CN107286920A - Double combed block polymer profile control agents of a kind of microspheroidal and preparation method thereof - Google Patents
Double combed block polymer profile control agents of a kind of microspheroidal and preparation method thereof Download PDFInfo
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- CN107286920A CN107286920A CN201610227506.5A CN201610227506A CN107286920A CN 107286920 A CN107286920 A CN 107286920A CN 201610227506 A CN201610227506 A CN 201610227506A CN 107286920 A CN107286920 A CN 107286920A
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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Abstract
The invention provides double combed block polymer profile control agents of a kind of microspheroidal and preparation method thereof.The preparation method includes acrylamide monomer, long-chain epoxyalkane, acrylamido sulfonate, the acrylic monomers aqueous solution is made, and adds pH adjusting agent, and regulation pH value is 68；At 0 DEG C 15 DEG C, nitrogen is passed through, redox composite initiator, polyase 13 h 10h is added；1h 4h, 60 DEG C 90 DEG C dry 4h 8h, crushing, sievings are hydrolyzed under 70 DEG C of 90 DEG C of bath temperatures；It is dissolved in liphophilic solvents, 1h 4h is stirred under 20 DEG C of 35 DEG C of bath temperatures；40 DEG C 50 DEG C are heated to, the double combed block polymer profile control agents of microspheroidal are made in granulation.Present invention also offers the double combed block polymer profile control agents of the microspheroidal prepared by the above method.The double combed block polymer profile control agents of the microspheroidal of the present invention have good adaptability with reservoir, can be efficiently entering earth formation deep, realize efficient profile modification, increase substantially oil recovery factor.
Description
Technical field
The present invention relates to a kind of profile control agent and preparation method thereof, more particularly to a kind of microspheric parent of controllable swelling time
Combed block macromolecular polymer profile control agent of water-hydrophobic pair and preparation method thereof, belongs to high molecular polymer technology of preparing
Field.
Background technology
Constantly accelerate with oilfield exploitation paces, the most of oil field of China or even the whole world has come into the rank of High water cut
Section, this proposes new requirement and challenge to how further to improve oil recovery factor.
Nowadays, water injection well transfer drive and water shutoff in oil well have become the important technical of tertiary oil recovery, equally
It is to improve water flooding effect, realize oil reservoir stable yields, improve the indispensable supporting technology of oil recovery factor technology.
Research at present to profile control agent is increasingly extensive, and existing profile control agent includes chromium, the zirconium used for high-permeability pay
Jelly system, phenolic resin system, clay/cement dispersion, milk of lime, hydroexpanding body；Suitable for low permeability pay
Silicic acid, aluminium hydroxide gel micro-sphere etc..
But, found by long-term field application, the initial particles of existing most of profile control agents is big, crosslinking time
Short, the speed of viscosity increasement is too fast, mobility is excessively poor, it is just started expansion before unimplanted well casing, is difficult to be delivered to deeper
Stratum.Even if into stratum, also due to profile control agent matches somebody with somebody premature inflation in liquid pool on ground, causing water blockoff particle to exist
Enter and extruded by stratum shearing force and screen casing to rupture during pump, and then lose water blockoff transfer drive ability.
Therefore, traditional water blockoff profile control agent is only capable of playing transfer drive effect on the layer position shallower away from water injection well, it is difficult to be deep into
The inside on stratum.Deep profile correction technology for Thief zone oil field is still the problem of urgently further research at present.
The content of the invention
In order to solve the above-mentioned technical problem, it is an object of the invention to provide a kind of initial particle is suitable, crosslinking time length,
The speed of viscosity increasement is moderate, the profile control agent suitable for Thief zone high salt reservoir depth transfer drive of mobility and saline-alkaline tolerance by force.
