CN102304200A - Crosslinked polymer microspheres and preparation method thereof - Google Patents
Crosslinked polymer microspheres and preparation method thereof Download PDFInfo
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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 gets into 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, improves the volumetric conformance efficiency that injects liquid and improves two types of displacement efficiencies in the swept volume and can be divided into 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 through deep profile controlling; 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 the chemical flooding displacing fluid and the oil recovery factor in follow-up water drive stage.This wherein; With cross-linked polymer flow-gel, cross-linked polymer solution, cross-linked polymer microsphere is that the deep profile controlling technology of representative is to have superiority economically; Effect is obvious; Meet long-term injection, be beneficial to the technology of environmental protection; On profound level more,, adjustment, the nonuniformity of improving oil reservoir there is very important meaning to the research and the improvement of this method.
At present; Preparation is used for the method for 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 interior multiple monomeric copolymerization; 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 flow changed course; The real nonuniformity that realizes adjustment and improve 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 public reported 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 of Chinese patent ZL 200710063645.X public reported 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, ore deposit factory also finds in using; 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 said 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 said aqueous dispersions is respectively 1.0%～10.0%, 10.0%～40.0% and 0.001%～3.0%; The quality percentage composition that said polymerization single polymerization monomer accounts for said aqueous dispersions is 1.0%～40.0%.
Among the above-mentioned preparation method, the quality percentage composition of macromolecule dispersing agent described in the said 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 said aqueous dispersions; The quality percentage composition of cross-linking monomer specifically can be 0.45% or 0.46% in the said aqueous dispersions; The quality percentage composition that said polymerization single polymerization monomer accounts for said aqueous dispersions specifically can be 5.68% or 5.7%.
Among the above-mentioned preparation method, said 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: monomeric corresponding salt 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, said 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, said cross-linking monomer can be the polyfunctional monomer that contains two or more pairs key in the molecular structure, and distance can be regulated through 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 '; 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; Said macromolecule dispersing agent can be selected commercially available macromolecule dispersing agent; For example adopt commercially available: relative molecular mass is homopolymer or multipolymer of the polyvinyl alcohol of 4000-20000, polyvinylamine that relative molecular mass is 5000-30000, vinyl pyrrolidone etc., wherein adopts the homopolymer of vinyl pyrrolidone or multipolymer effect better; Or through the dilute solution polymerization of the said polymerization single polymerization monomer of ionic acquisition accordingly in the molecular structure of said 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, said 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 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, said 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 said dispersion liquid.
Among the above-mentioned preparation method; Said oxidative initiator can be ammonium persulphate; Said oxidative initiator can separately or be carried out oxidation-reduction reaction with reducing gas and formed free radical; Initiated polymerization; Said reducing gas is preferably sulfurous gas; The quality percentage composition that the add-on of said oxidative initiator can account for said aqueous dispersions is 0.0001%-0.0005%, as 0.00025% or 0.0003%; Said 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; Said water-soluble thermal decomposition initiating is used for the said polymerization single polymerization monomer of polymerization later stage initiation residue; Reduce polymerization single polymerization monomer content remaining in the aqueous dispersions of said cross-linked polymer microsphere; The quality percentage composition that the add-on of said water-soluble thermal decomposition initiating can account for said aqueous dispersions is 0.0001%-0.0008%, as 0.0005% or 0.00075%; Said sequestrant is a disodium ethylene diamine tetraacetate; Be used for slowing down, eliminating of the influence of polymer monomer heavy metal ion to polyreaction; The quality percentage composition that the add-on of said sequestrant can account for said aqueous dispersions is 0.0001%-0.0005%, as 0.0005%; Said pH value conditioning agent is sodium hydroxide, yellow soda ash or sodium hydrogencarbonate, is used to regulate the pH value of aqueous dispersions, guarantees the acid-basicity that aqueous dispersions is suitable; Said 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 said solubility promoter can account for said aqueous dispersions is 0.001%-0.005%, as 0.001%.
