CN104341548A - Micron-grade copolymer microspheres and preparation method thereof - Google Patents
Micron-grade copolymer microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention provides micron-grade copolymer microspheres and a preparation method thereof, wherein the micron-grade copolymer microspheres have regular surface morphology, controllable spherical degree, high-temperature and high-salinity resistance and good blocking characteristic. The copolymer microspheres are formed by copolymerizing an oleophylic monomer, a hydrophilic monomer and a cross-linking agent and comprise the raw materials in parts by mass: 80.0-99.0 parts of the oleophylic monomer, 0.5-10.0 parts of the hydrophilic monomer, and 0.5-10.0 parts of the cross-linking agent. The preparation method comprises the steps: firstly adding a suspending agent and deionized water into a reactor, next stirring evenly the oleophylic monomer, the hydrophilic monomer, an initiator and the cross-linking agent in a beaker at the room temperature, then adding into the reactor, under conditions of nitrogen protection, the temperature of 80 DEG C and the stirring speed of 300-400 r/min, carrying out a reaction for 6-8 hours, and thus obtaining the copolymer microspheres. The copolymer microsphere preparation method provided by the invention is mild in reaction conditions and easy to implement, and the obtained copolymer microspheres have good dispersity and high thermal stability, have the size controllable at 1-70 [mu]m, and are used as a blocking agent for blocking oil and gas reservoir pore passages.
Description
Technical field
The present invention relates to a kind of high-molecular copolymer microballoon, particularly relate to a kind of micron order copolymer microsphere and preparation method, described micron order copolymer microsphere is used as oilfield exploitation plugging agent or plugging agent.
Background technology
At present, most of oil gas reservoir is aeolotropic characteristics, and enters High water cut or super-high water-cut stage.This kind of Heterogeneous Oil And Gas Reservoirs, compared to Uniform premixing, shows the feature that hydrocarbon resources utilization ratio is low, development benefit is low.In this kind of Heterogeneous Oil And Gas Reservoirs process of water flooding recovery, in the deep channelling between hydrocarbon zone and layer, to stream phenomenon serious in deep, causes to inject water and ooze band or predominant pathway is advanced by leaps and bounds along high, produces inefficient cycle.In middle low osmoticing oil-gas layer water flooding recovery, floood conformance less than position by effect very low, cause the rate of oil and gas recovery very low.In recent years, the polymer microballoon technology of development is a kind of plugging technology of novel Deep Oil-gas layer, this technical project principle is the scale feature for Reservoir rocks pore throat, synthesize the polymer microballoon matched with it, these microballoons produce migration, shutoff, distortion and shutoff effect of migrating again in hydrocarbon zone pore throat, until in depths, stratum shutoff water breakthrough predominant pathway step by step, the tune realizing duct, hydrocarbon zone deep blocks up effect, thus improves the recovery ratio of water displacing oil.
In fact, polymer microballoon of the prior art, also for the shutoff of drilling well, Well Completion Engineering of Oil Reservoirs or the plugging agent of water-blocking operation.The acrylamido copolymer of prior art introduces novel thermo-salt resistance monomer copolymerization or crosslinked, provides multiple polymers microballoon plugging agent.But, polymer microballoon synthesized by these prior aries is under the multiple factors effects such as local water, reservoir temperature, pressure, salinity, the problems such as easy generation degraded, flocculation sediment, inefficacy, make it adjust stifled effect not remarkable, this mainly comes from validity and the copolyreaction characteristic thereof of comonomer.
In prior art, for shutoff or the water-plugging technique requirement of dissimilar reservoir characteristic and different development phases, develop serial water shutoff material.Water shutoff material of the prior art is categorized as: (1) cement class blocking agent, as oil based cement, water-based cements, activated cement and fine cement etc.; (2) inorganic salt precipitation class blocking agent, based on water glass; (3) Ploymer Gel Plugging Agent, mainly comprises synthetic polymer, Natural and Modified Natural Materials, biological polymer etc.; (4) particulate species blocking agent, comprises sodium bentonite, shell, bluestone powder, milk of lime, lightly crosslinked polyacrylamide particle, granule of polyvinyl alcohol etc.; (5) change the blocking agent of rock wettability, mainly comprise cationic polyacrylamide plugging agent, silicone based plugging agent, active thickened oil, cyanogen solidifying etc.
