CN102797443B - Method for exploiting residual crude oil in low-permeability oilfield by using polymer micro/nanoparticle - Google Patents
Method for exploiting residual crude oil in low-permeability oilfield by using polymer micro/nanoparticle Download PDFInfo
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Abstract
The invention relates to a method for exploiting residual crude oil in a low-permeability oilfield by using a polymer micro/nanoparticle, comprising the following steps of: (1) carrying out prior period water drive on the low-permeability oilfield; (2) measuring the average throat radius of the low-permeability oilfield to determine the particle size r of the polymer micro/nanoparticle, wherein the particle size r of the polymer micro/nanoparticle meets a formula shown in the specification; (3) carrying out copolymerization by using a distillation-precipitation method according to the determined particle size r of the polymer micro/nanoparticle to obtain the polymer micro/nanoparticle; and (4) injecting the polymer micro/nanoparticle obtained in the step (3) into an oil layer, and carrying out the following water drive on the low-permeability oilfield. The method of the invention has the advantages that the used polymer micro/nanoparticle injection system can selectively enter large, medium and small ducts, a stronger wave and volume expanding function and an oil washing capacity are achieved, the residual oil on a low-permeability layer is better exploited, the crude oil exploiting yield is increased, and the economic benefit is increased.
Description
Technical field
The invention belongs to field of oil field oil extraction, relate to tertiary oil production in oil field technology, be specifically related to a kind of use and receive the method for micron polymer particle exploitation low permeability oil field residual crude oil.
Background technology
At present, domestic a lot of oil field is in the stage of High water cut, high recovery percent of reserves, and comprehensive recovery is lower, many wells low yield.The eighties in 20th century, China has developed chemical flooding tertiary oil recovery technology.Tertiary oil recovery contrast primary oil recovery, secondary oil recovery.At the oil exploitation initial stage, the natural energy recover petroleum just utilizing stratum is primary oil recovery, and recovery ratio is only about 10%; Be secondary oil recovery by carrying out the method for recover petroleum to stratum water filling, gas injection, recovery ratio generally also can only reach about 25% ~ 40%; Tertiary oil recovery is then utilize physics, chemistry and the means such as biological, continues the residual petroleum of recovery of subterranean.
Present chemical flooding technology is in the flourish stage, and the chemical flooding research work carried out mainly comprises polymer flooding, alkali-polymer flooding, surfactant-alkali drives, surfactant and polymer drives and alkali, surfactant and polymer drives.These chemical combined floodings have not only carried out machanism research widely, have also carried out Pilot trial at the scene, and have achieved obvious effect.
And these chemical flooding tertiary oil recovery methods are mainly applicable to middle and high infiltration oil field at present.Surfactant and microbial process is had for low permeability oil field, but because the reasons such as technology, economy and low permeability oil field yield poorly make these class methods be difficult to be applied, in addition tertiary oil recovery method is applicable to high water cut rate more and uses, and the more major issue that low permeability oil field solves is flowing and controls moisture content rising problem.The method of current improvement flowing (improving the seepage flow situation in shaft bottom) has the retentively measure such as stressor layer, pressure break, water filling, optimized well pattern, horizontal wells.But these methods are also difficult to the exploitation effect forming large area scale, adopt horizontal well development often also not reach expected effect due to hyposmosis supply capacity deficiency, exploitation effective time is short, recovery ratio is low.
Summary of the invention
The present invention, in order to solve the problem, in conjunction with a kind of novel micron polymer particle of receiving, provides a kind of new method of exploiting low permeability oil field residual crude oil.
The invention provides a kind of utilization and receive the method for micron polymer particle exploitation low permeability oil field residual crude oil, employing be the method for " water drive+micro-nano polymer beads drives ", concrete steps are as follows:
(1) low permeability oil field water drive in early stage;
(2) the average throat radius of low permeability oil field is measured
determine to receive the r of micron polymer particle
particle diameter, wherein receive micron polymer particle particle size meet
(3) according to the r receiving micron polymer particle determined
particle diameter, adopt distillation precipitation method multi-component copolymer to obtain receiving micron polymer particle;
(4) the micron polymer particle of receiving of step (3) is injected oil reservoir, low permeability oil field sequent water flooding.
Wherein adopt in step (3) distillation precipitation method multi-component copolymer to obtain receiving the concrete steps of micron polymer particle to be:
(3-1) acrylamide is got, with the mixture of one or more of acrylic acid and derivative thereof, wherein the mol ratio of the mixture of one or more of acrylamide and acrylic acid and derivative thereof is 1:10-10:1, join in reaction vessel, in reaction vessel, add solvent, fully mix, then ultrasonic disperse is opened, in reaction vessel, add crosslinking agent and initator, also ultrasonic disperse is opened; (3-2) heater heat temperature raising, heated to fluidized state in 10-18 minute, then oil bath temperature was remained on about 90 DEG C, kept this state 15 minutes; (3-3) regulate heter temperature to 110-120 DEG C, strengthen distillation intensity, the solvent in reaction vessel constantly flow in receiving vessel, and after 90-100 minute, the solvent in reaction vessel all distills; (3-4) stop heating, in reaction vessel, add ethanol, and ultrasonic disperse, then the centrifugation microballoon that goes out to be obtained by reacting; (3-5) purify: again with EtOH Sonicate dispersion, centrifugal twice, to purify obtained microballoon; (3-6) then the described microballoon obtained after purification is put in 10-14 hour in the baking oven of 40-60 DEG C, dries the composition polymer microballoon obtaining needing.