In order to realize above-mentioned technical purpose, the invention provides a kind of system of the double combed block polymer profile control agents of microspheroidal
Preparation Method, the preparation method comprises the following steps：
Step one：Acrylamide monomer, long-chain epoxyalkane, acrylamido sulfonate, acrylic monomers are made
Mass concentration is the 5%-40% aqueous solution, adds pH adjusting agent, and regulation pH value is 6-8, obtains solution；Wherein,
In terms of molfraction, the acrylamide monomer, long-chain epoxyalkane, acrylamido sulfonate, acrylic monomers
Mixed proportion be 30-80：5-30：5-40：1-20；
Step 2：At 0 DEG C -15 DEG C, it is passed through into solution after nitrogen 20min-60min, adds redox and be combined and draw
Agent is sent out, polyase 13 h-10h obtains gum-like product；Wherein, the process of step 2 keeps being passed through for nitrogen；Wherein, institute
The addition for stating redox composite initiator is the 0.2%-0.5% of monomer gross mass, and the monomer gross mass refers to third
The quality for the aqueous solution that acrylamide monomer, long-chain epoxyalkane, acrylamido sulfonate, acrylic monomers are made is total
With the quality not comprising water；
Step 3：Gum-like product is hydrolyzed into 1h-4h under 70 DEG C of -90 DEG C of bath temperatures, 60 DEG C -90 DEG C dry 4h-8h,
Crush, sieve, obtain double combed block copolymerization powders；Wherein, sieve selection mesh screen be the purpose of 400 mesh -800
Mesh screen；
Step 4：Double combed block copolymerization powders are dissolved in liphophilic solvents, under 20 DEG C of -35 DEG C of bath temperatures
1h-4h is stirred, emulsion is obtained；Wherein, powdered pair of combed block copolymerization powder is with 100ppm-2000ppm's
Concentration is dissolved in liphophilic solvents, and mixing speed is 50rad/min-200rad/min；
Step 5：Emulsion is heated to 40 DEG C -50 DEG C, granulated by aerosol apparatus, the microspheroidal is made
Double combed block polymer profile control agents.
In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that the long-chain of use
Epoxyalkane includes one kind or several in oxepane, octylene oxide, 1,2- Epoxydodecanes and the 1,2- epoxy tetradecanes
The combination planted.In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that use
Acrylamido sulfonate include 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamido tetradecane sulfonic acid and
One or more of combinations in 2- acrylamido hexadecane sulfonic acid, above-mentioned raw materials are by lark prestige Science and Technology Ltd.
There is provided.
According to the embodiment of the present invention, the preparation side of the double combed block polymer profile control agents of microspheroidal of the invention
In method, the nitrogen used is 99.999% high pure nitrogen, when being passed through nitrogen with being capable of starvation and hybrid reaction is molten
Liquid does not spray.
In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that the pH of use
Conditioning agent include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium acid carbonate, saleratus, monoethanolamine,
One or more combinations in diethanol amine, triethanolamine and ammoniacal liquor.
In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that with the oxidation
Reduce the gross mass of composite initiator to count for 100wt%, the raw material composition of the redox composite initiator included
Sulfate, bisulfites, the water of aminated compounds and surplus, wherein, the persulfate, bisulfites and
The mass ratio of aminated compounds is 0.2wt%-20wt%：0.1wt%-10wt%：0.1wt%-30wt%.
In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that the over cure of use
Hydrochlorate includes ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that the sulfurous of use
Sour hydrogen salt includes ammonium bisulfite, sodium hydrogensulfite or potassium bisulfite.
In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that the amine of use
Compound includes N, N- diethyl ethylenediamines, diethylenetriamine, N, N, N ', N '-tetraethylethylenediamine, N, N- bis- are different
Propyl group ethylenediamine and N, N, N ', one or more of combinations in N '-tetraallylethylene diamine.
In the preparation method of the double combed block polymer profile control agents of microspheroidal of the present invention, it is preferable that the oleophylic of use
Property solvent include n-hexane, hexamethylene, benzene, toluene, carbon tetrachloride or chlorobenzene.
Present invention also offers a kind of double combed block polymer profile control agents of microspheroidal, it is by the double combs of above-mentioned microspheroidal
What the preparation method of type block polymer profile control agent was prepared.
In the double combed block polymer profile control agents of microspheroidal that the present invention is provided, it is preferable that the double combed blocks of the microspheroidal
The particle diameter of polymer profile control agent is 2 μm -8 μm.
Invention further provides a kind of aerosol apparatus, the aerosol apparatus is used for the double combed block polymerizations of above-mentioned microspheroidal
In the preparation method of thing profile control agent, the aerosol apparatus includes：
Mother liquor tank, spray gun, the first screening tower, the second screening tower, the 3rd screening tower, air blower and air-introduced machine；
Wherein, mother liquor tank is connected with the first screening tower, and spray gun is provided between mother liquor tank and the first screening tower；
First screening tower, the second screening tower, the 3rd screening tower are sequentially communicated；
Air blower is connected with the described first screening tower；
Air-introduced machine is connected with the described 3rd screening tower.
In the aerosol apparatus that the present invention is provided, the spray gun of use includes single spraying rifle, three spray guns, four spray guns, six sprays
Rifle or eight spray guns.According to bottom porosity demand select evaporability thus select different spray guns, people in the art
Member can be selected as the case may be.
In the aerosol apparatus that the present invention is provided, the pipette tips of spray gun are arranged on the upper end inside the first screening tower.
