CN103739778A - Core-shell polyacrylamide microsphere profile controlling oil displacement agent and preparation method thereof - Google Patents
Core-shell polyacrylamide microsphere profile controlling oil displacement agent and preparation method thereof Download PDFInfo
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- CN103739778A CN103739778A CN201410009263.9A CN201410009263A CN103739778A CN 103739778 A CN103739778 A CN 103739778A CN 201410009263 A CN201410009263 A CN 201410009263A CN 103739778 A CN103739778 A CN 103739778A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 39
- 239000004005 microsphere Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006073 displacement reaction Methods 0.000 title abstract description 7
- 239000011258 core-shell material Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000000178 monomer Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 13
- 125000002091 cationic group Chemical group 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 66
- 239000003921 oil Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 230000002459 sustained effect Effects 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- -1 acrylyl Chemical group 0.000 claims description 7
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical class CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical group C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 230000009514 concussion Effects 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- IMOLAGKJZFODRK-UHFFFAOYSA-N 2-phenylprop-2-enamide Chemical compound NC(=O)C(=C)C1=CC=CC=C1 IMOLAGKJZFODRK-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000012674 dispersion polymerization Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 238000009434 installation Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000011435 rock Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000505 pernicious effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a core-shell polyacrylamide microsphere profile controlling oil displacement agent and a preparation method thereof. The method comprises the following steps: fully stirring and dissolving acrylamide, cationic monomer, a crosslinking agent and an initiator to synthetize a core part by adopting a dispersion polymerization method; fractionally adding a mixed solution of the acrylamide, anionic monomer, third monomer, the crosslinking agent and the initiator into a reaction device, controlling reaction conditions to be invariant, and reacting on the surface of the core to generate a shell part, thereby obtaining the core-shell polyacrylamide microsphere profile controlling oil displacement agent taking the cationic polyacrylamide as the core and taking the anionic polyacrylamide polymerized on the surface of the core as the shell, wherein the particle size range of the microsphere profile controlling oil displacement agent is from 1micrometer to100 micrometers. The microsphere profile controlling oil displacement agent has the advantages that the microsphere has an interpenetrating polymer network system and is capable of forming a viscoelastic body after absorbing water and forming a gel body after a certain time, so that the oil displacement agent is long in plugging time and little in leakage and is capable of bearing the pressure of more than 5MPa.
Description
Technical field
The present invention relates to a kind of nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent and preparation method.
Background technology
Because domestic most oil producing region formation lithology changes, hole, crack, solution cavity developmental state difference, the reason complexity of leakage, leakage type difference, restraining factors are more, and the specific aim of leakage stopping technology is stronger, be difficult to so far carry out leakproof and leak stopping by a general pattern.Particularly bore fissured formation leakage problem even more serious.According to incompletely statistics, the reserves of domestic Fractured bad ground account for 50% of total reserves, but grow because of formation fracture, hole, and leakage problem is difficult to solve, the loss causing and serious.Therefore, the pernicious leakage problem of Fractured bad ground has become the emphasis that drilling well circle is paid close attention to.
Fractured reservoir leakage is to affect drilling engineering safety, efficiency, the cost important factor that even hydrocarbon zone is found and protected.Fissured formation mesoporosity, crack, solution cavity intersection exist, also can Individual existence.Particularly bore and meet large-scale solution cavity or crack while there is pernicious leakage, leak stopping difficulty, conventional patching materials plugging effect is poor.In order to ensure safety drilling, improve drilling efficiency, reduce construction cost, and improve reservoir protection effect, the efficient patching materials that research tackles fissured formation leakage is very necessary.
Profile control and water plugging technology is that oil field is improved waterflooding development effect, realized the effective means that oil reservoir increases production always.For profile control and water plugging, deep transfer drive technology is a kind of technology of carrying out limited tertiary oil recovery when bringing into play to greatest extent secondary oil recovery effect.It is high that the easy precipitation of traditional Inorganic Profile Modification can not enter earth formation deep shutoff, the crosslinked poor controllability of movable weak gel, cost, and Swellable particulate gel particle is large, has the contradiction of injecting between the degree of depth and plugging strength, loses efficacy very fast; The novel deep of the one transfer drive technology that polymer microballoon Novel technique of in-depth profile control grows up in order to solve above contradiction just.