Preferably, acrylic acid derivative is 2-acrylamido-methyl propane sulfonic acid (AMPS) or methyl methacrylate (MMA).
Preferably, acrylic acid is 1:3 with the mol ratio mixed of methyl methacrylate.
Preferably, described solvent is acetonitrile, methyl alcohol, ethanol, one or more in ethyl acetate and oxolane, consumption be the 17.3-36.5 of acrylamide molal weight doubly.
Preferably, it is characterized in that described crosslinking agent is N, N-methylene-bisacrylamide or divinylbenzene, consumption is the 1-10%(mol percentage of acrylamide); Described initator is azodiisobutyronitrile, ABVN or azo-bis-iso-dimethyl, and consumption is the 0.5-2%(mol percentage of acrylamide).
Preferably, in step (3-3), keep being back to solvent in reaction vessel and the velocity ratio of solvent that distills about 2.
Preferably, the micro-nano polymer beads slug size injected in described step (4) is 0.1 ~ 0.3PV.
Preferably, the micron polymer granule density scope of receiving injected in described step (4) is 1000 ~ 2500mg/L.
Preferably, the micron polymer granule density of receiving injected in described step (4) is 1000mg/L or 1500mg/L or 2500mg/L.
Further, wherein, the micron polymer particle initial particle distribution of receiving of use is 200nm ~ 1.2 μm, and after aquation, particle size distribution scope is 400nm ~ 13 μm; Wherein, micron polymer particle of receiving has hydration swelling characteristic.
Further, wherein, the size of micron polymer particle received used in described step (2) meets
time belong to flows at nanoscale, when
time belong to micron order flowing.
The invention has the advantages that: used micron polymer particle injection system of receiving can optionally enter large, medium and small duct, there is stronger expansion swept volume effect and washing oil ability, better exploitation less permeable layer remaining oil, improves oil recovery factor, increases economic benefit.
Accompanying drawing explanation
Fig. 1 receives micron polymer particle and drives with water drive oil moisture content with production time variation relation
Fig. 2 receives micron polymer particle and drives with water drive oil recovery percent of reserves with production time variation relation
Fig. 3 receive micron polymer particle in narrow and small pore channel rapidly by or distortion pass through;
Fig. 4 receive micron polymer particle large interstitial space place be detained or slowly flow;
Fig. 5 recovery ratio and injection pore volume multiple relation curve;
Fig. 6 is the schematic diagram of this method polymerisation apparatus;
Fig. 7 is the scanning electron microscope (SEM) photograph (in figure, scale is 5 μm) of the composite drying microballoon of four groups of different aquation grain size gradings.
In Fig. 6,1 is round-bottomed flask, and 2 is reactant liquor, and 3 is condensing reflux pipe, and 4 is chilled joint, and 5 is receiving vessel,
6 is heater.
Detailed description of the invention
Utilize the present invention to test in multiple field test district such as Daqing oil field, Shengli Oil Field, all receive significant development effectiveness.Recover the oil for grand celebration the oil reservoir of two factories, three factories, nine factories below, further illustrates the present invention by reference to the accompanying drawings.
Example one:
Recover the oil south two, three district of two factories of grand celebration is positioned at the south of Saar arch structure, and the western wing in inclination angle on stratum is 10 ° more suddenly, and it is 3.5 ° that the eastern wing comparatively delays; South two, three district's high beach dumping site depositional environments are mainly leading edge outside delta and deposit mutually, and lithology is based on packsand, fine sandstone and argillaceous siltstoue, and containing a small amount of illite/smectite mixed layer, dilatancy is not strong, and chlorite content is higher.Show the lithology of internal layer based on thin, siltstone, average air permeability 22.5mD, average pore 27.12%, average initial oil saturation 62.37%.
According to well selecting principle and standard, the well in two, three high beach dumping site areas, district, south is analyzed, profile control well group is by high 163-47, high 163-49, high 164-49, high 165-49, high 165-51, high 167-51, high 169-53, high 170-53 totally 8 mouthfuls of water well constructions, wellblock has 21 mouthfuls of oil wells, center extraction Jing6Kou.Profile control wellblock area 1.209km
2, high I, II group oil in place 263.9994 × 10
4t.
Inject and receive the contrast of micron polymer particle oil displacement efficiency.Laboratory experiment devises that water drive+micron polymer particle of receiving drives, water drive+polymer flooding, water drive three sets of plan carry out oil displacement efficiency contrast.It is minimum that result shows the moisture content that water drive+micron polymer particle of receiving drives, and improves recovery ratio amplitude maximum.As Fig. 1,2.This is because receive micron polymer as a kind of novel profile control agent step by step, physical and chemical changes can be there is in oil reservoir deep, realize the changed course of liquid stream.Simultaneously, the feature that micron polymer particle transfer drive of receiving has " stifled very much not stifled little ", make the effect reaching profile control step by step in macrovoid with the flowing of net distribution form or delay, its two-phase relative permeability obviously changes to the direction being conducive to displacement compared with water drive, expands swept volume to a certain extent.Wherein, water drive+polymer flooding, water drive all adopt mode well known in the art to carry out.
