then, polyreaction was carried out 4 hours, temperature is risen to 50 ℃ again, continued 6 hours, obtain the aqueous dispersions of cross-linked polymer microsphere, its viscosity is 848mPa.s in the time of 25 ℃, its size-grade distribution intermediate value 14.5 μ m.
The aqueous dispersions that contains cross-linked polymer microsphere that takes out the above-mentioned preparation of part is dissolved in water, in this aqueous solution, add dehydrated alcohol as precipitation agent, be settled out the cross-linked polymer microsphere that particle diameter is 14.5 μ m, through the sherwood oil extracting, drying is made the cross-linked polymer microsphere powder.
Massfraction is that the above-mentioned cross-linked polymer microsphere of 400mg/kg obtained the linked polymer coil aqueous solution in 96 hours in the simulation curing in water of SZ36-1 oil field, 60 ℃ of Bohai Sea, is 2.0 μ m to perm-plug method
2Synthetic core carry out the displacement test of SZ36-1 oil field, Bohai Sea simulated oil, record under the experiment condition and can improve simulated oil recovery ratio 20.6%.
The preparation of embodiment 2, cross-linked polymer microsphere
Gas gas ingress pipe is being housed, thermometer, add polyvinylpyrrolidone (K-17) 2.50 grams in the jacketed reactor of constant speed stirrer, ammonium sulfate 17.50 grams, sodium-chlor 1.50 grams, acrylamide (AM) 5.68 grams, sodium acrylate 1.02 grams, 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 3.30 grams, N, N '-diallyl-N, N, N ', own dichloride ammonium 0.45 gram of N '-tetramethyl-, 0.50 milligram of sequestrant disodium ethylene diamine tetraacetate, 1.0 milligrams of ureas, more than various compositions be dissolved in 66.00 grams ultrapure waters (specific conductivity≤4 μ S/cm), and be 7.5-8.5 with 35% sodium hydrate regulator solution pH value.In the above-mentioned aqueous dispersions, the quality percentage composition of ammonium sulfate and sodium-chlor is 19.0%; The quality percentage composition of acrylamide is 5.68%; The quality percentage composition of polyvinylpyrrolidone, sodium acrylate and 2-acrylamide-2-methyl propane sulfonic acid is 6.82%; N, N '-diallyl-N, N, N ', the quality percentage composition of the own dichloride ammonium of N '-tetramethyl-is 0.45%; The quality percentage composition of disodium ethylene diamine tetraacetate is 0.0005%; The quality percentage composition of urea is 0.001%.
Setting 35 ℃ is kick off temperature, at first feed the rare gas element high pure nitrogen in the above-mentioned saline aqueous dispersions and drive oxygen, oxygen level in the reduction system (≤0.3 μ g/g) is convenient to polyreaction and is initiated, add 0.30 milligram of ammonium persulphate (the quality percentage composition that accounts for aqueous dispersions is 0.0003%), 2,0.50 milligram of 2 '-azo two (2-amidine propane) dihydrochloride (the quality percentage composition that accounts for aqueous dispersions is 0.0005%), feed the compound formation oxidation-reduction trigger system of reducing gas sulfurous gas and aqueous phase ammonium persulphate then, polyreaction was carried out 4 hours, temperature is risen to 50 ℃ again, continued 6 hours, obtain large size cross-linked polymer microsphere aqueous dispersions, its viscosity is 640mPa.s in the time of 25 ℃, its size-grade distribution intermediate value 9.6 μ m.
The cross-linked polymer microsphere aqueous dispersions that contains that takes out the above-mentioned preparation of part is dissolved in water, in its aqueous solution, add dehydrated alcohol as precipitation agent, be settled out the cross-linked polymer microsphere that particle diameter is 9.6 μ m, through the sherwood oil extracting, drying is made large size cross-linked polymer microsphere powder.
Massfraction is that the above-mentioned large size cross-linked polymer microsphere of 400mg/kg obtained the linked polymer coil aqueous solution in 96 hours in the simulation curing in water of SZ36-1 oil field, 60 ℃ of Bohai Sea, is 2.0 μ m to perm-plug method
2Synthetic core carry out the displacement test of SZ36-1 oil field, Bohai Sea simulated oil, record under the experiment condition and can improve simulated oil recovery ratio 18.2%.