Cross-linked polymer microsphere is the broad-spectrum absorbent resin of a class, its chemical constitution is mainly take polyacrylamide material as main, thereby the acylamide polymer that utilizes microsphere surface can be swelling under specific environment, gelation in gap or pore throat place form effective shutoff, improve oil extraction in oil field rate.Take polyacrylamide as main polymer microballoon, in the advantage of profile adjustment and oil displacement field, oil field application, be that construction technology is simple and convenient, can directly by waterflood-transmission line, inject, abandoned traditional profile control pump injection mode; Quality control aspect can realize automatization, the stdn of dosing process, has avoided the artificial dosing link in scene complicated in traditional profile control technology, has stopped the impact of human factor on quality control; Sealing characteristics aspect, has good endurance of cutting, and underground self-crosslinking, repeat crosslinking feature.
Nucleocapsid structure polymer microballoon provided by the invention, take micron-sized cationic-type polyacrylamide as kernel, by chemical bond, anion-polyacrylamide is wrapped in to core surface outward and form shell, under linking agent effect, between cationic-type polyacrylamide kernel, anion-polyacrylamide shell and kernel and shell, form and pass mutually network structure.The nucleocapsid structure polymer microballoon providing has good water-absorbent and elasticity, can in regular hour and temperature range, water-swelling be cross-linked to form polymer gel, can keep for a long time good plugging strength.The well-regulated spherical morphology of prepared microballoon tool, particle size range is controlled at micron order and particle diameter, is applicable to different size ground layer gap and hole and shouts big or small reservoir condition.
Summary of the invention
The object of the invention is to utilize dispersion polymerization technology to prepare micron order nucleocapsid structure polyacrylamide microsphere, there is outstanding water-swelling property, kept again higher intensity and temperature resistant antisalt simultaneously, and well-regulated spherical morphology and uniform size distribution.
Technical scheme of the present invention is as follows:
A kind of nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent of the present invention, take cationic-type polyacrylamide as kernel, in core surface polymerization, obtain anion-polyacrylamide shell, the particle size range of nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent is 1～100 μ m.
Nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent preparation method of the present invention, concrete steps are as follows:
(1) be incorporated as the acrylamide of core total solution weight 1～40%, 1～10% cationic monomer, 0.1～15% stablizer; Being incorporated as the linking agent of acrylamide and cationic monomer gross weight 0.1～8%, is the initiator of polymerization single polymerization monomer gross weight 0.01～5% again, and concussion, to dissolving completely, obtains solution A;
(2) be incorporated as the acrylamide of shell total solution weight 1～40%, 1～5% anionic monomer, 0.1～15% stablizer, 0.1～3% the 3rd monomer; Be incorporated as the linking agent of acrylamide, anionic monomer and the 3rd total monomer weight 0.1～8%, concussion, to dissolving completely, obtains solution B again;
(3) by for the initiator of step (2) mesochite solution polymerization total monomer weight 0.01～5% joins in solvent, shake to dissolving completely, obtain solution C;
(4) A solution 1/3 is added in reaction vessel, in solution, pass into N
2emptying 0.5h, controlling temperature is 40～80 ℃, stirring velocity is 200～500r/min; Then isothermal reaction 3h, obtains prepolymer solution; Control above-mentioned reaction conditions constant, residue A solution is joined in reaction system to sustained reaction 3h; Obtain microballoon core mixed solution;
(5) reaction conditions of control step 4 is constant, solution C is added to the microballoon core mixed solution obtaining, N
2environment continues absorption 1h; Then solution B is slowly added drop-wise in reaction system, controls reaction conditions constant sustained reaction 3h, finally cooling, filter, the dry nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent that obtains.