In the preparation method for the double combed block polymer profile control agents of microspheroidal that the present invention is provided：By acrylamide, propylene
Acid, long-chain epoxyalkane and acrylamido sulfonate copolymerization, form hydrophilic-hydrophobic block type water soluble polymer
Polymer.Wherein, acrylamido sulfonate is as multi-functional anionic monomer, with good polymerization activity,
The two S-O coordinate bonds contained in sulfonic acid group in acrylamido sulfonate, can effectively hinder extraneous cation
Attack, and then improve the heatproof of polymer, anti-salt property；The carboxylic acid ion (- COOH) having in acrylic acid (AA)
Dissolubility of the polymer in water can be significantly improved, dissolution velocity is improved；Hydrophobic grouping is set as with long branched chain structure
Epoxyalkane, after alkyl carbon chain lengths are more than 6, required hydrophobicity can be achieved, epoxyalkane belongs to three
Yuan of rings, because its tension force is big, C-O bond polarities are acted in addition, make it in sour (cation), alkali (anion)
And in neutral (water), can occur C-O keys and be broken and open loop, the product of epoxy alkane ring opening polymerization is polyethers,
Mainly act on the prepolymer of nonionic surfactant.Wherein, the long chain alkane side base after open loop block is used as main body
Hydrophobic grouping.
The double combed block polymer profile control agents of microspheroidal of the present invention are due to micron order initial particle, and outer layer is by growing
Chain hydrophobic alkyl serves as " diaphragm ", shape-changeable ball can be made smoothly to go deep into inside stratum, is dissolved with simulation salt solution
The extension of time, hydrone penetrates progressively through shape-changeable ball duct, into inside the block copolymer that hydrophobic alkyl chain is wrapped up,
Contacted with hydrophilic radical, cause endless chain to be gradually swelled, it is final fully open.Hydrophilic radical is fully exposed in salt solution,
And hydrophobic grouping starts aggregation due to hydrophobic effect, make occur association between macromolecular chain, form dynamic physical crosslinking
Network, causes the increase of its hydrodynamic volume, and solution viscosity is increased substantially, and then blocks hypertonic in water filling stratum
Saturating circulation road, and it is stifled without dead, realize the purpose of steady oil control water.Compared with traditional oil displacement agent, its drive is substantially increased
Oily ability.
The preparation method of the double combed block polymer profile control agents of microspheroidal that the present invention is provided by molecular scale and
The design of macro-scale, can reasonably and effectively control to adjust the stifled time, adjust stifled property poor, no while solving profile control agent
The problems such as heatproof, not salt resistance.
The double combed block polymer profile control agents of microspheroidal that the present invention is provided polymerize for hydrophilic-hydrophobic block graft ball-type
Thing, outside side base is hydrophobic grouping, and hydrophilic radical is equally inwardly arranged in order as side base, forms micron order " controllable
Molten type shape-changeable ball ".Meanwhile, pass through aerosol process, the particle diameter of the double combed block polymer profile control agents of control microspheroidal
For 2 μm -8 μm.
The preparation technology flow of the preparation method for the double combed block polymer profile control agents of microspheroidal that the present invention is provided is simple；
The double combed block polymer profile control agents of microspheroidal that the present invention is provided are a kind of deformable materials of controllable swelling time, are solved
The tune of existing profile control agent block up property it is poor, not heatproof, not salt resistance the problems such as.
The micron order initial particle having in the double combed block polymer profile control agents of microspheroidal that the present invention is provided with it is hydrophobic
" diaphragm " of group shell parcel so that the profile control agent has good adaptability with reservoir, can be efficiently entering ground
Layer depth portion, and controllability adjusts itself swelling time, realizes efficient profile modification, increases substantially oil recovery factor.
Brief description of the drawings
Fig. 1 be embodiment 1 in aerosol device structural representation.
Fig. 2 changes with time rule for the apparent viscosity of the double combed block polymer profile control agents of microspheroidal of embodiment 6
Curve.
Main Reference symbol description
The spray gun 3 first of the 1 mother liquor tank 2 screening screening screening tower of tower 5 the 3rd of tower 4 second
The post pump plug of 6 air blower, 7 air-introduced machine 8
Embodiment
In order to which technical characteristic, purpose and beneficial effect to the present invention are more clearly understood from, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
The present embodiment provide firstly a kind of aerosol apparatus, and its structure is as shown in figure 1, the aerosol apparatus includes：
Mother liquor tank 1, three spray guns 2, the first screening screening screening of tower the 4, the 3rd of tower 3, second tower 5, the and of air blower 6
Air-introduced machine 7；
Wherein, mother liquor tank 1 is connected with the first screening tower 3, and spray gun is provided between the screening tower 3 of mother liquor tank 1 and first
2；Plunger pump 8 is provided with spray gun 2；The first screening screening screening tower 5 of tower the 4, the 3rd of tower 3, second is sequentially communicated；
Air blower 6 is connected with the first screening tower 3；Air-introduced machine 7 is connected with the 3rd screening tower 5；The pipette tips of spray gun 2 are arranged on
Upper end inside first screening tower 3.