The preparation of embodiment 3, cross-linked polymer microsphere
Prepare cross-linked polymer microsphere aqueous solution powder according to the method identical with embodiment 1.
Massfraction is that the cross-linked polymer microsphere of the above-mentioned preparation of 400mg/kg obtained the linked polymer coil aqueous solution in 96 hours in the simulation curing in water of SZ36-1 oil field, 60 ℃ of Bohai Sea, is 3.5 μ m to perm-plug method
2Synthetic core carry out the displacement test of SZ36-1 oil field, Bohai Sea simulated oil, record under the experiment condition and can improve simulated oil recovery ratio 18.6%.
The preparation of embodiment 4, cross-linked polymer microsphere
In the jacketed reactor that gas gas ingress pipe, thermometer, constant speed stirrer are housed, add acrylamide (AM) 1.42 grams, 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 6.40 grams, ultrapure water (specific conductivity≤4 μ S/cm) 42 grams, logical nitrogen 30 minutes, add 0.46 milligram of ammonium persulphate, 0.26 milligram of sodium bisulfite, 35 ℃ of kick off temperatures react and obtained the AM-AMPS copolymer solution as dispersion agent in 4 hours.
Continuation adds ammonium sulfate 43.80 grams in reactor, sodium-chlor 3.80 grams, acrylamide (AM) 14.20 grams, sodium acrylate 2.55 grams, 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 8.30 grams, N, N '-diallyl-N, N, N ', own dichloride ammonium 1.15 grams of N '-tetramethyl-, 1.25 milligrams of sequestrant disodium ethylene diamine tetraacetate, 2.5 milligrams of ureas, ultrapure water (specific conductivity≤4 μ S/cm) 120.00 grams, and be 7.5-8.5 with 35% sodium hydrate regulator solution pH value, in the above-mentioned aqueous dispersions, the quality percentage composition of ammonium sulfate and sodium-chlor is 19.0%; The quality percentage composition of acrylamide is 5.7%; The quality percentage composition of sodium acrylate and 2-acrylamide-2-methyl propane sulfonic acid is 4.3%; N, N '-diallyl-N, N, N ', the quality percentage composition of the own dichloride ammonium of N '-tetramethyl-is 0.46%; The quality percentage composition of disodium ethylene diamine tetraacetate is 0.0005%; The quality percentage composition of urea is 0.001%.
Setting 35 ℃ is kick off temperature, at first feed the rare gas element high pure nitrogen in the above-mentioned saline aqueous dispersions and drive oxygen, oxygen level in the reduction system (≤0.3 μ g/g) is convenient to polyreaction and is initiated, add 0.25 milligram of ammonium persulphate (the quality percentage composition that accounts for aqueous dispersions is 0.00025%), 2,0.75 milligram of 2 '-azo two (2-amidine propane) dihydrochloride (the quality percentage composition that accounts for aqueous dispersions is 0.00075%), feed the compound formation oxidation-reduction trigger system of reducing gas sulfurous gas and aqueous phase ammonium persulphate then, polyreaction was carried out 4 hours, temperature is risen to 50 ℃ again, continued 6 hours, obtain large size cross-linked polymer microsphere aqueous dispersions, its viscosity is 940mPa.s in the time of 25 ℃, its size-grade distribution intermediate value 15.6 μ m.
The aqueous dispersions that contains cross-linked polymer microsphere that takes out the above-mentioned preparation of part is dissolved in water, in its aqueous solution, add dehydrated alcohol as precipitation agent, be settled out the cross-linked polymer microsphere that particle diameter is 15.6 μ m, through the sherwood oil extracting, drying is made large size cross-linked polymer microsphere powder.
Massfraction is that the above-mentioned cross-linked polymer microsphere of 400mg/kg obtained the linked polymer coil aqueous solution in 96 hours in the simulation curing in water of SZ36-1 oil field, 60 ℃ of Bohai Sea, is 3.5 μ m to perm-plug method
2Synthetic core carry out the displacement test of SZ36-1 oil field, Bohai Sea simulated oil, record under the experiment condition and can improve simulated oil recovery ratio 19.5%.