Described cationic monomer is selected from acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, N, N'-dimethylamino ethyl acrylic acid hydrochloride, beta-amido ethylacrylic acid hydrochloride or N, the one in N'-dimethylamino ethyl ethyl propenoate.
Described anionic polyacrylamide shell is selected from as follows:
(1) anionic monomer is selected from acrylate, sulfonated α-olefin, 2-acrylamide-2-methylpro panesulfonic acid salt, β-allylsulfonate, Sodium styrene sulfonate, the one in 2-acrylamide-2-methylpro panesulfonic acid;
(2) the 3rd monomers are selected from vinylbenzene, vinylformic acid, lauryl methacrylate(LMA), N-(4-ethyl) Phenyl Acrylamide, methyl methacrylate, the one in 4-vinylpridine;
Selected solvent can be good at dissolving required each monomer, comprises acrylamide, ion monomer I, ion monomer II, the 3rd monomer, linking agent, initiator and stablizer, but does not dissolve their copolymerization product simultaneously.
Described solvent is: methyl alcohol, ethanol, propyl alcohol, butanols, acetone, benzene, toluene, hexanaphthene, kerosene, diesel oil, white oil, methylene dichloride, chloroform or their mixed solvent, or the mixed solution of above organic solvent and water.
Described initiator is selected from the one in tetrazo initiator, organo-peroxide or redox class initiator.
Described stablizer is selected from the one in polyoxyethylene glycol, hydroxypropylcellulose, castor oil polyoxyethylene ether, polyvinylpyrrolidone, polyvinyl alcohol or Sodium dodecylbenzene sulfonate.
Described linking agent is selected from Vinylstyrene, vulcabond, N, N'-methylene-bisacrylamide, pentaerythritol triacrylate, the one in dimethyl diallyl ammonium chloride or polyethyleneglycol diacrylate.
The solution composition of core part is: be the acrylamide of core part total solution weight 1～40%, 1～10% cationic monomer, 0.1～15% stablizer, is the linking agent of acrylamide and cationic monomer gross weight 0.1～8%, for the initiator of each total monomer weight 0.01～5%, all the other are solvent.
The solution composition of shell part is: be the acrylamide of shell part total solution weight 1～40%, 1～5% anionic monomer, 0.1～3% the 3rd monomer, 0.1～15% stablizer, for the linking agent of acrylamide, anionic monomer and the 3rd total monomer weight 0.1～8%, for the initiator of each total monomer weight 0.01～5%, all the other are solvent.
Utilize this synthetic method, by changing reaction process condition, prepare the nucleocapsid structure polyacrylamide microsphere that is applicable to Different Strata pore throat diameter.
In the preparation process of nucleocapsid structure polymer microballoon provided by the present invention, the organic solvent in reaction system can high-level efficiency recycling, realizes the green circulatory of production technique.
The present invention, by abundant to acrylamide, cationic monomer, linking agent and initiator stirring and dissolving, adopts the synthetic kernel portion of dispersion copolymerization method; Then, the mixing solutions gradation of acrylamide, anionic monomer, the 3rd monomer, linking agent and initiator is added in reaction unit, control reaction conditions is constant, in core surface reaction, generate shell part, obtain take cationic-type polyacrylamide as kernel, in core surface polymerization, obtain the nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent of anion-polyacrylamide shell; Nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent of the present invention has the following advantages:
(l) microballoon has interpenetrating network system, forms viscoelastic body after water suction, through certain hour, forms gelinite, and the shutoff time is long, and wastage is few, as long as selected appropriate particle size, dosage and injection pressure, all can within the short time, see effect;
(2) microballoon has nucleocapsid structure, and injection efficiency is good, injection technology is simple;
(2) pressure-bearing is effective, at least bears pressure more than 5MPa;
(3) microspherulite diameter is controlled, when shutoff drop ply, can select as required the particle diameter of microballoon.