Prior art (Wang Yanli, Tan Dexin, Zhang Mingxu, Zhang Bin. soap-free emulsion prepares minimicrosphere aggretion type P (AMPS-MMA) microballoon, polymer material science and engineering, 2010, 26 (4): 149-152.), 2-acrylamide-2-methylpro panesulfonic acid (AMPS) is adopted to carry out soap-free silicone-acrylic emulsion as function monomer and methyl methacrylate (MMA), obtain minimicrosphere assembly type P (AMPS-co-MMA) microballoon, median size is approximately 20 μm, in monodispersity, each microballoon is polymerized by less microballoon, the particle diameter of minimicrosphere is about 0.1 μm, but this system due to the microballoon sphericity not adding linking agent and cause synthesizing bad, and percent polymerization is low.
Existing tune blocks up or plugging technology technology, Problems existing can be summed up as: (1) Inorganics cording has higher intensity, energy shutoff high permeability zone, but easily block oil gas flow passage, block section is in shallow-layer, block section difficulty is mobile or do not move, this is unfavorable for that hydrocarbon zone deep and follow-up tune deblocking technology are implemented all very much; (2) organic-compound system stifled and not dead, removable, deep can be realized adjust stifled, but plugging strength is low, shutoff validity period is short; (3) polyacrylamide is main cross-linking system, and Gelation Conditions is harsh, chocking-up degree is low, is not suitable for hydrocarbon zone macropore and fractured reservoir.
For prior art Problems existing, the deficiency of especially polymer microballoon plugging technology existence, the present invention proposes to adopt suspension polymerization technique, provides a kind of micron order copolymer microsphere and preparation method.The present invention adopts lipophilicity monomer, hydrophilic monomer and linking agent etc. to be raw material, prepares a kind of micron-level crosslinked copolymerization microsphere, and this copolymer microsphere is as heat and salinity tolerance blocking agent, and the tune for Heterogeneous Oil And Gas Reservoirs is stifled, stifled or shutoff temporarily.
Compared with prior art, the preparation method of copolymerization microsphere provided by the invention is easy to implement, and reaction conditions is gentle; Prepared microsphere features smooth surface, size tunable, in polymolecularity, the tune in suitable complex hydrocarbon duct is stifled, stifled or shutoff temporarily; Prepared copolymerization microsphere viscosity is low, and easily pump into, have thermo-salt resistance, available waste water, has water swellability, shutoff oil reservoir duct or crack after water-swelling.
For achieving the above object, a kind of micron order copolymer microsphere provided by the invention is obtained by lipophilicity monomer, hydrophilic monomer and linking agent copolymerization; Described micron order copolymer microsphere, the raw material formed by mass parts and treating processes thereof are: first, 80.0 ~ 99.0 parts of lipophilicity monomers, be washed till colourless with isopyknic mass concentration 5.0% sodium hydroxide solution before reaction, then extremely neutral with deionized water wash, anhydrous sodium sulfate drying, more namely underpressure distillation obtains the monomer of purification; Secondly, described 80.0 ~ 99.0 treated lipophilicity monomers, 0.5 ~ 10.0 part of hydrophilic monomer, 0.5 ~ 10.0 part of linking agent, 0.5 ~ 6.0 part of initiator and 0.5 ~ 6.0 part of suspension agent, anabolic reaction system.