Wherein water drive of the present invention+micron polymer particle of receiving drives employing following steps:
(1) low permeability oil field water drive in early stage;
(2) the average throat radius of low permeability oil field is measured
determine to receive the r of micron polymer particle
particle diameter, wherein receive micron polymer particle particle size meet
(3) according to the r receiving micron polymer particle determined
particle diameter, adopt distillation precipitation method multi-component copolymer to obtain receiving micron polymer particle;
(4) the micron polymer particle of receiving of step (3) is injected oil reservoir, low permeability oil field sequent water flooding.
Inject and receive the determination of micron polymer grain diameter size and throat radius relation.Record according to rate-controlled mercury
calculate known, when
time, micron polymer particle of receiving can, smoothly by duct, be flows at nanoscale; When
time, micron polymer particle radius of receiving is several nanometer ~ several micron, and seepage flow shows as elastomeric deformable to be passed through, and there is resistance, is micron order flowing; When
time, there is larger resistance by duct in micron polymer particle of receiving, is difficult to pass through, and forms blocking.Can find out in micromodel test indoor, that injects stratum receives micron polymer particle at the rapid Deformation Flow of narrow and small oil reservoir pore channel by (Fig. 3), and occur at large interstitial space place being detained or slow flow phenomenon (Fig. 4), reach the effect increasing displacement swept volume, improve tertiary recovery rate.Also can adopt additive method well known in the art to measure
Inject and receive the determination of micron polymer particle slug size.Laboratory core experimental design is under the fixed concentration 1500mg/l, micron polymer particle slug size 0.05PV, 0.1PV, 0.15PV, 0.2PV, 0.25PV, 0.3PV six sets of plan is received in injection, and its recovery ratio increment is respectively 7.96%, 12.86%, 15.42%, 17.63%, 19.12%, 20.28%.Therefrom can find out, inject and receive oil production after micron polymer particle and obviously increase, and when injection 0.1PV receives micron polymer particle, recovery ratio increases most pronounced effects (Fig. 5), in conjunction with medicament expense and risk return profile, its ratio for input and output is maximum, and 0.2PV takes second place.In view of this, inject slug and select scheme 1, namely noting 0.1PV, to receive the displacement of reservoir oil of micron polymer particle better.
Inject and receive the determination of micron polymer particle slug concentration.Laboratory core test devises under best PV number simultaneously, injects difference and receives micron polymer particle slug concentration to the impact of cumulative recovery.In table 1.Result shows, increase oily really not obvious in 100 ~ 300mg/l timeliness when polymer beads injects solubility, recovery ratio increase rate is little; When implantation concentration reaches 500mg/l, effect is just able to clear embodiment; When implantation concentration is 1000mg/l, oil displacement efficiency is better, to 2009 the end of the year comparable water drive improve recovery ratio 15.66%, in conjunction with medicament expense with and risk return profile know, its ratio for input and output is maximum; When implantation concentration is more than 1500mg/l, medicament expense has high input, and it is little to increase oily amplitude, and ratio for input and output is undesirable.
Table 1 slug concentration is on the impact of cumulative recovery
| Scheme | Slug concentration (mg/l) | To 09 year moisture content (%) | To 09 year recovery ratio (%) |
| 1 | 100 | 98.8 | 23.32 |
| 2 | 300 | 98.8 | 27.68 |
| 3 | 500 | 98.7 | 31.46 |
| 4 | 1000 | 98.3 | 35.95 |
| 5 | 1500 | 98.6 | 38.62 |
| 6 | 2000 | 98.9 | 39.40 |
| 7 | Water drive | 97.0 | 20.29 |
According to the optimal parameter that above laboratory test is determined, in south, two, three oil field, district practice can obtain, after implementing to receive micron depth profile control being imitated step by step, individual well oil increasing effect is obvious, block moisture content declines and output increases, and profile control, to terminating, adds up in 5 years to increase oil 20400 tons.
Inject the economic benefit after micron polymer particle.Micron polymer grain emulsion 761.12 tons need be received, medicament expense unit price 2.16 ten thousand yuan/ton, injection device expense totally 32 ten thousand yuan, the expenses such as site operation about 860,000 yuan, drop into total cost 1762.09 ten thousand yuan.Market oil price about 3,500 ten thousand yuan/ton, obtain economic benefit 1716.4 ten thousand yuan, ratio for input and output reaches 4.05.