Embodiment
Embodiment 1
Microballoon preparation experiment
Take successively the acrylamide of 1g (1%), the N of 3g (3%), N'-dimethylamino ethyl acrylic acid hydrochloride, the Vinylstyrene of 0.32g (8%), the Diisopropyl azodicarboxylate of 0.043g (1%), the polyoxyethylene glycol of 0.1g (0.1%), adds ethanol and butanols mixed solvent to 100g, wherein ethanol, with butanols than being 4:6, is stirred well to completely and dissolves; Add in reaction vessel 1/3 of solution, in solution, pass into N
2emptying 0.5h, controlling temperature is 40 ℃, stirring velocity is 300r/min; Then isothermal reaction 3h; Obtain prepolymer solution; Control above-mentioned reaction conditions constant, surplus solution is evenly added drop-wise in reaction system to sustained reaction 3h; White solid is on the increase, and obtains microballoon core mixed solution;
Take the Diisopropyl azodicarboxylate of 0.6g (1%), add ethanol and butanols mixed solvent to 10g, wherein ethanol, with butanols than being 4:6, is stirred well to completely and dissolves, and joins in microballoon core mixed solution, controls reaction conditions constant, isothermal reaction 1h; Take successively the acrylamide of 24g (40%), the 2-acrylamide-2-methylpro panesulfonic acid of 0.6g (1%), the vinylbenzene of 1.8g (3%), the Vinylstyrene of 4.8g (8%), the polyoxyethylene glycol of 0.6g (0.1%), adds ethanol and butanols mixed solvent to 50g, be stirred well to completely and dissolve, the above-mentioned solution preparing is evenly added drop-wise in above-mentioned solution, controls 40 ℃, 300r/min, N
2the lower sustained reaction 3h of protection, obtains white opacity system;
Finally cooling, filter, washing, gained solid drying obtains white powder.Through characterizing, measure, powder particle particle diameter is 63 μ m left and right, and wherein, microballoon size of cores is 41 μ m left and right, and water absorbent rate is 64 times.
No. 1 rock sample plugging agent evaluation experiment of microballoon shutoff
Accurately take the nucleocapsid structure polyacrylamide microsphere 0.5g preparing in embodiment 1, add oil field stratum water 99.5g, after fully disperseing, obtain 5 ‰ microballoon dispersion liquid, constant temperature 5～24 hours under 60 ℃ of conditions, obtains uniform microballoon dispersion system.Under 60 ℃ of constant temperatures, first oil field stratum water is injected to No. 1 rock sample plugging agent evaluation experimental installation of microballoon shutoff, treat that raw data acquisition is complete, the microballoon dispersion liquid configuring is injected to shutoff core plugging agent evaluation experimental installation, image data shows, injection pressure increases 5.64MPa, permeability plugging 14.72md during than water filling.
Embodiment 2
Microballoon preparation experiment
Take successively the acrylamide of 7g (10%), the dimethyl diallyl ammonium chloride of 0.7g (1%), the N of 0.154g (2%), N'-methylene-bisacrylamide, the benzoyl peroxide of 0.235g (3%), the castor oil polyoxyethylene ether of 0.7g (1%), adds hexanaphthene to 70g, is stirred well to completely and dissolves; Add in reaction vessel 1/3 of solution, in solution, pass into N
2emptying 0.5h, controlling temperature is 60 ℃, stirring velocity is 200r/min; Then isothermal reaction 3h; Obtain prepolymer solution; Control above-mentioned reaction conditions constant, surplus solution is evenly added drop-wise in reaction system to sustained reaction 3h; White solid is on the increase, and obtains microballoon core mixed solution;
Take the benzoyl peroxide of 0.436g (3%), add hexanaphthene to 5g, be stirred well to completely and dissolve and join in microballoon core mixed solution, control reaction conditions constant, isothermal reaction 1h; Take successively the acrylamide of 12g (30%), the acrylate of 0.6g (1.5%), the lauryl methacrylate(LMA) of 1g (2.5%), the N of 0.952g (7%), N'-methylene-bisacrylamide, the castor oil polyoxyethylene ether of 0.6g (1%), add hexanaphthene to 35g, be stirred well to completely and dissolve, the above-mentioned solution preparing is evenly added drop-wise in above-mentioned solution, control 40 ℃, 300r/min, N
2the lower sustained reaction 3h of protection, obtains white opacity system;
Finally cooling, filter, washing, gained solid drying obtains white powder.Through characterizing, measure, powder particle particle diameter is 86 μ m left and right, and wherein, microballoon size of cores is 54 μ m left and right, and water absorbent rate is 68 times.