Summary of the invention
A kind of micron order copolymer microsphere, each component is composed as follows relative to monomer total mass part:
Described micron order copolymer microsphere preparation method carries out as follows: first, adds the suspension agent of 0.5 ~ 6.0 mass parts and a certain amount of deionized water, stirring and dissolving in 50 DEG C of waters bath with thermostatic control, and be uniformly dispersed in reactor, obtained aqueous phase; Secondly, the lipophilicity monomer of 80.0 ~ 99.0 mass parts of purifying with the sodium hydroxide solution of 5.0% mass percentage concentration, this lipophilicity monomer after process and the linking agent of 0.5 ~ 10.0 mass parts and the initiator of 0.5 ~ 6.0 mass parts are added in reactor, stirred at ambient temperature mixes 1 hour, obtained oil phase; Again, the hydrophilic monomer solution of 0.5 ~ 10.0 obtained mass parts is slowly added drop-wise in above-mentioned oil phase, continues under room temperature to be uniformly mixed 1 hour, obtained mix monomer phase; Finally, under nitrogen protection, mix monomer is dropwise instilled in above-mentioned aqueous phase mutually, makes water and monomer total mass ratio be 1.0 ~ 10.0, after dropwising, bath temperature is risen to 80 DEG C, under 80 DEG C and stirring velocity 300 ~ 400r/min, sustained reaction 6 ~ 8 hours.After this reaction terminates, reaction system is left standstill cooling, suction filtration, deionized water wash 3 ~ 5 times, oven dry, grinds and cross 200 mesh sieves, namely required copolymer microsphere particle is synthesized, its polymerization yield rate is 50 ~ 95%, and particle size distribution is (particle size and pattern are shown in Figure of description 1) between 1 ~ 70 μm;
Described a kind of micron order copolymer microsphere, is characterized in that described lipophilicity monomer is methyl methacrylate or butyl acrylate, and the mass parts of lipophilicity monomer is 80.0 ~ 99.0.
Described a kind of micron order copolymer microsphere, is characterized in that described hydrophilic monomer is 2-acrylamide-2-methylpro panesulfonic acid sodium or sodium acrylate, and the mass parts of hydrophilic monomer is 0.5 ~ 10.0.
Described a kind of micron order copolymer microsphere, it is characterized in that described linking agent is divinylbenzene, diacrylate-BDO ester, ethylene glycol dimethacrylate or N,N methylene bis acrylamide, the mass parts of linking agent is 0.5 ~ 10.0.
Described a kind of micron order copolymer microsphere, is characterized in that described suspension agent is polyvinylpyrrolidone, polyvinyl alcohol, Walocel MT 20.000PV, tricalcium phosphate or magnesium chloride, and the mass parts of suspension agent is 0.5 ~ 6.0.
Described a kind of micron order copolymer microsphere, it is characterized in that described initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dicumyl peroxide or di-t-butyl peroxide, initiator mass parts is 0.5 ~ 6.0.
Described a kind of micron order copolymer microsphere, is characterized in that described water and monomer total mass ratio are 1.0 ~ 10.0.
Described a kind of micron order copolymer microsphere, it is characterized in that described microsphere particle size range is 1 ~ 70 μm, dimensional tolerances is 1 ~ 30%.
Described a kind of micron order copolymer microsphere, it is characterized in that described microballoon has the sphericity of desirable rule, shared by spherical irregular particle, overall particle per-cent is less than 1%.
Described a kind of micron order copolymer microsphere, is characterized in that described microballoon expansion rate of water absorption is 1 ~ 20, for shutoff hydrocarbon zone crack or hole duct.
Described a kind of micron order copolymer microsphere, is characterized in that the described microsphere particle suspension concentration for shutoff is 100 ~ 5000mgL
-1.
Described a kind of micron order copolymer microsphere, is characterized in that the sealing ratiod of described microballoon in the rock core duct of rate of permeation 1000 ~ 5000mD is 70 ~ 90%.Sealing ratiod is higher, and shutoff or stop drilling fluid or drilling fluid filtrate during drilling well, the ability to the infiltration of reservoir deep is stronger, produces and better protects Hydrocarbon Reservoir Permeability or permeability effects.
Described a kind of micron order copolymer microsphere, is characterized in that the hydrocarbon zone for Well Completion Engineering of Oil Reservoirs is blocked up temporarily, the micron order duct that reservoir protec-tion is natural, makes hydrocarbon zone duct keep original efficient perviousness or rate of permeation.
Described a kind of micron order copolymer microsphere, in the profile adjustment and oil displacement engineering of hydrocarbon zone, more effectively can adjust fluid flow profile and duct rate of permeation homogeneity, improves the rate of oil and gas recovery.