Adopt distillation precipitation method multi-component copolymer to obtain receiving the embodiment of micron polymer particle to be specially:
Embodiment 1:
Get acrylamide 1mol, acrylic acid 10mol, join single necked round bottom flask 1(reaction vessel) in, the acetonitrile solvent of 35.6mol is added in bottle, after abundant mixing, after ultrasonic disperse is opened, add the N-N methylene-bisacrylamide (MBAA) of 0.1mol in round-bottomed flask, the azodiisobutyronitrile (AIBN) adding 0.02mol also ultrasonic disperse is opened; (2) round-bottomed flask that reactant liquor 2 is housed is placed in oil bath pan (heater 6), downward-sloping certain angle, and such as 30 ° install condensing reflux pipe 3, chilled joint 4 and receiving vessel 5; (3) oil bath pan starts to heat up, and in 15 minutes, rise to fluidized state from normal temperature, oil bath pan temperature remains on about 90 DEG C, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 110 DEG C, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 90 minutes, the solvent in flask almost all distills.When ensureing this distilling effect, can adopt any condensing unit set-up mode, the condensing unit that such as the present invention preferably adopts is set to: keep being back to solvent in reaction flask and the velocity ratio of solvent that distills about 2.(5) stop reaction, the white solid in flask, scatter, and centrifugation out by adding EtOH Sonicate; (6) purify: again with EtOH Sonicate cleaning, centrifugal twice, purify the microballoon obtained; (7) then the solid obtained to be put in the baking oven of 40-60 DEG C 14 hours, to dry the polymer microballoon powder obtaining needing, weigh after grinding and install.The microballoon that this embodiment obtains is acrylamide and acrylic acid composition polymer microballoon P (AM-AA).
Embodiment 2:
Get acrylamide 10mol, 2-acrylamido-methyl propane sulfonic acid (AMPS) 1mol, join in single necked round bottom flask, the acetonitrile solvent of 173mol is added in bottle, after abundant mixing, after ultrasonic disperse is opened, add the divinylbenzene of 0.1mol in round-bottomed flask, the ABVN adding 0.05mol also ultrasonic disperse is opened; (2) round-bottomed flask that reactant liquor is housed is placed in oil bath pan (heater), downward-sloping certain angle, and such as 30 ° install condensing reflux pipe, chilled joint and receiving vessel; (3) oil bath pan starts to heat up, and in 18 minutes, rise to fluidized state from normal temperature, oil bath pan temperature remains on about 90 DEG C, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 120 DEG C, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 100 minutes, the solvent in flask almost all distills.When ensureing this distilling effect, can adopt any condensing unit set-up mode, the condensing unit that such as the present invention preferably adopts is set to: keep being back to solvent in reaction flask and the velocity ratio of solvent that distills about 2.(5) stop reaction, the white solid in flask, scatter, and centrifugation out by adding EtOH Sonicate; (6) purify: again with EtOH Sonicate cleaning, centrifugal twice, purify the microballoon obtained; (7) then the solid obtained to be put in the baking oven of 40-60 DEG C 10 hours, to dry the polymer microballoon powder obtaining needing, weigh after grinding and install.The microballoon that this embodiment obtains is the composition polymer microballoon P (AM-AMPS) of acrylamide and 2-acrylamido-methyl propane sulfonic acid (AMPS).
Embodiment 3:
Get acrylamide 1mol, methyl methacrylate (MMA) 5mol, join in single necked round bottom flask, the acetonitrile solvent of 24.4mol is added in bottle, after abundant mixing, after ultrasonic disperse is opened, add the N-N methylene-bisacrylamide (MBAA) of 0.05mol in round-bottomed flask, the azo-bis-iso-dimethyl adding 0.01mol also ultrasonic disperse is opened; (2) round-bottomed flask that reactant liquor is housed is placed in oil bath pan (heater), downward-sloping certain angle, and such as 30 ° install condensing reflux pipe, chilled joint and receiving vessel; (3) oil bath pan starts to heat up, and in 10 minutes, rise to fluidized state from normal temperature, oil bath pan temperature remains on about 90 DEG C, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 115 DEG C, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 100 minutes, the solvent in flask almost all distills.When ensureing this distilling effect, can adopt any condensing unit set-up mode, the condensing unit that such as the present invention preferably adopts is set to: keep being back to solvent in reaction flask and the velocity ratio of solvent that distills about 2.(5) stop reaction, the white solid in flask, scatter, and centrifugation out by adding EtOH Sonicate; (6) purify: again with EtOH Sonicate cleaning, centrifugal twice, purify the microballoon obtained; (7) then the solid obtained to be put in the baking oven of 40-60 DEG C 12 hours, to dry the polymer microballoon powder obtaining needing, weigh after grinding and install.The microballoon that this embodiment obtains is the composition polymer microballoon P (AM-MMA) of acrylamide and methyl methacrylate
Embodiment 4:
Get acrylamide 1mol, acrylic acid 1mol, methyl methacrylate 3mol, join in single necked round bottom flask, the acetonitrile solvent of 36.5mol is added, fully after mixing, after ultrasonic disperse is opened in bottle, in round-bottomed flask, add the N-N methylene-bisacrylamide (MBAA) of 0.08mol, the azodiisobutyronitrile (AIBN) adding 0.007mol also ultrasonic disperse is opened; (2) round-bottomed flask that reactant liquor is housed is placed in oil bath pan (heater), downward-sloping certain angle, and such as 30 ° install condensing reflux pipe, chilled joint and receiving vessel; (3) oil bath pan starts to heat up, and in 20 minutes, rise to fluidized state from normal temperature, oil bath pan temperature remains on about 90 DEG C, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 110-120 DEG C, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 100 minutes, the solvent in flask almost all distills.When ensureing this distilling effect, can adopt any condensing unit set-up mode, the condensing unit that such as the present invention preferably adopts is set to: keep being back to solvent in reaction flask and the velocity ratio of solvent that distills about 2.(5) stop reaction, the white solid in flask, scatter, and centrifugation out by adding EtOH Sonicate; (6) purify: again with EtOH Sonicate cleaning, centrifugal twice, purify the microballoon obtained; (7) then the solid obtained to be put in the baking oven of 40-60 DEG C 14 hours, to dry the polymer microballoon powder obtaining needing, weigh after grinding and install.The microballoon that this embodiment obtains is the composition polymer microballoon P (AM-AA-MMA) of acrylamide and acrylic acid, methyl methacrylate ternary polymerization.