A kind of preparation method of the double combed block polymer profile control agents of microspheroidal is present embodiments provided, is specifically included following
Step：
(1) preparation of solution：In terms of molar part, acrylamide monomer, oxepane, by 2- acrylamidos -2-
Methyl propane sulfonic acid monomer is with acrylic acid according to 40:25:12:7 proportions add pH into the aqueous solution that concentration is 30%
Conditioning agent (sodium hydroxide and diethanol amine), adjusts pH to 7；
(2) polymerization process：Be continually fed under the conditions of 5 DEG C of constant temperature after 99.999% high pure nitrogen, 50min successively plus
Enter redox composite initiator (by N, N- diethyl diamines, sodium peroxydisulfate, sodium hydrogensulfite composition, each component
Mass ratio be 7:5:1), this process is continually fed into high pure nitrogen, and the addition of redox composite initiator is monomer
(monomer refers to the monomer summation that acrylamide monomer, oxepane are configured in the aqueous solution that concentration is 30%, does not wrap
It is aqueous) gross mass 0.3%, add redox composite initiator after be continually fed into after high pure nitrogen 60min seal,
4h is reacted in confined conditions, produces blob of viscose；
(3) blob of viscose is post-processed：Blob of viscose is blended, and cures at 80 DEG C and to be carried out at 1.5h, 60 DEG C after drying 6h
Crushing, screening process, the mesh screen of 500 mesh of selection are sieved, and obtain double combed block copolymerization powders；
(4) preparation of microspheroidal transfer drive agent emulsion：Double combed block copolymerization powders are molten with 500ppm concentration
In n-hexane liphophilic solvents, 3h is stirred at 30 DEG C of bath temperature, mixing speed is 150rad/min, is obtained
Emulsion；
(5) granulation of polymer：Emulsion is preheated to 40 DEG C, and granulated by above-mentioned aerosol apparatus,
The double combed block polymer profile control agents of microspheroidal, code T Q-1 are finally made.
Granulation is carried out by above-mentioned aerosol apparatus and specifically includes below scheme：
Emulsion in mother liquor tank 1 is preheated to 40 DEG C, entered emulsion by mother liquor tank 1 in the presence of plunger pump 8
In spray gun 2；By tower top shower nozzle, it is sprayed onto in 50 DEG C -80 DEG C of atomizing angle with vaporific in the first screening tower 3, while through
Filtered air enters first by air blower 6 and sieved in tower 3, and evenly distributed hot-air is filled with tower intrinsic fog material
The heat exchange divided, moisture evaporation is through 180 DEG C big revolution after heat exchange, and the atomization material discharged at top sequentially enters second
The screening tower 5 of tower the 4, the 3rd is sieved, siccative falls into the bottom of the first screening tower 3 in powdery, by the 3rd screening tower 5
The atomization material of top discharge is by entering vulcanization bed, and the fine particle by boiling heating, cooling is entered by shaking sieve
Collecting tank, collects finished product, obtains the double combed block polymer profile control agents of microspheroidal.Wherein, the mother in aerosol apparatus
Flow container 1, the surface of the screening screening screening tower 5 of tower the 4, the 3rd of tower 3, second of spray gun 2, first are all covered with heat-insulation layer,
It is that pelletization is in progress in isoperibol.
Embodiment 2
A kind of preparation method of the double combed block polymer profile control agents of microspheroidal is present embodiments provided, is specifically included following
Step：
(1) preparation of solution：In terms of molar part, acrylamide monomer, octylene oxide, 2- acrylamido -2- first
Base propane sulfonic acid is with acrylic monomers according to 50:23:19:7 proportions add pH and adjusted into the aqueous solution that concentration is 28%
Agent (sodium acid carbonate) is saved, pH to 7.5 is adjusted；
(2) polymerization process：Sequentially added after being continually fed into 99.999% high pure nitrogen, 40min at 12 DEG C of constant temperature
Redox composite initiator (is made up of, the mass ratio of each component diethylenetriamine, potassium peroxydisulfate, potassium bisulfite
For 3:2:1), this process is continually fed into high pure nitrogen, and (monomer is for monomer for the addition of redox composite initiator
Refer to the monomer summation that acrylamide monomer, oxepane are configured in the aqueous solution that concentration is 28%, not comprising water) it is total
The 0.25% of quality, adds and sealing after high pure nitrogen 60min is continually fed into after redox composite initiator, closed
Under the conditions of react 3h, produce blob of viscose；
(3) blob of viscose is post-processed：Blob of viscose is blended, and cures at 85 DEG C and to carry out powder after drying 5h at 2h, 85 DEG C
Broken, screening process, the mesh screen of 600 mesh of selection is sieved, and obtains double combed block copolymerization powders；
(4) preparation of microspheroidal transfer drive agent emulsion：By above-mentioned pair of combed block copolymerization powder with the dense of 1000ppm
Degree is dissolved in n-hexane liphophilic solvents, and in 30 DEG C of stirring 2.5h of bath temperature, mixing speed is 150rad/min, is obtained
To emulsion；
(5) granulation of polymer：Emulsion is preheated to 40 DEG C, and made by the aerosol apparatus of embodiment 1
Grain, is finally made the double combed block polymer profile control agents of microspheroidal, numbering is TQ-2.