Accompanying drawing explanation
Scanning electronic microscope (SEM) figure (mean particle size 49.5 μm, size deviation 6.92%) of Fig. 1 embodiment 18 gained copolymer microsphere
Embodiment
The invention will be further described to enumerate specific embodiment below, but embodiments of the present invention are not limited thereto.
Embodiment 1
The deionized water (mass ratio of monomer total mass and water is 1: 4) of the suspension agent polyvinyl alcohol of 1.0 mass parts and metering is added in the 500mL reactor with agitator, stirring and dissolving in 50 DEG C of waters bath with thermostatic control, and be uniformly dispersed, obtained aqueous phase; Then by the lipophilicity monomers methyl methacrylate of 80.0 ~ 99.0 mass parts of purification, (linking agent is selected from divinylbenzene, diacrylate-1 with the linking agent of 1.0 mass parts, 4-butanediol ester, ethylene glycol dimethacrylate or N, N-methylene-bisacrylamide), the initiator Diisopropyl azodicarboxylate of 1.0 mass parts mixes 1 hour in stirred at ambient temperature, obtained oil phase; Again the hydrophilic monomer 2-acrylamide-2-methylpro panesulfonic acid sodium solution of 0.5 ~ 10.0 mass parts is dropwise added drop-wise in oil phase, is uniformly mixed 1 hour, obtained mix monomer phase; Then, under nitrogen protection condition, dropwise instilled mutually in aqueous phase by mix monomer, after dropwising, react 8 hours at 80 DEG C, stirring velocity controls as 400r/min.Copolymerization product microballoon pattern, sphericity and systematicness is observed by scanning electronic microscope (SEM).
Embodiment 2-5
Embodiment with embodiment 1, unlike:
For selected linking agent, respectively by 1.5,2.5,3.5,4.5 mass parts, add in the reaction system of embodiment 1 and react, observed the pattern of thus obtained microsphere product by SEM, this pattern comparing result is in table 1.
Embodiment 6
The deionized water (mass ratio of monomer total mass and water is 1: 4) of the suspension agent polyvinyl alcohol of 0.1 mass parts and metering is added in the 500mL reactor with agitator, stirring and dissolving in 50 DEG C of waters bath with thermostatic control, and be uniformly dispersed, obtained aqueous phase; Then by the lipophilicity monomers methyl methacrylate of 80.0 ~ 99.0 mass parts of purification, 1 hour is mixed with the linking agent ethylene glycol dimethacrylate of 4.0 mass parts, the initiator Diisopropyl azodicarboxylate of 1.5 mass parts in stirred at ambient temperature, obtained oil phase; Again the hydrophilic monomer 2-acrylamide-2-methylpro panesulfonic acid sodium solution of 0.5 ~ 10.0 mass parts is dropwise added drop-wise in oil phase, is uniformly mixed 1 hour, obtained mix monomer phase; Then, under nitrogen protection condition, dropwise instilled mutually in aqueous phase by mix monomer, after dropwising, react 8 hours at 80 DEG C, stirring velocity is 400r/min, and the median size of reacting final gained particle is 65.5 μm, and size deviation is 21.31%.
Described microsphere average grain diameter d and size deviation δ is calculated as follows:
In above formula: δ is size deviation, d is the median size of microballoon, d
ifor the particle diameter of i-th microballoon selected in scanning electronic microscope (SEM) picture, n is the quantity of microballoon selected in SEM picture.
Embodiment 7-10
Embodiment with embodiment 6, unlike:
Respectively the mass parts of suspension agent polyvinyl alcohol is added in the reaction system of embodiment 6 by 0.5,1.2,1.5,2.0, after reaction, obtain corresponding mean particle size d and size deviation δ, in table 2.