No. 2 rock sample plugging agent evaluation experiments of microballoon shutoff
Accurately take the nucleocapsid structure polyacrylamide microsphere 0.5g preparing in embodiment 2, add oil field stratum water 99.5g, after fully disperseing, obtain 5 ‰ microballoon dispersion liquid, constant temperature 5～24 hours under 60 ℃ of conditions, obtains uniform microballoon dispersion system.Under 60 ℃ of constant temperatures, first oil field stratum water is injected to No. 2 rock sample plugging agent evaluation experimental installations of microballoon shutoff, treat that raw data acquisition is complete, the microballoon dispersion liquid configuring is injected to shutoff core plugging agent evaluation experimental installation, image data shows, injection pressure increases 6.17MPa, permeability plugging 17.53md during than water filling.
Embodiment 3
Microballoon preparation experiment
Take successively the acrylamide of 20g (40%), the N of 5g (10%), N'-dimethylamino ethyl ethyl propenoate, the polyethyleneglycol diacrylate of 0.75g (3%), the benzoyl peroxide of 0.003g (0.01%), the polyvinyl alcohol of 2g (4%), adds toluene to 50g, is stirred well to completely and dissolves; Add in reaction vessel 1/3 of solution, in solution, pass into N
2emptying 0.5h, controlling temperature is 80 ℃, stirring velocity is 200r/min; Then isothermal reaction 3h; Obtain prepolymer solution; Control above-mentioned reaction conditions constant, surplus solution is evenly added drop-wise in reaction system to sustained reaction 3h; White solid is on the increase, and obtains microballoon core mixed solution;
Take the benzoyl peroxide of 0.003g (0.01%), add toluene to 10g, be stirred well to completely and dissolve and join in microballoon core mixed solution, control reaction conditions constant, isothermal reaction 1h; Take successively the acrylamide of 28g (35%), the sulfonated α-olefin of 4g (5%), the 4-vinylpridine of 1.2g (1.5%), the polyethyleneglycol diacrylate of 0.996g (3%), the polyvinyl alcohol of 0.6g (4%), adds toluene to 70g, be stirred well to completely and dissolve, the above-mentioned solution preparing is evenly added drop-wise in above-mentioned solution, controls 80 ℃, 300r/min, N
2the lower sustained reaction 3h of protection, obtains white opacity system;
Finally cooling, filter, washing, gained solid drying obtains white powder.Through characterizing, measure, powder particle particle diameter is 24 μ m left and right, and wherein, microballoon size of cores is 18 μ m left and right, and water absorbent rate is 56 times.
No. 3 rock sample plugging agent evaluation experiments of microballoon shutoff
Accurately take the nucleocapsid structure polyacrylamide microsphere 0.5g preparing in embodiment 3, add oil field stratum water 99.5g, after fully disperseing, obtain 5 ‰ microballoon dispersion liquid, constant temperature 5～24 hours under 60 ℃ of conditions, obtains uniform microballoon dispersion system.Under 60 ℃ of constant temperatures, first oil field stratum water is injected to No. 3 rock sample plugging agent evaluation experimental installations of microballoon shutoff, treat that raw data acquisition is complete, the microballoon dispersion liquid configuring is injected to shutoff core plugging agent evaluation experimental installation, image data shows, injection pressure increases 5.83MPa, permeability plugging 21.04md during than water filling.