Embodiment 3
A kind of preparation method of the double combed block polymer profile control agents of microspheroidal is present embodiments provided, is specifically included following
Step：
(1) preparation of solution：In terms of molar part, acrylamide monomer, 1,2- Epoxydodecanes, 2- acrylamidos
Tetradecane sulfonic acid is with acrylic monomers according to 45:25:12:5 proportions add pH into the aqueous solution that concentration is 35%
Conditioning agent (sodium acid carbonate), adjusts pH to 7；
(2) polymerization process：Sequentially added after being continually fed into 99.999% high pure nitrogen, 30min at 15 DEG C of constant temperature
Redox composite initiator (by N, N, N ', N '-tetraethylethylenediamine, ammonium persulfate, ammonium bisulfite composition, respectively
The mass ratio of component is 4:2:1), this process is continually fed into high pure nitrogen, and the addition of redox composite initiator is
Monomer (monomer refers to the monomer summation that acrylamide monomer, oxepane are configured in the aqueous solution that concentration is 35%,
Not comprising water) gross mass 0.4%, add redox composite initiator after be continually fed into after high pure nitrogen 45min
Sealing, reacts 2.5h, produces blob of viscose in confined conditions；
(3) blob of viscose is post-processed：Blob of viscose is blended, and cures at 90 DEG C and to be carried out at 2.5h, 90 DEG C after drying 2h
Crushing, screening process, the mesh screen of 700 mesh of selection are sieved, and obtain double combed block copolymerization powders；
(4) preparation of microspheroidal transfer drive agent emulsion：By above-mentioned pair of combed block copolymerization powder with the dense of 600ppm
Degree is dissolved in n-hexane liphophilic solvents, stirs 2.5h at 25 DEG C of bath temperature, mixing speed is 180rad/min,
Obtain emulsion；
(5) granulation of polymer：Emulsion is preheated to 40 DEG C, and granulated by aerosol apparatus, final system
The double combed block polymer profile control agents of microspheroidal are obtained, numbering is TQ-3.
Embodiment 4
A kind of preparation method of the double combed block polymer profile control agents of microspheroidal is present embodiments provided, is specifically included following
Step：
(1) preparation of solution：In terms of molar part, acrylamide monomer, 1, the 2- epoxies tetradecane, 2- acrylamidos
Hexadecane sulfonic acid monomer is according to 7:3:2:1 proportions add pH adjusting agent (carbon into the aqueous solution that concentration is 40%
Sour hydrogen sodium), adjust pH to 6.5；
(2) polymerization process：Sequentially added after being continually fed into 99.999% high pure nitrogen, 40min at 12 DEG C of constant temperature
Redox composite initiator (by N, N, N ', N '-tetraallylethylene diamine, sodium peroxydisulfate, sodium hydrogensulfite composition,
The mass ratio of each component is 11:6:3), this process is continually fed into high pure nitrogen, the addition of redox composite initiator
Measure for monomer (monomer refers to the monomer summation that acrylamide monomer, oxepane are configured in the aqueous solution that concentration is 40%,
Not comprising water) gross mass 0.3%, add redox composite initiator after be continually fed into after high pure nitrogen 60min
Sealing, reacts 3h, produces blob of viscose in confined conditions；
(3) blob of viscose is post-processed：Blob of viscose is blended, and cures at 80 DEG C and to carry out powder after drying 5h at 4h, 80 DEG C
Broken, screening process, the mesh screen of 800 mesh of selection is sieved, and obtains double combed block copolymerization powders；
(4) preparation of microspheroidal transfer drive agent emulsion：By above-mentioned pair of combed block copolymerization powder with the dense of 600ppm
Degree is dissolved in n-hexane liphophilic solvents, stirs 4h at 35 DEG C of bath temperature, mixing speed is 200rad/min,
Obtain emulsion；
(5) granulation of polymer：Emulsion is preheated to 50 DEG C, and granulated by aerosol apparatus, final system
The double combed block polymer profile control agents of microspheroidal are obtained, numbering is TQ-4.