Embodiment 11
The deionized water (mass ratio of monomer total mass and water is 1: 4) of the suspension agent polyvinyl alcohol of 1.0 mass parts and metering is added in the 500mL reactor with agitator, stirring and dissolving in 50 DEG C of waters bath with thermostatic control, and be uniformly dispersed, obtained aqueous phase; Then by the lipophilicity monomers methyl methacrylate of 80.0 ~ 99.0 mass parts of purification, 1 hour is mixed with the linking agent ethylene glycol dimethacrylate of 4.0 mass parts, the initiator Diisopropyl azodicarboxylate of 0.5 mass parts in stirred at ambient temperature, obtained oil phase; Again the hydrophilic monomer 2-acrylamide-2-methylpro panesulfonic acid sodium solution of 0.5 ~ 10.0 mass parts is dropwise added drop-wise in oil phase, is uniformly mixed 1 hour, obtained mix monomer phase; Then, under nitrogen protection condition, dropwise instilled mutually in aqueous phase by mix monomer, after dropwising, react 8 hours at 80 DEG C, stirring velocity controls at 400r/min.Reaction gained polymerisate is after suction filtration, washing, oven dry, and calculating final polymerization yield rate is 76.7%.
Described polymerization yield rate is calculated as follows:
In above formula, P
yfor polymerization yield rate, %; W
1for the quality after copolymer microsphere oven dry, g; W
2for reacting the total mass of front monomer, g.
Embodiment 12-15
Embodiment with embodiment 11, unlike:
Respectively the mass parts of initiator Diisopropyl azodicarboxylate is added in the reaction system of embodiment 11 by 0.8,1.2,1.5,2.0, be obtained by reacting corresponding copolymerization microsphere productive rate and be respectively 80.2%, 83.0%, 84.1%, 82.7%, in table 3.
Embodiment 16
The deionized water (mass ratio of monomer total mass and water is 1: 2) of the suspension agent polyvinyl alcohol of 1.0 mass parts and metering is added in the 500mL reactor with agitator, stirring and dissolving in 50 DEG C of waters bath with thermostatic control, and be uniformly dispersed, obtained aqueous phase; Then by the lipophilicity monomers methyl methacrylate of 80.0 ~ 99.0 mass parts of purification, 1 hour is mixed with the linking agent ethylene glycol dimethacrylate of 4.0 mass parts, the initiator Diisopropyl azodicarboxylate of 1.5 mass parts in stirred at ambient temperature, obtained oil phase; Again the hydrophilic monomer 2-acrylamide-2-methylpro panesulfonic acid sodium solution of 0.5 ~ 10.0 mass parts is dropwise added drop-wise in oil phase, is uniformly mixed 1 hour, obtained mix monomer phase; Then, under nitrogen protection condition, dropwise instilled mutually in aqueous phase by mix monomer, after dropwising, react 8 hours at 80 DEG C, stirring velocity is 400r/min.Reaction gained polymerisate is after suction filtration, washing, oven dry, and calculating final polymerization yield rate is 58.3%.
Embodiment 17-20
Embodiment with embodiment 16, unlike:
Add in the reaction system of embodiment 16 by the mass ratio of monomer total mass and water by 1: 3,1: 4,1: 6,1: 7 respectively, corresponding copolymer microsphere productive rate is respectively 72.1%, 86.5%, 59.2%, 51.7%; Observe by scanning electronic microscope (SEM) copolymer microsphere product morphology that embodiment 18 obtains and thermogravimetric analysis is carried out to it, seeing accompanying drawing 1 and table 4.
Embodiment 21
It is 500mgL that copolymer microsphere prepared by embodiment 18 is mixed with mass concentration
-1suspension, rock core displacement device carries out reservoir core plugging simulated experiment.Testing rock core used is standard rock core: length 10cm, and diameter 2.5cm has hole duct and duct, crack, and its gas phase permeability is 2500mD; Experiment injection speed is 0.4mLmin
-1; Experimentally obtained data are calculated as follows sealing ratiod η, and experimental calculation the results are shown in Table 5.
In formula (4), K is the water phase permeability of rock core, μm
2; Q is injection speed, mls
-1; μ is injected fluid viscosity, mpas; L is rock core length, cm; A is the sectional area of rock core, cm
2; Δ P is rock core two ends pressure reduction, 10
-1mpa.
In formula (5), η is sealing ratiod, %; K
1for the original permeability of rock core, μm
2; K
2for the rate of permeation of rock core during following injected water, μm
2.