Among the above-mentioned preparation method, said method also comprise with said cross-linked polymer microsphere precipitate, refining and exsiccant step.
Among the above-mentioned preparation method, the temperature of said polyreaction can be 5 ℃-85 ℃, as 35 ℃ or 50 ℃; The time of said 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, like 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 said cross-linked polymer microsphere or said 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 through water injection well, reach the purpose of improving the oil reservoir nonuniformity, improving the waterflooding reservoir oil recovery factor.When cross-linked polymer microsphere according to the 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 come concrete its actual functional quality mark and injection mode of confirming through early stage laboratory experiment, numerical simulation.
In the profile control of oil reservoir is handled; Through 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 flow 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 like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
Adopting the cross-linked polymer microsphere aqueous solution of confirming volume is 2.0 μ m to perm-plug method
2The shutoff 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 use 35% sodium hydrate regulator solution pH value to be 7.5-8.5; 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 initiation temperature; At first in above-mentioned saline aqueous dispersions, feed the inert gas high pure nitrogen and drive oxygen; Oxygen content in the reduction system (≤0.3 μ g/g) is convenient to polymerisation and is initiated; Add 0.30 milligram of ammonium persulfate (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 reducibility gas sulfur dioxide and aqueous phase ammonium persulfate then; Polymerisation 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 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 processed the cross-linked polymer microsphere powder.
Massfraction be the above-mentioned cross-linked polymer microsphere of 400mg/kg the Simulated Water matured obtained the linked polymer coil aqueous solution in 96 hours in SZ36-1 oil field, 60 ℃ of Bohai Sea, be 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 use 35% sodium hydrate regulator solution pH value to be 7.5-8.5.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 initiation temperature; At first in above-mentioned saline aqueous dispersions, feed the inert gas high pure nitrogen and drive oxygen; Oxygen content in the reduction system (≤0.3 μ g/g) is convenient to polymerisation and is initiated; Add 0.30 milligram of ammonium persulfate (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 reducibility gas sulfur dioxide and aqueous phase ammonium persulfate then; Polymerisation was carried out 4 hours; Temperature is risen to 50 ℃ again; Continued 6 hours; Obtain large scale cross-linked polymer microsphere aqueous dispersions; Its viscosity is 640mPa.s in the time of 25 ℃, its size 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 processed large size cross-linked polymer microsphere powder.
Massfraction be the above-mentioned large size cross-linked polymer microsphere of 400mg/kg the Simulated Water matured obtained the linked polymer coil aqueous solution in 96 hours in SZ36-1 oil field, 60 ℃ of Bohai Sea, be 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
According to preparing cross-linked polymer microsphere aqueous solution powder with embodiment 1 identical method.
Massfraction be the cross-linked polymer microsphere of above-mentioned preparation of 400mg/kg the Simulated Water matured obtained the linked polymer coil aqueous solution in 96 hours in SZ36-1 oil field, 60 ℃ of Bohai Sea, be 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 using 35% sodium hydrate regulator solution pH value to be 7.5-8.5, 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 initiation temperature; At first in above-mentioned saline aqueous dispersions, feed the inert gas high pure nitrogen and drive oxygen; Oxygen content in the reduction system (≤0.3 μ g/g) is convenient to polymerisation and is initiated; Add 0.25 milligram of ammonium persulfate (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 reducibility gas sulfur dioxide and aqueous phase ammonium persulfate then; Polymerisation was carried out 4 hours; Temperature is risen to 50 ℃ again; Continued 6 hours; Obtain large scale cross-linked polymer microsphere aqueous dispersions; Its viscosity is 940mPa.s in the time of 25 ℃, its size 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 processed large size cross-linked polymer microsphere powder.
Massfraction be the above-mentioned cross-linked polymer microsphere of 400mg/kg the Simulated Water matured obtained the linked polymer coil aqueous solution in 96 hours in SZ36-1 oil field, 60 ℃ of Bohai Sea, be 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
Prepare according to embodiment 5 among the preparation method of Chinese patent ZL 200710063645.X public reported and to contain the w/o type dispersion liquid that particle diameter is the linked polymer coil of bimodal distribution;
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 processed the linked polymer coil powder that particle diameter is bimodal distribution.