Although the present invention gives four kinds of embodiments, limitation of the present invention can not be interpreted as.Although reaction dissolvent have employed acetonitrile solvent.But any is that oil-dissolving solvent can be applied in the present invention, as methyl alcohol, ethanol, ethyl acetate, one or more in methyl ethyl ketone and oxolane.Although the present invention have employed N-N methylene-bisacrylamide as crosslinking agent, also can adopt any crosslinking agent, such as adopt divinylbenzene, chemical pure rank, the impurity namely not containing the free radical stoped in polymerization process; Although the present invention have employed azodiisobutyronitrile (AIBN) as initator, any oil-soluble azo-initiator also can be adopted, as azodiisobutyronitrile, ABVN or azo-bis-iso-dimethyl.Adopt oil bath pan as heater in the present invention in polymerization process, but any type heater is all fine, such as can also sand-bath, hot air bath, electric furnace or other heater of thermal source can be provided; Although the present invention have employed round-bottomed flask as reaction vessel, it should be appreciated by those skilled in the art that the common container in any this area can as reaction vessel; Condensation reflux unit is downward-sloping certain angle, the such as 30 degree condensing reflux pipes installed, chilled joint and receiving vessel, or directly with a liebig's condensing tube, but also can adopt any common condensation reflux unit in this area, as long as can distilling effect be ensured.The microspherulite diameter distribution wherein obtained is homogeneous, and microballoon is controlled between 200nm to 12 μm, solves that to receive microspherulite diameter in micron polymer microsphere building-up process chaotic, problem not of uniform size; And the microballoon prepared all is not easy to reunite, in good monodisperse status in oil phase and aqueous phase solvent; Whole course of reaction is simple to operation, still-process is exactly the removal process of solvent, reclaim the solvent obtained can reuse, the step of carrying out secondary purification or removing polymerization inhibitor is not needed yet, compensate for because monomer concentration is lower, expending the shortcoming that quantity of solvent is large, thus contribute to suitability for industrialized production, is a kind of excellent method preparing composition polymer microballoon.According to the microballoon of preparation, carry out corresponding aquation experiment, find that microballoon can expand in water, different microballoons has different hydration capabilities, obtains from the microballoon of the different-grain diameter classification between 200nm to 12 μm that (Fig. 7, only gives four kinds of different particle diameters, but different particle diameters can be selected as required), optionally can be injected in stratum, thus reach water plugging and profile controlling, improve the object of recovery ratio.
First solvent will meet solvent polymerization reaction monomers, and can be settled out the character of the corresponding polymer obtained.Like this, in reaction system, along with temperature rises, decomposition of initiator produces free radical, this free radical can react to obtain free radical newly with polymerization single polymerization monomer wherein, then new monomer is attacked again, such free radical chain constantly increases, self polarity is caused to change, by the similar principle that mixes, molecular weight with polymer chain increases, solubility in reaction medium reduces gradually, after reaching critical chain length, from medium, precipitating out, many segments mutually tangle and form stable core suspension in media as well, monomer in the elementary growth core absorption reaction medium formed and free radical, polymerisation is proceeded in core, form polymer microballoon.But free radical runs into the higher molecule of some activity in the solution, such as oxygen atom, just can react with it and stop the growth of free radical chain, thus there is oxygen in solvent can hinder polymerisation.According to gas Henry's law, the solubility of oxygen in the solvent of boiling is almost nil.Thus the polymerization in the solvent of boiling does not need nitrogen protection device and step.
In addition, because acetonitrile solvent can be good at dissolving the monomer and initator added, the system starting stage is a homogeneous phase solution, along with the carrying out of reaction, system reaches fluidized state, and now heat transfer and mass transfer all reach maximum, there is no need to add mixing plant in system, once add stirring, can cause on the contrary the polymer microballoon sphericity obtained good not or reunite.This preparation method has following advantage:
(1) uniform particle diameter: dry microspheres diameter is less, the diameter of various different dry microspheres is all within the scope of 200nm to 12 μm, and diameter distribution is very narrow, can within 4%.Be easy to large-scale production: under fluidized state, system is in isotropism, the heat transfer of storeroom, and mass transfer is all in maximum rating, is very beneficial for large-scale polymerisation.