Embodiment 22-23
Embodiment with embodiment 21, unlike:
The concentration of the copolymer microsphere in embodiment 21 is pressed 1000mgL respectively
-1, 2000mgL
-1test, the sealing ratiod of its correspondence is in table 5.
Embodiment 24
Weigh the copolymer microsphere 0.20g prepared by embodiment 18, put into experiment tea-bag, claim its quality m
1, immerse and be equipped with in the weighing disk of deionized water, 25 DEG C of hydration swellings 3 days, reach after swelling equilibrium, taken out by experiment tea-bag, hang airing until it, the free water of removing microsphere surface, claims its quality m
2, be calculated as follows the expansion rate of water absorption P of microballoon
s, the results are shown in Table 6.
In above formula, P
sfor expansion rate of water absorption, gg
-1; m
1for the dry weight before water suction, g; m
2for the weight after water suction, g.
Embodiment 25-28
Embodiment with embodiment 24, unlike:
Experimental temperature in embodiment 24 tested by 45 DEG C, 60 DEG C, 75 DEG C, 90 DEG C respectively, the expansion rate of water absorption of its correspondence is in table 6.
Embodiment 29
Embodiment with embodiment 24, unlike:
Deionized water in embodiment 24 being changed into mass concentration is 5742.8mgL
-1simulated formation water (this Simulated Water is formulated by Shengli Oil Field Simulated Water ion) test, the expansion rate of water absorption of its correspondence is in table 6.
Embodiment 30-33
Embodiment with embodiment 29, unlike:
Experimental temperature in embodiment 29 tested by 45 DEG C, 60 DEG C, 75 DEG C, 90 DEG C respectively, the expansion rate of water absorption of its correspondence is in table 6.
Comparative example 1
Take AMPS and MMA that mass ratio is 1: 9, first AMPS is dissolved in the deionized water of 60mL, pH is regulated to be about 7 with the sodium hydroxide solution that mass concentration is 1.0%, add in the there-necked flask that agitator, prolong and nitrogen airway are housed, low whipping speed is under 350r/min, logical nitrogen, react 6 hours at 80 DEG C, Resorcinol is used to stop polyreaction, dehydrated alcohol breakdown of emulsion is added after emulsion freeze for some time, then filter, wash, vacuum-drying, last polymerization yield rate is about 65.4%.
Comparative example 2
Ultrasonic emulsifier-free emulsion polymerization prepares AMPS/MMA copolymer microsphere: take 1.33g AMPS and be dissolved in the distilled water of 60mL, regulates the pH=7.5 of AMPS solution, then adds 5.66mLMMA solution, mix with the sodium hydroxide solution of mass concentration 5%.Logical N
2gas is about 15min except O
2gas, temperature controls at 45 DEG C, and ultrasonic output rating is about 200W, N
2gas velocity is 100mL/min, and after reaction 90min, stopped reaction, obtains white emulsion.By emulsion after-15 DEG C of freezing 16h, add after dehydrated alcohol makes emulsion breaking flocculation, filtration, washing, vacuum-drying and obtain white powder copolymerization microsphere, its polymerization yield rate is 83%.
Comparative example 3
Ethanol and deionized water that volume ratio is 7: 1 is added in 500mL there-necked flask, the polyvinylpyrrolidone (PVP) of 1.0 mass parts is added after stirring, stirring and dissolving is closed and is added a certain amount of methyl methacrylate (MMA) by feed ratio, Sodium styrene sulfonate (SSS) and 2-acrylamide-2-methylpro panesulfonic acid sodium (AMPS-Na), stirring and dissolving, after being warming up to 50 DEG C, the ammonium persulfate-sodium bisulfite initiator of 1.5 mass parts is added drop-wise in above-mentioned reaction system, isothermal reaction 6 hours, then be that precipitation agent carries out polymer emulsion precipitation with ethanol, absolute ethanol washing 3 ~ 5 times, the residual PVP of removing and unreacted monomer and homopolymer, finally by product in 80 DEG C of dryings, mill and obtain product, final polymerization yield rate about 75.8%.