Embodiment 5
It is 1.28 × 10 in total salinity5Mg/L, calcium ions and magnesium ions total concentration for 425mg/L simulation salt solution in, add
The double combed block polymer profile control agents of the microspheroidal of embodiment 1- embodiments 4, it is the poly- of 500mg/L to be configured to concentration
Compound saline solution.Laser particle analyzer test result shows, the material can directly rapid dispersion, grain in simulation salt solution
At 2 μm -8 μm, as a result as shown in table 1 footpath controls.
Table 1
| Sample number into spectrum | TQ-1 | TQ-2 | TQ-3 | TQ-4 |
| Particle diameter/μm | 8.0 | 7.8 | 3.3 | 2.2 |
Embodiment 6
The present embodiment has carried out apparent viscous to the double combed block polymer profile control agents of microspheroidal of embodiment 1- embodiments 4
Degree test, at 120 DEG C, the polymer salt aqueous solution of 1500mg/L concentration is 1.28 × 10 in total salinity5Mg/L,
Calcium ions and magnesium ions total concentration for 425mg/L simulation salt solution in, 7.34s-1Initial apparent viscosity is 11.6mPas down.With
The extension of time, hydrone passes through the microballoon shaped polymer wrapped up by hydrophobic grouping, with the hydrophilic radical inside the centre of sphere
It is combined, causes microspheroidal material to be gradually swelled, final fully open, what formation was unfolded has hydrophilic-hydrophobic group concurrently
Block copolymer.After the end of the chain is opened ,-the SO in block copolymer3Na groups can effectively completely cut off bivalent cation,
Suppress Ca2+With Mg2+Ion is combined with the profile control agent, prevents molecular chain rupture, occurs sedimentation deactivation phenomenom, performance
Excellent saline-alkaline tolerance is gone out.Apparent viscosity is promoted to rapidly 25.7mPas in continuance test, 3h-9h, and in 96h
Within, viscosity keeps stable, as a result as shown in Figure 2.Fig. 2 result shows, embodiment 1- embodiments 4 it is micro-
Spherical pair of combed block polymer profile control agent viscosity during stratum is goed deep into slowly is lifted, and can be finally promoted to original
2.2 times or so, with micron order initial particle, can smoothly enter stratum inside.
Furthermore it is noted that the double combed block polymer profile control agents of the microspheroidal of embodiment 1- embodiments 4
Dissolution velocity is in reverse correlation with hydrophobic grouping proportion.Wherein, TQ-1 and hydrophobic grouping in TQ-3 profile control agents
Proportion is respectively 26.6% and 25.8%；And hydrophobic grouping proportion is respectively in TQ-2 and TQ-4 profile control agents
19.2% and 20%.It can be found that in 0-9 days, TQ-2 and TQ-4 slope are significantly greater than TQ-1 from Fig. 2
The latter is significantly faster than that with TQ-3, i.e. the former rate of dissolution.
Embodiment 7
The present embodiment has carried out anti-aging to the double combed block polymer profile control agents of microspheroidal of embodiment 1- embodiments 4
Aptitude tests, detailed process is as follows：
First, fresh sample viscosity is tested：Using Kazakhstan's high salinity simulation water：Total salinity is
1.28×105Mg/L, calcium ions and magnesium ions total concentration is 425mg/L, and the double combed of the microspheroidal of embodiment 1- embodiments 4 are embedding
Section polymer profile control agent is diluted to 1500ppm concentration, measures 85 DEG C, 7.34cm-1The viscosity of above-mentioned sample under rotating speed；
2nd, burin-in process is carried out：Vacuumize, at 120 DEG C, sealed 90 days under oxygen free condition；
3rd, aged samples viscosity is tested：Above-mentioned sample is taken out, stands after normal temperature, tests 85 DEG C of its constant temperature, 7.34cm-1
The aging viscosity of the sample under rotating speed；
4th, viscosity retention rate calculating=(fresh sample viscosity-aged samples viscosity)/fresh sample viscosity × 100%.Survey
Test result is as shown in table 2.
The result of table 2 shows, under 120 DEG C of oxygen free conditions, the double combed blocks of microspheroidal of embodiment 1- embodiments 4
After polymer profile control agent aging 90 days, viscosity retention rate is up to 90%-96%.