The preparation of Comparative Examples 1, linked polymer coil
Embodiment 5 prepares and contains the w/o type dispersion liquid that particle diameter is the linked polymer coil of bimodal distribution among the preparation method who openly reports according to Chinese patent ZL 200710063645.X;
The above-mentioned w/o type dispersion liquid that particle diameter is the linked polymer coil of bimodal distribution that contains takes a morsel, add dehydrated alcohol and be settled out the linked polymer coil that particle diameter is bimodal distribution as precipitation agent, through the sherwood oil extracting, drying is made the linked polymer coil powder that particle diameter is bimodal distribution.
Massfraction is that the linked polymer coil of 400mg/kg obtained the linked polymer coil aqueous solution in 96 hours in the simulation curing in water of SZ36-1 oil field, 60 ℃ of Bohai Sea, is 2.0 μ m to perm-plug method
2Synthetic core carry out the displacement test of SZ36-1 oil field, Bohai Sea simulated oil, record under the experiment condition and can improve simulated oil recovery ratio 15.0%, experimental result is as shown in table 1.
The result of each embodiment and Comparative Examples comprehensively lists in the table 1.
Table 1, reference examples and each embodiment improve recovery ratio relatively
Comparative examples 1 and 3 as can be seen, the cross-linked polymer microsphere of the present invention's preparation is to the shutoff profile control effect difference of the rock core of different rate of permeation, this just exists the size of cross-linked polymer microsphere of the present invention and the matching problem in rock core duct, need macromolecule dispersing agent, the consumption of inorganic salt and/or the massfraction of linked polymer coil realize when regulating polymerization targetedly.
Comparative examples 1,2 and 4 as can be seen, the raising recovery ratio ability of the cross-linked polymer microsphere of the present invention preparation can by regulate molecular structure, the preparation method regulate.
The effect that above embodiment and comparative result have only pointed out preparation method of the present invention to reach, that is, different large size cross-linked polymer microspheres can carry out adaptive producing according to oil reservoir feature, recovery percent of reserves.
On the other hand, relatively Comparative Examples 1 and four specific embodiments are as can be seen, identical at massfraction, salinity is identical, temperature is identical, the amendment aqueous solution that is used for the shutoff profile control that obtains under the identical condition of curing time, when the identical rock core of perm-plug method is carried out oil displacement experiment, adopt the recovery ratio that improves simulated oil preferably of the cross-linked polymer microsphere aqueous solution that present method obtains, illustrate that to adopt the cross-linked polymer microsphere aqueous solution that present method obtains to have the less linked polymer coil solution of the size that obtains with the employing emulsion polymerisation process for the higher permeability porous medium identical, or more superior shut-off capacity.
Claims (6)
1. the preparation method of a cross-linked polymer microsphere comprises the steps: under inert atmosphere, and polymerization single polymerization monomer carries out polyreaction and obtains described cross-linked polymer microsphere in the aqueous dispersions that is dissolved with macromolecule dispersing agent, inorganic salt and cross-linking monomer;
The quality percentage composition of macromolecule dispersing agent, inorganic salt and cross-linking monomer described in the described aqueous dispersions is respectively 1.0%～10.0%, 10.0%～40.0% and 0.001%～3.0%; The quality percentage composition that described polymerization single polymerization monomer accounts for described aqueous dispersions is 1.0%～40.0%;
Described polymerization single polymerization monomer is acrylamide, Methacrylamide or N,N-DMAA;
Described inorganic salt are at least a in ammonium sulfate, sodium sulfate, vitriolate of tartar, ammonium chloride, Repone K and the sodium-chlor;
Described cross-linking monomer is N, N '-diallyl-N, N, N ', the own dichloride ammonium of N '-tetramethyl-or N, N '-two couple vinyl benzyl-N, N, N ', the own dichloride amine of N '-tetramethyl-;
Described macromolecule dispersing agent is vinyl pyrrolidone homopolymer, vinylpyrrolidone copolymer or 2-acrylamide-2-methyl propane sulfonic acid sodium homopolymer.
2. preparation method according to claim 1 is characterized in that: also comprise in oxidative initiator, water-soluble thermal decomposition initiating, sequestrant, pH value conditioning agent and the solubility promoter at least a in the described dispersion liquid.