Embodiment 4
Microballoon preparation experiment
Take successively the acrylamide of 37.5g (25%), the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 10.5g (7%), the vulcabond of 0.048g (0.1%), the Diisopropyl azodicarboxylate of 2.402g (5%), the Sodium dodecylbenzene sulfonate of 0.9g (0.6%), add benzene to 50g, be stirred well to completely and dissolve; Add in reaction vessel 1/3 of solution, in solution, pass into N
2emptying 0.5h, controlling temperature is 50 ℃, stirring velocity is 500r/min; Then isothermal reaction 3h; Obtain prepolymer solution; Control above-mentioned reaction conditions constant, surplus solution is evenly added drop-wise in reaction system to sustained reaction 3h; White solid is on the increase, and obtains microballoon core mixed solution;
Take the Diisopropyl azodicarboxylate of 0.125g (5%), add benzene to 7g, be stirred well to completely and dissolve and join in microballoon core mixed solution, control reaction conditions constant, isothermal reaction 1h; Take successively the acrylamide of 0.5g (1%), β-allylsulfonate of 1.5g (3%), N-(4-ethyl) Phenyl Acrylamide of 0.5g (1%), the vulcabond of 0.003g (0.1%), the Sodium dodecylbenzene sulfonate of 0.3g (0.6%), adds benzene to 43g, be stirred well to completely and dissolve, the above-mentioned solution preparing is evenly added drop-wise in above-mentioned solution, controls 80 ℃, 300r/min, N
2the lower sustained reaction 3h of protection, obtains white opacity system;
Finally cooling, filter, washing, gained solid drying obtains white powder.Through characterizing, measure, powder particle particle diameter is 40 μ m left and right, and wherein, microballoon size of cores is 38 μ m left and right, and water absorbent rate is 72 times.
No. 4 rock sample plugging agent evaluation experiments of microballoon shutoff
Accurately take the nucleocapsid structure polyacrylamide microsphere 0.5g preparing in embodiment 4, add oil field stratum water 99.5g, after fully disperseing, obtain 5 ‰ microballoon dispersion liquid, constant temperature 5～24 hours under 60 ℃ of conditions, obtains uniform microballoon dispersion system.Under 60 ℃ of constant temperatures, first oil field stratum water is injected to No. 4 rock sample plugging agent evaluation experimental installations of microballoon shutoff, treat that raw data acquisition is complete, the microballoon dispersion liquid configuring is injected to shutoff core plugging agent evaluation experimental installation, image data shows, injection pressure increases 6.38MPa, permeability plugging 15.71md during than water filling.
Embodiment 5
Microballoon preparation experiment
Take successively the acrylamide of 6g (20%), the acrylyl oxy-ethyl-trimethyl salmiac of 1.5g (5%), the dimethyl diallyl ammonium chloride of 0.45g (6%), the Potassium Persulphate of 0.038g (0.5%), the polyvinylpyrrolidone of 4.5g (15%), add ethanol, water mixed liquid to 30g, wherein alcohol water, than being 7:3, is stirred well to completely and dissolves; Add in reaction vessel 1/3 of solution, in solution, pass into N
2emptying 0.5h, controlling temperature is 65 ℃, stirring velocity is 400r/min; Then isothermal reaction 3h; Obtain prepolymer solution; Control above-mentioned reaction conditions constant, surplus solution is evenly added drop-wise in reaction system to sustained reaction 3h; White solid is on the increase, and obtains microballoon core mixed solution;
Take the Potassium Persulphate of 0.7g (0.5%), add ethanol, water mixed liquid to 25g, wherein alcohol water, than being 7:3, is stirred well to completely and dissolves, and joins in microballoon core mixed solution, controls reaction conditions constant, isothermal reaction 1h; Take successively the acrylamide of 14g (10%), the 2-acrylamide-2-methylpro panesulfonic acid salt of 5.6g (4%), the vinylformic acid of 0.14g (0.1%), the dimethyl diallyl ammonium chloride of 1.184g (6%), the polyvinylpyrrolidone of 4.2g (3%), add ethanol, water mixed liquid to 115g, wherein alcohol water is than being 7:3, be stirred well to completely and dissolve, the above-mentioned solution preparing is evenly added drop-wise in above-mentioned solution, control 65 ℃, 400r/min, N
2the lower sustained reaction 3h of protection, obtains white opacity system;
Finally cooling, filter, washing, gained solid drying obtains white powder.Through characterizing, measure, powder particle particle diameter is 15 μ m left and right, and wherein, microballoon size of cores is 10 μ m left and right, and water absorbent rate is 61 times.