The sample viscosity retention rate of 2 embodiment 1- embodiments of table 4
Embodiment 8
The present embodiment is simulated respectively to the double combed block polymer profile control agents of microspheroidal of embodiment 1- embodiments 4
Core flooding test is tested.
First,
Boring sample：Sample length is 25cm, a diameter of 3.5cm Kazakhstan's oil field block rock core；
Kazakhstan's high salinity simulation water：Total salinity is 1.28 × 105Mg/L, calcium ions and magnesium ions total concentration is
425mg/L；
The measure of water phase permeability before stifled：Rock core vacuumizing is injected into Kazakhstan high-salinity brine and injects water to full
With with 1L/min flow water drive to pressure stability, the water phase permeability for measuring rock core is 189 × 103μm2；
Simulation core oil displacement test：In injecting Kazakhstan's oil field block dewatered oil under 120 DEG C of constant temperature, by this
Rock core carries out saturated process, 24h water drives to residual oil state；
Constant temperature 72h at microspheroidal double combed block polymer profile control agent TQ-1 of 2PV embodiments 1,120 DEG C is injected,
And continue displacement with Kazakhstan's high-salinity brine, it is 5.2 × 10 to measure the water phase permeability after closure3μm2,
It is 97.2% to calculate sealing ratiod.
2nd,
Boring sample：Sample length is 30cm, a diameter of 4.0cm Kazakhstan's oil field block rock core；
Kazakhstan's high salinity simulation water：Total salinity is 1.28 × 105Mg/L, calcium ions and magnesium ions total concentration is
425mg/L；
The measure of water phase permeability before stifled：Rock core vacuumizing is injected into Kazakhstan high-salinity brine and injects water to full
With with 1L/min flow water drive to pressure stability, the water phase permeability for measuring rock core is 201 × 103μm2；
Simulation core oil displacement test：In injecting Kazakhstan's oil field block dewatered oil under 110 DEG C of constant temperature, by this
Rock core carries out saturated process, 24h water drives to residual oil state；
Inject constant temperature 72h at microspheroidal double combed block polymer profile control agent TQ-2 of 2PV embodiments 2,110 DEG C.
And continue displacement with Kazakhstan's high-salinity brine, it is 2.6 × 10 to measure the water phase permeability after closure3μm2,
It is 98.7% to calculate sealing ratiod.
3rd,
Boring sample：Sample length is 27cm, a diameter of 3.8cm Kazakhstan's oil field block rock core；
Kazakhstan's high salinity simulation water：Total salinity is 1.28 × 105Mg/L, calcium ions and magnesium ions total concentration is
425mg/L；
The measure of water phase permeability before stifled：Rock core vacuumizing is injected into Kazakhstan high-salinity brine and injects water to full
With with 1L/min flow water drive to pressure stability, the water phase permeability for measuring rock core is 197 × 103μm2；
Simulation core oil displacement test：In injecting Kazakhstan's oil field block dewatered oil under 85 DEG C of constant temperature, by this
Rock core carries out saturated process, 24h water drives to residual oil state；
Inject constant temperature 72h at microspheroidal double combed block polymer profile control agent TQ-3 of 2PV embodiments 3,85 DEG C.
And continue displacement with Kazakhstan's high-salinity brine, it is 3.1 × 10 to measure the water phase permeability after closure3μm2,
It is 98.5% to calculate sealing ratiod.
4th,
Boring sample：Sample length is 33cm, a diameter of 4.1cm Kazakhstan's oil field block rock core；
Kazakhstan's high salinity simulation water：Total salinity is 1.28 × 105Mg/L, calcium ions and magnesium ions total concentration is
425mg/L；
The measure of water phase permeability before stifled：Rock core vacuumizing is injected into Kazakhstan high-salinity brine and injects water to full
With with 1L/min flow water drive to pressure stability, the water phase permeability for measuring rock core is 176 × 103μm2；
Simulation core oil displacement test：In injecting Kazakhstan's oil field block dewatered oil under 95 DEG C of constant temperature, by this
Rock core carries out saturated process, 24h water drives to residual oil state；
Inject constant temperature 72h at microspheroidal double combed block polymer profile control agent TQ-4 of 2PV embodiments 4,95 DEG C.
And continue displacement with Kazakhstan's high-salinity brine, it is 2.1 × 10 to measure the water phase permeability after closure3μm2,
It is 98.8% to calculate sealing ratiod.
Above example illustrates the preparation work of the preparation method of the double combed block polymer profile control agents of the microspheroidal of the present invention
Skill flow is simple；The micron order initial particle having in the double combed block polymer profile control agents of the microspheroidal of the present invention, with
Reservoir has good adaptability, can be efficiently entering earth formation deep, and controllability adjusts itself swelling time, realizes high
Profile modification is imitated, oil recovery factor is increased substantially.