3. preparation method according to claim 2, it is characterized in that: described oxidative initiator is ammonium persulphate; Described water-soluble thermal decomposition initiating is 2,2 '-azo two 2-[1-(2-hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] and propane } dihydrochloride, 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane) dihydrochloride or 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane) dihydrochloride; Described sequestrant is disodium ethylene diamine tetraacetate; Described pH value conditioning agent is sodium hydroxide, yellow soda ash or sodium bicarbonate; Described solubility promoter is urea.
4. preparation method according to claim 1 and 2 is characterized in that: described method also comprise with described cross-linked polymer microsphere precipitate, refining and dry step.
5. the cross-linked polymer microsphere of arbitrary described method preparation among the claim 1-4; The particle diameter of described cross-linked polymer microsphere is 3 μ m-50 μ m.
6. the described cross-linked polymer microsphere of claim 5 is as the application of oil-displacing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110140086 CN102304200B (en) | 2011-05-27 | 2011-05-27 | Crosslinked polymer microspheres and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110140086 CN102304200B (en) | 2011-05-27 | 2011-05-27 | Crosslinked polymer microspheres and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102304200A CN102304200A (en) | 2012-01-04 |
| CN102304200B true CN102304200B (en) | 2013-08-21 |
Family
ID=45378130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110140086 Active CN102304200B (en) | 2011-05-27 | 2011-05-27 | Crosslinked polymer microspheres and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102304200B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021159A (en) * | 2018-06-08 | 2018-12-18 | 中国石油天然气股份有限公司 | A kind of oilwell water shutoff agent and its preparation method and application |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9902829B2 (en) * | 2012-05-30 | 2018-02-27 | Akzo Nobel Chemicals International B.V. | Microspheres |
| CN103408703B (en) * | 2013-08-06 | 2015-07-22 | 西安石油大学 | Liquid polymeric microspheres and synthetic method thereof |
| CN103806889B (en) * | 2014-03-04 | 2016-08-17 | 中国石油集团渤海钻探工程有限公司 | Infinite stages chemical stratification pressure break or the method for acidifying |
| EP3184558B1 (en) * | 2014-08-19 | 2018-08-29 | Fujifilm Corporation | Composition for forming polymeric membrane, process for producing same, polymeric membrane, separation membrane module, and ion exchange device |
| CN104194753A (en) * | 2014-08-25 | 2014-12-10 | 孙安顺 | Water dispersible profile control agent for oil extraction and preparation method thereof |
| CN105399873B (en) * | 2014-09-03 | 2017-06-30 | 中国石油化工股份有限公司 | Water-soluble azo initiator and acrylamide polymer and its preparation method and application |
| CN105482033B (en) * | 2014-09-19 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of polymer microballoon and its preparation method and application |
| CN105524215B (en) * | 2014-10-24 | 2019-07-05 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt acrylamide copolymer microballoon dispersion and its preparation method and application |
| CN105273145B (en) * | 2014-11-07 | 2017-11-17 | 中国石油化工股份有限公司 | A kind of weak cross-linked particles profile control agent for improving oil recovery and preparation method thereof |
| US10450500B2 (en) | 2015-01-12 | 2019-10-22 | Ecolab Usa Inc. | Thermally stable polymers for enhanced oil recovery |
| CN105622842B (en) * | 2016-03-22 | 2018-05-22 | 浙江理工大学 | Azacyclopropane and N- vinyl acetamides or the synthetic method with N- methyl-Nvinylacetamide copolymers |
| EP3483192B1 (en) | 2016-07-08 | 2021-11-17 | Nippon Shokubai Co., Ltd. | N-vinyl lactam-based crosslinked polymer, cosmetic, absorbent agent for ink, and absorbent composite |
| CN106279525A (en) * | 2016-08-08 | 2017-01-04 | 东营华力石油技术股份有限公司 | Tertiary oil recovery surface-active polymer oil displacement agent and preparation method thereof |
| FR3061909B1 (en) * | 2017-01-19 | 2019-05-24 | S.P.C.M. Sa | PROCESS FOR ASSISTED OIL RECOVERY BY INJECTION OF A POLYMERIC AQUEOUS COMPOSITION CONTAINING MICROGELS |