Comparative example 4
Adopt conversed phase micro emulsion copolymerization legal system for cross-linked polymer microsphere, adopt Gudao area of Shengli Oilfield waste water mass concentration 2000mg/L cross-linked polymer microsphere dispersion system, fill out sand tube core plugging is carried out in rock core displacement device, fill out sand tube rock core length is 50cm, diameter 2.5cm, rate of permeation 2300mD, when injecting 0.5 times of volume of voids, sealing ratiod is 92.16%.
Comparative example 5
Adopt emulsion polymerization to prepare polyacrylamide emulsion microballoon, form the coalescence body that particle diameter is tens microns after hydration swelling, for reservoir plugging macropore.In the back-up sand basket of rate of permeation 2000 ~ 2500mD, respectively implantation quality concentration be 1000,2000,3000, emulsion microballoon 0.3 times of volume of voids after 4000mg/L hydration swelling, corresponding reservoir core plugging rate is respectively 37.90%, 47.09%, 61.97%, 76.86%, and average sealing ratiod is about 55.96%.
Table 1 embodiment 1-5
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Dosage of crosslinking agent (mass parts) | 1.0 | 1.5 | 2.5 | 3.5 | 4.5 |
| Sphericity | Irregular | Irregular | More regular | Rule | More regular |
Remarks: for microsphere particle, block, bar-shaped, pole shape, strip, the granule-morphology such as coniform all belong to irregular spherical." irregular " represents that particle balling preparation is poor, and irregular spheroidal particle per-cent is greater than 60%; " more regular " represents that balling-up is better, 10% irregular spheroidal particle of having an appointment; " rule " represents that particle balling preparation is good, and irregular spheroidal particle is less than 1%;
Table 2 embodiment 6-10
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Suspension agent consumption (mass parts) | 0.1 | 0.5 | 1.0 | 1.5 | 2.0 |
| Particle average size d (μm) | 65.5 | 58.3 | 49.7 | 49.2 | 43.1 |
| Size deviation δ (%) | 21.31 | 14.23 | 8.17 | 6.85 | 8.39 |
Remarks: particle average size d and size deviation δ calculates as shown in formula (1), (2).
Table 3 embodiment 11-15
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | |
| Initiator amount (mass parts) | 0.5 | 0.8 | 1.2 | 1.5 | 2.0 |
| Polymerization yield rate (%) | 76.7 | 80.2 | 83.0 | 84.1 | 82.7 |
Table 4 embodiment 16-20
| Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | |
| Water and monomer total mass ratio | 2 | 3 | 4 | 6 | 7 |
| Polymerization yield rate (%) | 58.3 | 72.1 | 86.5 | 59.2 | 51.7 |
| Temperature of initial decomposition (DEG C) | -- | -- | 159 | -- | -- |
| Decomposition mechanism temperature (DEG C) | -- | -- | 366 | -- | -- |
| Stop decomposition temperature (DEG C) | -- | -- | 403 | -- | -- |
Table 5 embodiment 21-23
Remarks: L, D are respectively length and the diameter of rock core; η is sealing ratiod, %; K
1for the original permeability of rock core, μm
2; K
2for the rate of permeation of rock core during following injected water, μm
2; Wherein K, η calculate as shown in formula (4), (5).
Table 6 embodiment 24-33
Remarks: P
scalculate by formula (6): it is formulated that simulated formation water presses the simulation of Shengli Oil Field local water ion content composition, and its salinity is 5742.8 mgL
-1.
Table 7 embodiment 18 compares with comparative example 1-3's
Remarks: for microsphere particle, block, bar-shaped, pole shape, strip, the granule-morphology such as coniform all belong to irregular spherical." irregular " represents that particle balling preparation is poor, and irregular spheroidal particle per-cent is greater than 60%; " rule " represents that particle balling preparation is good, and irregular spheroidal particle per-cent is less than 1%.