Claims (10)
1. a kind of preparation method of the double combed block polymer profile control agents of microspheroidal, the preparation method comprises the following steps：
Step one：Acrylamide monomer, long-chain epoxyalkane, acrylamido sulfonate, acrylic monomers are made
Mass concentration is the 5%-40% aqueous solution, adds pH adjusting agent, and regulation pH value is 6-8, obtains solution；Wherein,
In terms of molfraction, the acrylamide monomer, long-chain epoxyalkane, acrylamido sulfonate, acrylic monomers
Mixed proportion be 30-80：5-30：5-40：1-20；
Step 2：At 0 DEG C -15 DEG C, it is passed through into the solution after nitrogen 20min-60min, adds redox and answer
Initiator is closed, polyase 13 h-10h obtains gum-like product；Wherein, the process of step 2 keeps being passed through for nitrogen；Wherein,
The addition of the redox composite initiator is the 0.2%-0.5% of monomer gross mass, and the monomer gross mass refers to
The quality for the aqueous solution that acrylamide monomer, long-chain epoxyalkane, acrylamido sulfonate, acrylic monomers are made
Summation, the quality not comprising water；
Step 3：The gum-like product is hydrolyzed into 1h-4h, 60 DEG C of -90 DEG C of dryings under 70 DEG C of -90 DEG C of bath temperatures
4h-8h, crushing, sieving, obtain double combed block copolymerization powders；Wherein, sieve selection mesh screen be 400 mesh
The mesh screen of -800 mesh；
Step 4：Described pair of combed block copolymerization powder is dissolved in liphophilic solvents, in 20 DEG C of -35 DEG C of water-bath temperature
The lower stirring 1h-4h of degree, obtains emulsion；Wherein, the powdered pair of combed block copolymerization powder with
100ppm-2000ppm concentration is dissolved in liphophilic solvents, and the mixing speed is 50rad/min-200rad/min；
Step 5：The emulsion is heated to 40 DEG C -50 DEG C, granulated by aerosol apparatus, is made described micro-
Spherical pair of combed block polymer profile control agent.
2. the preparation method of the double combed block polymer profile control agents of microspheroidal according to claim 1, wherein,
The long-chain epoxyalkane is included in oxepane, octylene oxide, 1,2- Epoxydodecanes and the 1,2- epoxy tetradecanes
One or more of combinations.
3. the preparation method of the double combed block polymer profile control agents of microspheroidal according to claim 1, wherein,
The acrylamido sulfonate include 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamido tetradecane sulfonic acid and
One or more of combinations in 2- acrylamido hexadecane sulfonic acid.
4. the preparation method of the double combed block polymer profile control agents of microspheroidal according to claim 1, wherein,
The pH adjusting agent include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium acid carbonate, saleratus,
One or more combinations in monoethanolamine, diethanol amine, triethanolamine and ammoniacal liquor.
5. the preparation method of the double combed block polymer profile control agents of microspheroidal according to claim 1, wherein,
Counted using the gross mass of the redox composite initiator as 100wt%, the raw material of the redox composite initiator
Composition includes the water of persulfate, bisulfites, aminated compounds and surplus, wherein, the persulfate, Asia
The mass ratio of disulfate and aminated compounds is 0.2wt%-20wt%：0.1wt%-10wt%：0.1wt%-30wt%.
6. the preparation method of the double combed block polymer profile control agents of microspheroidal according to claim 5, wherein,
The persulfate include ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate, the bisulfites include ammonium bisulfite,
Sodium hydrogensulfite or potassium bisulfite.
7. the preparation method of the double combed block polymer profile control agents of microspheroidal according to claim 5, wherein,
The aminated compounds includes N, N- diethyl ethylenediamines, diethylenetriamine, N, N, N ', N '-tetraethylethylenediamine,
N, N- diisopropyl ethylenediamine and N, N, N ', one or more of combinations in N '-tetraallylethylene diamine.
8. the preparation method of the double combed block polymer profile control agents of microspheroidal according to claim 1, wherein,
The liphophilic solvents include n-hexane, hexamethylene, benzene, toluene, carbon tetrachloride or chlorobenzene.
9. a kind of double combed block polymer profile control agents of microspheroidal, it is by described in claim any one of 1-8
What the preparation method of the double combed block polymer profile control agents of microspheroidal was prepared.
10. the double combed block polymer profile control agents of microspheroidal according to claim 9, wherein, the microspheroidal is double
The particle diameter of combed block polymer profile control agent is 2 μm -8 μm.
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