| CN106832146B (en) * | 2017-01-26 | 2019-02-22 | 中国海洋石油集团有限公司 | One kind can viscosify profile control agent and preparation method thereof |
| WO2019024531A1 (en) * | 2017-07-31 | 2019-02-07 | 中国石油天然气股份有限公司 | Method for deep profile modification and flooding of low-permeability reservoir |
| CN107795296A (en) | 2017-07-31 | 2018-03-13 | 中国石油天然气股份有限公司 | A kind of method of low-permeability oil deposit deep profile correction |
| 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 |
| CN108929404B (en) * | 2018-07-20 | 2020-04-28 | 四川大学 | Preparation method of hydrophilic acrylamide-based crosslinked polymer microspheres |
| CN109320972A (en) * | 2018-09-27 | 2019-02-12 | 江南大学 | A kind of preparation method of porous polyethylene imines microballoon |
| CN114478897B (en) * | 2021-11-24 | 2024-02-23 | 四川轻化工大学 | Slow-expansion type pre-crosslinked gel particles and preparation method thereof |
| CN114736659B (en) * | 2022-03-16 | 2024-03-26 | 长江大学 | Preparation method of high-temperature high-density water-based drilling fluid filtrate reducer composition |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229509A (en) * | 2008-02-05 | 2008-07-30 | 南京大学 | Method of synthetizing closely graded polymer high efficiency liquid chromatography stuffing |
| CN101549270A (en) * | 2009-04-03 | 2009-10-07 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
| AU2009232000A1 (en) * | 2008-04-03 | 2009-10-08 | Baxter International Inc. | Hemostatic microspheres |
| CN101612543A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | Be used for the preparation of the polystyrene-divinylbenzene microspheres of blood purification |
| CN101759838A (en) * | 2009-12-30 | 2010-06-30 | 中国石油大学(华东) | Preparation method of profile control and oil displacement system of polyacrylamide nanometer microsphere with low interfacial tension |
| CN101773812A (en) * | 2010-01-12 | 2010-07-14 | 南京大学 | High-specific surface polymer microsphere resin with even particle size and preparation method thereof |
| CN101798372A (en) * | 2010-04-13 | 2010-08-11 | 苏州大学 | Polymer microsphere and preparation method thereof |
| CN101805423A (en) * | 2009-12-30 | 2010-08-18 | 中国石油大学(华东) | Method for preparing polyacrylamide nano microsphere system |
| CN101816909A (en) * | 2009-03-20 | 2010-09-01 | 兰州理工大学 | Preparation method of poly(phenylethylene-acrylic acid) magnetic polymer microsphere |
| EP2295480A1 (en) * | 2009-09-10 | 2011-03-16 | Occlugel | Implantable bio-resorbable polymer |
-
2011
- 2011-05-27 CN CN 201110140086 patent/CN102304200B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229509A (en) * | 2008-02-05 | 2008-07-30 | 南京大学 | Method of synthetizing closely graded polymer high efficiency liquid chromatography stuffing |
| AU2009232000A1 (en) * | 2008-04-03 | 2009-10-08 | Baxter International Inc. | Hemostatic microspheres |
| CN101612543A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | Be used for the preparation of the polystyrene-divinylbenzene microspheres of blood purification |
| CN101816909A (en) * | 2009-03-20 | 2010-09-01 | 兰州理工大学 | Preparation method of poly(phenylethylene-acrylic acid) magnetic polymer microsphere |
| CN101549270A (en) * | 2009-04-03 | 2009-10-07 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
| EP2295480A1 (en) * | 2009-09-10 | 2011-03-16 | Occlugel | Implantable bio-resorbable polymer |
| CN101759838A (en) * | 2009-12-30 | 2010-06-30 | 中国石油大学(华东) | Preparation method of profile control and oil displacement system of polyacrylamide nanometer microsphere with low interfacial tension |
| CN101805423A (en) * | 2009-12-30 | 2010-08-18 | 中国石油大学(华东) | Method for preparing polyacrylamide nano microsphere system |
| CN101773812A (en) * | 2010-01-12 | 2010-07-14 | 南京大学 | High-specific surface polymer microsphere resin with even particle size and preparation method thereof |
| CN101798372A (en) * | 2010-04-13 | 2010-08-11 | 苏州大学 | Polymer microsphere and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 双水相中制备交联泊洛沙姆亲水凝胶微球;徐晖等;《沈阳药科大学学报》;20010530(第03期);全文 * |
| 徐晖等.双水相中制备交联泊洛沙姆亲水凝胶微球.《沈阳药科大学学报》.2001,(第03期), |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021159A (en) * | 2018-06-08 | 2018-12-18 | 中国石油天然气股份有限公司 | A kind of oilwell water shutoff agent and its preparation method and application |