No. 5 rock sample plugging agent evaluation experiments of microballoon shutoff
Accurately take the nucleocapsid structure polyacrylamide microsphere 0.5g preparing in embodiment 5, add oil field stratum water 99.5g, after fully disperseing, obtain 5 ‰ microballoon dispersion liquid, constant temperature 5～24 hours under 60 ℃ of conditions, obtains uniform microballoon dispersion system.Under 60 ℃ of constant temperatures, first oil field stratum water is injected to No. 5 rock sample plugging agent evaluation experimental installations of microballoon shutoff, treat that raw data acquisition is complete, the microballoon dispersion liquid configuring is injected to shutoff core plugging agent evaluation experimental installation, image data shows, injection pressure increases 5.38MPa, permeability plugging 18.79md during than water filling.
Embodiment 6
Microballoon preparation experiment
Take successively the acrylamide of 42g (30%), the beta-amido ethylacrylic acid hydrochloride of 10.5g (7.5%), the pentaerythritol triacrylate of 1.575g (3%), the Diisopropyl azodicarboxylate of 1.352g (2.5%), the hydroxypropylcellulose of 2.8g (2%), add tetracol phenixin to 140g, be stirred well to completely and dissolve; Add in reaction vessel 1/3 of solution, in solution, pass into N
2emptying 0.5h, controlling temperature is 50 ℃, stirring velocity is 300r/min; Then isothermal reaction 3h; Obtain prepolymer solution; Control above-mentioned reaction conditions constant, surplus solution is evenly added drop-wise in reaction system to sustained reaction 3h; White solid is on the increase, and obtains microballoon core mixed solution;
Take the Diisopropyl azodicarboxylate of 0.209g (2.5%), add tetracol phenixin to 7g, be stirred well to completely and dissolve, join in microballoon core mixed solution, control reaction conditions constant, isothermal reaction 1h; Take successively the acrylamide of 6g (10%), the Sodium styrene sulfonate of 1.2g (2%), the methyl methacrylate of 0.9g (1.5%), the pentaerythritol triacrylate of 0.243g (3%), the hydroxypropylcellulose of 9g (15%), add tetracol phenixin to 53g, be stirred well to completely and dissolve, the above-mentioned solution preparing is evenly added drop-wise in above-mentioned solution, control, 50 ℃, 300r/min, N
2the lower sustained reaction 3h of protection, obtains white opacity system;
Finally cooling, filter, washing, gained solid drying obtains white powder.Through characterizing, measure, powder particle particle diameter is 40 μ m left and right, and wherein, microballoon size of cores is 30 μ m left and right, and water absorbent rate is 71 times.
No. 6 rock sample plugging agent evaluation experiments of microballoon shutoff
Accurately take the nucleocapsid structure polyacrylamide microsphere 0.5g preparing in embodiment 6, add oil field stratum water 99.5g, after fully disperseing, obtain 5 ‰ microballoon dispersion liquid, constant temperature 5～24 hours under 60 ℃ of conditions, obtains uniform microballoon dispersion system.Under 60 ℃ of constant temperatures, first oil field stratum water is injected to No. 6 rock sample plugging agent evaluation experimental installations of microballoon shutoff, treat that raw data acquisition is complete, the microballoon dispersion liquid configuring is injected to shutoff core plugging agent evaluation experimental installation, image data shows, injection pressure increases 6.53MPa, permeability plugging 20.38md during than water filling.
The present invention is not limited to the technology described in embodiment; its description is illustrative; and nonrestrictive; authority of the present invention is limited by claim; based on the art personnel according to the technology related to the present invention that the present invention can change, the method such as restructuring obtains, all within protection scope of the present invention.