Table 8 embodiment 21-23 compares with comparative example 4-5's
| Comparative example 4 | Comparative example 5 | Embodiment 21 | Embodiment 22 | Embodiment 23 | |
| Sealing ratiod η (%) | 92.16 | 55.96 | 71.29 | 83.87 | 84.62 |
Claims (12)
1. a micron order copolymer microsphere, is characterized in that described copolymer microsphere particle is made up of following mass parts:
Described micron order copolymer microsphere preparation method carries out as follows: first, adds the suspension agent of 0.5 ~ 6.0 mass parts and a certain amount of deionized water, stirring and dissolving in 50 DEG C of waters bath with thermostatic control, and be uniformly dispersed in reactor, obtained aqueous phase; Secondly, adopt the lipophilicity monomer of sodium hydroxide solution purification 80.0 ~ 99.0 mass parts of 5.0% mass percentage concentration, this lipophilicity monomer, the linking agent of 0.5 ~ 10.0 mass parts and the initiator of 0.5 ~ 6.0 mass parts after process are added in reactor, stirred at ambient temperature mixes 1 hour, obtained oil phase; Secondly, the hydrophilic monomer solution of 0.5 ~ 10.0 obtained mass parts is slowly added drop-wise in above-mentioned oil phase mixed system, continues under room temperature to be uniformly mixed 1 hour, obtained mix monomer phase; Finally, under nitrogen protection, mix monomer is dropwise added in above-mentioned aqueous phase mutually, makes water and monomer total mass ratio be 1.0 ~ 10.0, after dropwising, bath temperature is risen to 80 DEG C, under 80 DEG C and stirring velocity 300 ~ 400r/min, sustained reaction 6 ~ 8 hours.After this reaction terminates, reaction system is left standstill cooling, suction filtration, deionized water wash 3 ~ 5 times, oven dry, grinds and cross 200 mesh sieves, and namely synthesize required copolymer microsphere particle, its polymerization yield rate is 50 ~ 95%, and particle size distribution is 1 ~ 70 μm.
2. a kind of micron order copolymer microsphere according to claim 1, is characterized in that described lipophilicity monomer is methyl methacrylate or butyl acrylate, and the mass parts of lipophilicity monomer is 80.0 ~ 99.0.
3. a kind of micron order copolymer microsphere according to claim 1, is characterized in that described hydrophilic monomer is 2-acrylamide-2-methylpro panesulfonic acid sodium or sodium acrylate, and the mass parts of hydrophilic monomer is 0.5 ~ 10.0.
4. a kind of micron order copolymer microsphere according to claim 1, it is characterized in that described linking agent is divinylbenzene, diacrylate-1,4-butanediol ester, ethylene glycol dimethacrylate or N,N methylene bis acrylamide, the mass parts of linking agent is 0.5 ~ 10.0.
5. a kind of micron order copolymer microsphere according to claim 1, is characterized in that described suspension agent is polyvinylpyrrolidone, polyvinyl alcohol, Walocel MT 20.000PV, tricalcium phosphate or magnesium chloride, and the mass parts of suspension agent is 0.5 ~ 6.0.
6. a kind of micron order copolymer microsphere according to claim 1, it is characterized in that described initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dicumyl peroxide or di-t-butyl peroxide, initiator mass parts is 0.5 ~ 6.0.
7. a kind of micron order copolymer microsphere according to claim 1, is characterized in that described water and monomer total mass ratio are 1.0 ~ 10.0.
8. a kind of micron order copolymer microsphere according to claim 1, is characterized in that described microsphere particle is of a size of 1 ~ 70 μm, and size deviation is 1 ~ 30%.
9. a kind of micron order copolymer microsphere according to claim 1, it is characterized in that described microballoon has the sphericity of desirable rule, shared by spherical irregular particle, the per-cent of overall particle is less than 1%.
10. a kind of micron order copolymer microsphere according to claim 1, is characterized in that described microballoon expansion rate of water absorption is 1 ~ 20, for shutoff hydrocarbon zone crack or hole duct.
11. a kind of micron order copolymer microspheres according to claim 1, is characterized in that the described microsphere particle suspension concentration for shutoff is 100 ~ 5000mgL
-1.
12. a kind of micron order copolymer microspheres according to claim 1, is characterized in that the sealing ratiod of described microballoon in the rock core duct of rate of permeation 1000 ~ 5000mD is 70 ~ 90%.
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