(2) reaction time is short: because polymerization temperature is at about 82 °, the initiation decomposition rate of initator and the rate of rise of free radical chain more much bigger than usually, thus greatly shorten polymerization time, namely conversion ratio reaches the time required for 90%.In this method, the whole reaction time only needs 2 hours.
(3) polymer microballoon of various difference in functionality group can be obtained by this kind of distillation precipitation method, as polyacrylamide microsphere (PAM), acrylamide and acrylic acid composition polymer microballoon P (AM-AA), the composition polymer microballoon P (AM-MAA) of acrylamide and methacrylic acid, the composition polymer microballoon P (AM-MMA) of acrylamide and methyl methacrylate, the composition polymer microballoon P (AM-AMPS) of acrylamide and 2-acrylamido-methyl propane sulfonic acid (AMPS), acrylamide and acrylic acid, the composition polymer microballoon P (AM-AA-MMA) of methyl methacrylate ternary polymerization.Because different monomers has different functional characteristics, such as, so the different composite polymer microballoon of preparation has different functions, because AMPS is due to the performance of high-temperature resisting and salt-resisting, obtain the performance that P (AM-AMPS) microballoon also has high-temperature-resistant high-salt.
(4) equipment is simple; be easy to operation: in the present invention, only need condensation reflux unit; do not need nitrogen protection device; do not need mixing plant; also do not need accurate temperature control equipment, because the boiling point of system only forms relevant with the pressure in the external world and system, under normal pressure, boiling point remains unchanged within the specific limits; thus the temperature of system is relatively stable, without the need to the temperature control equipment of precision.Three aspects integrate, and this polymerization unit is simplified greatly.
(5) environmental protection and economy: owing to needing in polymerization process to use distillation, and still-process is also the purification process of a solvent simultaneously, the solvent distilled can repeat polymerisation next time, not only economy but also environmental protection, and there is no other special purification requirement to participating in reaction medicine, save cost, improve reaction efficiency.
Example two:
Grand celebration is recovered the oil, and to be positioned at Daqing, Heilongjiang Province Dorbod Mongol Autonomous County domestic for the Longhupao oilfield of nine factories, construction location is positioned at Qijia-Gulong depression west side, Song-liao basin concavity district, is minor axis three grades of arch structures that dragon and tiger bubble-Hong Gang terrace the North axis is bordering on north and south.Employ oil area 27.5km
2, oil in place 1316 × 10
4t.Mined bed is Saar oil reservoir, Putaohua reservoir mainly.Sa, Portugal's oil reservoir air permeability generally between 1 ~ 100mD, mean permeability 57mD, average pore 20.6%.
According to receiving micron polymer particle depth profile control mechanism, test wellblock selection principle mainly considers that strong, the moisture height of non-homogeneity, pump pressure and oil pressure difference is greater than 2MPa and the block of remaining oil enrichment.According to this principle, carry out at each block of Longhupao oilfield the primary election testing wellblock.Primary election four wellblocks: imperial 21-18 wellblock (comprising imperial 21-18,25-18 two well groups), imperial 28-19 wellblock, imperial 79-20 wellblock (comprising imperial 77-19,79-20,81-19 tri-well groups), imperial 79-22 wellblock (comprising imperial 77-23,79-22,79-24,81-23 tetra-well groups).
Wherein water drive of the present invention+micron polymer particle of receiving drives employing following steps:
(1) low permeability oil field water drive in early stage;
(2) the average throat radius of low permeability oil field is measured
determine to receive the r of micron polymer particle
particle diameter, wherein receive micron polymer particle particle size meet
(3) according to the r receiving micron polymer particle determined
particle diameter, adopt distillation precipitation method multi-component copolymer to obtain receiving micron polymer particle;
(4) the micron polymer particle of receiving of step (3) is injected oil reservoir, low permeability oil field sequent water flooding.
Wherein adopt distillation precipitation method multi-component copolymer to obtain receiving the embodiment of micron polymer particle and adopt method preparation listed by embodiment one.
Inject and receive the determination of micron polymer particle slug size.Laboratory core test simulation devises injection and receives micron polymer particle slug size 0.05PV, 0.1PV, 0.15V, 0.2PV, 0.25PV, 0.3PV six sets of plan, and its recovery ratio increment is respectively 12.78%, 15.06%, 19.37%, 21.52%, 23.45%, 25.14%.Therefrom can find out, inject and receive oil production after micron polymer particle and obviously increase, and when inject 0.2PV receive micron polymer particle time, recovery ratio increase most pronounced effects (Fig. 5), in conjunction with medicament expense and risk return profile, its ratio for input and output is maximum.In view of this, inject slug and select scheme 4, namely noting 0.2PV, to receive the displacement of reservoir oil of micron polymer particle better.