Claims (9)
1. a nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent, it is characterized in that take cationic-type polyacrylamide as kernel, in core surface polymerization, obtain anion-polyacrylamide shell, the particle size range of nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent is 1～100 μ m.
2. the nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent preparation method of claim 1, is characterized in that described concrete steps are as follows:
(1) be incorporated as the acrylamide of core total solution weight 1～40%, 1～10% cationic monomer, 0.1～15% stablizer; Being incorporated as the linking agent of acrylamide and cationic monomer gross weight 0.1～8%, is the initiator of polymerization single polymerization monomer gross weight 0.01～5% again, and concussion, to dissolving completely, obtains solution A;
(2) be incorporated as the acrylamide of shell total solution weight 1～40%, 1～5% anionic monomer, 0.1～3% the 3rd monomer, 0.1～15% stablizer; Be incorporated as the linking agent of acrylamide, anionic monomer and the 3rd total monomer weight 0.1～8%, concussion, to dissolving completely, obtains solution B again;
(3) by for the initiator of step (2) mesochite solution polymerization total monomer weight 0.01～5% joins in solvent, shake to dissolving completely, obtain solution C;
(4) A solution 1/3 is added in reaction vessel, in solution, pass into N
2emptying 0.5h, controlling temperature is 40～80 ℃, stirring velocity is 200～500r/min; Then isothermal reaction 3h, obtains prepolymer solution; Control above-mentioned reaction conditions constant, residue A solution is joined in reaction system to sustained reaction 3h; Obtain microballoon core mixed solution;
(5) reaction conditions of control step 4 is constant, solution C is added to the microballoon core mixed solution obtaining, N
2environment continues absorption 1h; Then solution B is slowly added drop-wise in reaction system, controls reaction conditions constant sustained reaction 3h, finally cooling, filter, the dry nucleocapsid structure polyacrylamide microsphere profile control reservoir oil displacing agent that obtains.
3. method as claimed in claim 2, it is characterized in that described cationic monomer is selected from acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, N, N'-dimethylamino ethyl acrylic acid hydrochloride, beta-amido ethylacrylic acid hydrochloride or N, the one in N'-dimethylamino ethyl ethyl propenoate.
4. method as claimed in claim 2, is characterized in that described anionic polyacrylamide shell is selected from as follows:
(1) anionic monomer is selected from acrylate, sulfonated α-olefin, 2-acrylamide-2-methylpro panesulfonic acid salt, β-allylsulfonate, Sodium styrene sulfonate, the one in 2-acrylamide-2-methylpro panesulfonic acid;
(2) the 3rd monomers are selected from vinylbenzene, vinylformic acid, lauryl methacrylate(LMA), N-(4-ethyl) Phenyl Acrylamide, methyl methacrylate, the one in 4-vinylpridine.
5. method as claimed in claim 2, it is characterized in that selected solvent can be good at dissolving required each monomer, comprise acrylamide, ion monomer I, ion monomer II, the 3rd monomer, linking agent, initiator and stablizer, but do not dissolve their copolymerization product simultaneously.
6. method as claimed in claim 5, it is characterized in that described solvent is: methyl alcohol, ethanol, propyl alcohol, butanols, acetone, benzene, toluene, hexanaphthene, kerosene, diesel oil, white oil, methylene dichloride, chloroform or their mixed solvent, or the mixed solution of above organic solvent and water.
7. method as claimed in claim 2, is characterized in that described initiator is selected from the one in tetrazo initiator, organo-peroxide or redox class initiator.
8. method as claimed in claim 2, is characterized in that described stablizer is selected from the one in polyoxyethylene glycol, hydroxypropylcellulose, castor oil polyoxyethylene ether, polyvinylpyrrolidone, polyvinyl alcohol or Sodium dodecylbenzene sulfonate.
9. method as claimed in claim 2, is characterized in that described linking agent is selected from Vinylstyrene, vulcabond, N, N'-methylene-bisacrylamide, pentaerythritol triacrylate, the one in dimethyl diallyl ammonium chloride or polyethyleneglycol diacrylate.
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