| CN109021159B (en) * | 2018-06-08 | 2020-03-10 | 中国石油天然气股份有限公司 | Oil well water shutoff agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102304200A (en) | 2012-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102304200B (en) | Crosslinked polymer microspheres and preparation method thereof | |
| CN102304201B (en) | Hydrophobic association crosslinked polymer coil and preparation method thereof | |
| CN102399345B (en) | Emulsion deep profile/displacement control agent and preparation method of emulsion deep profile/displacement control agent containing gel microspheres of core shell structure | |
| CN102286274A (en) | Cross-linked polymer microsphere-polymer composite in-depth profile control and oil displacement agent and use method thereof | |
| AU2018238041A1 (en) | Fracturing fluid comprising a (co)polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid and hydraulic fracturing method | |
| AU2009239528B2 (en) | Composition and method for recovering hydrocarbon fluids from a subterranean reservoir | |
| CN109679639B (en) | Thick oil viscosity reducer and preparation method and application thereof | |
| CN107476779B (en) | A method of oilwell water shutoff is carried out using activation oil pool microorganisms galactopoiesis agent | |
| CN108250344B (en) | Low-expansion-speed nanoscale water-absorbing microsphere and preparation method thereof | |
| CN113912763B (en) | Fluorescent polymer microsphere profile control and flooding agent and preparation method and application thereof | |
| CN108484828A (en) | A kind of cation emulsion and preparation method thereof of water-in-water type nano-silica-containing core-shell particles | |
| Chen | Polyacrylamide and its derivatives for oil recovery | |
| CN106467599A (en) | A kind of self-association type linked polymer coil and preparation method thereof | |
| CN112980412A (en) | Modifying and flooding agent suitable for high-temperature high-salinity heavy oil reservoir and preparation method thereof | |
| Yu et al. | Degradable cross-linked polymeric microsphere for enhanced oil recovery applications | |
| CN101240044B (en) | Method for preparing cross-linking polymer clew with bimodal distribution grain diameter | |
| CN106467598B (en) | A kind of cross linked amphoteric polymeric ball of string and preparation method thereof | |
| CN110628410A (en) | High-temperature-resistant cross-linked acid system for acid fracturing and preparation method thereof | |
| CN100422227C (en) | Production of cationic microsphere with crosslinked swelling function | |
| CN114479817B (en) | Polymer microsphere and polymer compound system and preparation method and application thereof | |
| US20180371137A1 (en) | Salt-resistant hydrophobically modified copolymer nanostructures as viscosity increasing agents for enhanced oil recovery | |
| CN107686533B (en) | Polymer with selective water plugging function and preparation method and application thereof | |
| CN106467733B (en) | Cross linked amphoteric polymeric microballoon-hydrophobic associated polymer profile control agent and its application | |
| El-Hoshoudy et al. | Application of acrylates in enhanced oil recovery | |
| CN110317599B (en) | Hypersalinity-resistant slickwater resistance reducing agent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC Research Institute Patentee after: China University of Petroleum (Beijing) Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC Research Center Patentee before: China University of Petroleum (Beijing) |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: China University of Petroleum (Beijing) Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Research Institute Patentee before: China National Offshore Oil Corporation Co-patentee before: China University of Petroleum (Beijing) |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210804 Address after: 100010 No. 25 North Main Street, Dongcheng District, Beijing, Chaoyangmen Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC RESEARCH INSTITUTE Co.,Ltd. Address before: 100010 No. 25 North Main Street, Dongcheng District, Beijing, Chaoyangmen Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC RESEARCH INSTITUTE Co.,Ltd. Patentee before: China University of Petroleum (Beijing) |