Inject and receive the determination of micron polymer particle slug concentration.Laboratory core test devises injection difference simultaneously and receives micron polymer particle slug concentration to the impact of cumulative recovery.In table 2.Result shows, when polymer beads implantation concentration is 1500mg/l, oil displacement efficiency is better, and to comparable water drive raising in the end of the year 2009 recovery ratio 10.07%, ratio for input and output is maximum.
Table 2 slug concentration is on the impact of cumulative recovery
| Scheme | Slug concentration (mg/l) | To 09 year moisture content (%) | To 09 year recovery ratio (%) |
| 1 | 500 | 98.7 | 22.14 |
| 2 | 1000 | 98.5 | 25.59 |
| 3 | 1500 | 98.4 | 31.94 |
| 4 | 2000 | 98.6 | 37.75 |
| 5 | 2500 | 98.6 | 38.06 |
| 6 | 3000 | 98.7 | 40.37 |
| 7 | Water drive | 97.3 | 21.87 |
According to the optimal parameter that above laboratory test is determined, can obtain in Longhupao oilfield practice, after implementing to receive micron depth profile control being imitated step by step, the normal water filling of block cumulative water-oil ratio is low, maximum can be low 5 percentage points, centerwell Long79-23Jing can be low 10 percentage points; Block output is higher than normal water filling, and daily output amplification is maximum reaches 35%, and centerwell dragon 79-23 well daily output amplification is maximum reaches 100%.
Inject the economic benefit received after micron polymer particle.Micron polymer grain emulsion 954.02 tons need be received, medicament expense unit price 2.16 ten thousand yuan/ton; Injection device expense totally 35 ten thousand yuan, the expenses such as site operation about 900,000 yuan; Accumulative increasing oil 23700 tons in 5 years, oil price about 3500 yuan/ton.Receive after micron polymer particle profile control, drop into total cost 2185.68 ten thousand yuan, produce economic benefit 8,295 ten thousand yuan, ratio for input and output reaches 3.8.
Example three:
Grand celebration three factory East of the northern block of recovering the oil are positioned at the northern single oil area in Daqing placanticline Saar oil field, oil area 20.2km
2, oil in place 12336 × 104t.It is northern that this district is positioned at Saar oil field arch structure, and structure is comparatively mild, and stratigraphic dip about 2 °, landform is smooth, ground about sea level on the average 150.0m.Tomography 10 is grown in this district altogether, all belongs to normal fault, fault strike be north-northwest to, tomography mean obliquity is about 52 °, mean permeability value 101.23mD, average pore 24.71%.
According to well selecting principle and standard, the well in oil reservoir area, Dui Bei tri-district is analyzed, and selects 8 mouthfuls of well saliva wells to carry out water drive depth profile control, and profile control wellblock is that eight notes 21 are adopted.Profile control well group is by northern 3-4-467, northern 3-4-469, northern 3-4-496, northern 3-5-468, northern 3-5-68, northern 3-J6-467, northern 3-J6-469,3-J6-66, totally 8 mouthful water well construction, and wellblock has 21 mouthfuls of oil wells, center extraction Jing6Kou.Profile control wellblock area 3.169km
2, Sa l, II group oil in place 294.0897 × 10
4t, wellblock, center area 0.51km
2, its oil in place 97.3 × 10
4t.Wherein water drive of the present invention+micron polymer particle of receiving drives employing following steps:
(1) low permeability oil field water drive in early stage;
(2) the average throat radius of low permeability oil field is measured
determine to receive the r of micron polymer particle
particle diameter, wherein receive micron polymer particle particle size meet
(3) according to the r receiving micron polymer particle determined
particle diameter, adopt distillation precipitation method multi-component copolymer to obtain receiving micron polymer particle;
(4) the micron polymer particle of receiving of step (3) is injected oil reservoir, low permeability oil field sequent water flooding.
Wherein adopt distillation precipitation method multi-component copolymer to obtain receiving the embodiment of micron polymer particle and adopt method preparation listed by embodiment one.
Inject and receive the determination of micron polymer particle slug size.Laboratory core experimental design is injected and is received micron polymer particle slug size 0.1PV, 0.15V, 0.2PV, 0.25V, 0.3PV, 0.35PV six sets of plan, and its recovery ratio increment is respectively 12.38%, 14.56%, 16.93%, 19.42%, 24.35%, 26.94%.Therefrom can find out, inject and receive oil production after micron polymer particle and obviously increase, in conjunction with medicament expense with and situation of Profit, when inject 0.3V receive micron polymer particle time, recovery ratio increases most pronounced effects (Fig. 5), and ratio for input and output is maximum, and 0.35 takes second place.In view of this, inject slug and select scheme 5, namely noting 0.3V, functional to receive the displacement of reservoir oil of micron polymer particle better.
Inject and receive the determination of micron polymer particle slug concentration.Laboratory core test devises injection difference simultaneously and receives micron polymer particle slug concentration to the impact of cumulative recovery.In table 3.Result shows, when polymer beads implantation concentration is 2500mg/l, oil displacement efficiency is better, and to comparable water drive raising in the end of the year 2009 recovery ratio 16.79%, ratio for input and output is maximum.