Massfraction be the linked polymer coil of 400mg/kg the Simulated Water matured obtained the linked polymer coil aqueous solution in 96 hours in SZ36-1 oil field, 60 ℃ of Bohai Sea, be 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
Control Example 1 and 3 can be found out; The cross-linked polymer microsphere of the present invention's preparation is different to the shutoff profile control effect 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.
Control Example 1,2 and 4 can find out that the raising recovery ratio ability of the cross-linked polymer microsphere of the present invention's preparation can be regulated through adjusting molecular structure, preparation method.
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 characteristic, recovery percent of reserves.
On the other hand; Relatively Comparative Examples 1 and four specific embodiments can be found out; 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 (10)
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 said cross-linked polymer microsphere in the aqueous dispersions that is dissolved with macromolecule dispersing agent, inorganic salt and cross-linking monomer.
2. preparation method according to claim 1 is characterized in that: the quality percentage composition of macromolecule dispersing agent, inorganic salt and cross-linking monomer described in the said aqueous dispersions is respectively 1.0%～10.0%, 10.0%～40.0% and 0.001%～3.0%; The quality percentage composition that said polymerization single polymerization monomer accounts for said aqueous dispersions is 1.0%～40.0%.
3. preparation method according to claim 1 and 2; It is characterized in that: said polymerization single polymerization monomer is an acrylamide; Methacrylamide; The N-vinyl formamide; The N-vinyl acetamide; The N-vinyl pyrrolidone; N,N-DMAA; Vinyl cyanide; Diacetone acrylamide; (methyl) 2-hydroxyethyl acrylate acrylamide; Vinylcarbinol; (methyl) acrylate; Itaconicacid salt; Maleate; 2-acrylamide-2-methyl propane sulfonic acid salt; Vinylsulfonate; (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.
4. according to arbitrary described preparation method among the claim 1-3, it is characterized in that: said inorganic salt are at least a in ammonium sulfate, sodium sulfate, vitriolate of tartar, ammonium chloride, Repone K and the sodium-chlor.
5. according to arbitrary described preparation method among the claim 1-4; It is characterized in that: said cross-linking monomer is 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-, N; N '-two couple vinyl benzyl-N; N, N ', the own dichloride amine of N '-tetramethyl-, three vinylformic acid-(propyl group) trimethyl or pentaerythritol triallyl ether.
6. according to arbitrary described preparation method among the claim 1-5, it is characterized in that: said macromolecule dispersing agent is polyvinyl alcohol, polyvinylamine, vinyl pyrrolidone homopolymer, vinylpyrrolidone copolymer or 2-acrylamide-2-methyl propane sulfonic acid sodium homopolymer; Also comprise in oxidative initiator, water-soluble thermal decomposition initiating, sequestrant, pH value conditioning agent and the solubility promoter at least a in the said dispersion liquid.
7. preparation method according to claim 6 is characterized in that: said oxidative initiator is an ammonium persulphate; Said 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; Said sequestrant is a disodium ethylene diamine tetraacetate; Said pH value conditioning agent is sodium hydroxide, yellow soda ash or sodium hydrogencarbonate; Said solubility promoter is a urea.
8. according to arbitrary described preparation method among the claim 1-7, it is characterized in that: said method also comprise with said cross-linked polymer microsphere precipitate, refining and exsiccant step.
9. the cross-linked polymer microsphere of arbitrary said method preparation among the claim 1-8; The particle diameter of said cross-linked polymer microsphere is 3 μ m-50 μ m.
10. the described cross-linked polymer microsphere of claim 9 is as the application of oil-displacing agent.
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408703A (en) * | 2013-08-06 | 2013-11-27 | 西安石油大学 | Liquid polymeric microspheres and synthetic method thereof |
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