Table 3 slug concentration is on the impact of cumulative recovery
| Scheme | Slug concentration (mg/l) | To 09 year moisture content (%) | To 09 year recovery ratio (%) |
| 1 | 500 | 98.6 | 24.42 |
| 2 | 1000 | 98.6 | 26.39 |
| 3 | 1500 | 98.4 | 29.08 |
| 4 | 2000 | 98.2 | 33.17 |
| 5 | 2500 | 98.3 | 38.96 |
| 6 | 3000 | 98.7 | 42.13 |
| 7 | Water drive | 97.2 | 22.17 |
Inject the economic benefit received after micron polymer particle.Micron polymer particle of need receiving drives emulsion 1127.43 tons, medicament expense unit price 2.16 ten thousand yuan/ton, injection device expense totally 40 ten thousand yuan, the expenses such as site operation totally 102 ten thousand yuan, drops into total cost 2577.23 ten thousand yuan.According to predicting the outcome, injecting and receiving moisture decline 1.1 percentage points after the profile control of micron polymer granule wellblock, after profile control terminates, water drive moisture to 87.9% time, accumulatively in 5 years increase oil 29300 tons, market oil price about 3500 yuan/ton, obtaining economic benefit is 10,255 ten thousand yuan, and ratio for input and output reaches 3.98.
Claims (2)
1. a method for micron polymer particle exploitation low permeability oil field residual crude oil is received in utilization, it is characterized in that, employing be the method that water drive Ghana micron polymer particle drives, concrete steps are as follows:
(1) low permeability oil field water drive in early stage;
(2) the average throat radius of low permeability oil field is measured
determine to receive the r of micron polymer particle
particle diameter, wherein receive micron polymer particle particle size meet
(3) according to the r receiving micron polymer particle determined
particle diameter, adopt distillation precipitation method multi-component copolymer to obtain receiving micron polymer particle;
(4) the micron polymer particle of receiving of step (3) is injected oil reservoir, low permeability oil field sequent water flooding;
Adopt in described step (3) distillation precipitation method multi-component copolymer to obtain receiving the concrete steps of micron polymer particle to be:
(3-1) acrylamide is got, with the mixture of one or more of acrylic acid and derivative thereof, wherein the mol ratio of the mixture of one or more of acrylamide and acrylic acid and derivative thereof is 1:10-10:1, join in reaction vessel, in reaction vessel, add solvent, fully mix, then ultrasonic disperse is opened, in reaction vessel, add crosslinking agent and initator, also ultrasonic disperse is opened;
(3-2) heater heat temperature raising, heated to fluidized state in 10-18 minute, then oil bath temperature was remained on about 90 DEG C, kept this state 15 minutes;
(3-3) regulate heter temperature to 110-120 DEG C, strengthen distillation intensity, the solvent in reaction vessel constantly flow in receiving vessel, and after 90-100 minute, the solvent in reaction vessel all distills;
(3-4) stop heating, in reaction vessel, add ethanol, and ultrasonic disperse, then the centrifugation microballoon that goes out to be obtained by reacting;
(3-5) purify: again with EtOH Sonicate dispersion, centrifugal twice, to purify obtained microballoon;
(3-6) then the described microballoon obtained after purification is put in 10-14 hour in the baking oven of 40-60 DEG C, dries the composition polymer microballoon obtaining needing;
Acrylic acid derivative is 2-acrylamido-methyl propane sulfonic acid (AMPS) or methyl methacrylate (MMA);
Described solvent is acetonitrile, methyl alcohol, ethanol, one or more in ethyl acetate and oxolane, consumption be the 17.3-36.5 of acrylamide molal weight doubly;
Described crosslinking agent is N, N-methylene-bisacrylamide or divinylbenzene, and consumption is the 1-10% (mol percentage) of acrylamide; Described initator is azodiisobutyronitrile, ABVN or azo-bis-iso-dimethyl, and consumption is the 0.5-2% (mol percentage) of acrylamide;
In step (3-3), keep being back to solvent in reaction vessel and the velocity ratio of solvent that distills about 2;
The micron polymer particle slug size of receiving injected in described step (4) is 0.1 ~ 0.3PV;
The micron polymer granule density scope of receiving injected in described step (4) is 1000 ~ 2500mg/L;
The micron polymer particle initial particle distribution of receiving used is 200nm-1.2um, and after aquation, particle size distribution scope is 400nm-13um; Wherein, micron polymer particle of receiving has hydration swelling characteristic.
2. the method for claim 1, is characterized in that, described acrylic acid is 1:3 with the mol ratio mixed of methyl methacrylate.
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| CN106833586B (en) * | 2016-12-28 | 2019-12-10 | 浙江海洋大学 | nano-micron polymer particle and surfactant composite oil displacement method |
| CN107832871B (en) * | 2017-10-19 | 2022-04-19 | 北京科技大学 | Characterization method for improving water drive effect mode of nano-micron particle dispersion system |
| CN112727414B (en) * | 2021-01-10 | 2022-07-12 | 西南石油大学 | Method for improving crude oil recovery ratio by combining binary compound flooding and water flooding |
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