CN105985483A - Polymer particle for wrapping inorganic core and preparation method and application thereof - Google Patents
Polymer particle for wrapping inorganic core and preparation method and application thereof Download PDFInfo
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- CN105985483A CN105985483A CN201510062361.3A CN201510062361A CN105985483A CN 105985483 A CN105985483 A CN 105985483A CN 201510062361 A CN201510062361 A CN 201510062361A CN 105985483 A CN105985483 A CN 105985483A
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- 239000002245 particle Substances 0.000 title claims abstract description 65
- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 21
- 239000011147 inorganic material Substances 0.000 claims abstract description 21
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- -1 sorbitan fatty acid ester Chemical class 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 4
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 32
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000004576 sand Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000007771 core particle Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008398 formation water Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
Abstract
The invention provides a polymer particle for wrapping an inorganic core, a preparation method and application thereof. The preparation method comprises the following steps: 1) mixing 20-35 parts by weight of continuous phase with 6-15 parts by weight of emulsifier to prepare a first solution; 2) adding 0.5-5 parts by weight of inorganic material into the first solution to prepare a first mixed solution; 3) dissolving 10-20 parts by weight of acrylamide with 15-30 parts by weight of deionized water, adding 3-15 parts by weight of acrylic acid and 0.01-0.08 part by weight of N, N-methylene bisacrylamide, adjusting the degree of neutralization, and adding 0.1-0.2 part by weight of a first initiator to prepare a second solution; 4) adding the second solution into the first mixed solution to prepare a second mixed solution; 5) adding 0.01-0.08 weight part of second initiator to the second mixed solution in batches to prepare the polymer particles coating the inorganic core; wherein the surface of the inorganic material is not modified. The polymer particle for wrapping the inorganic core has stable property, simple process and low cost, and has good dispersibility and good plugging effect when being used for oilfield exploitation.
Description
Technical field
The invention belongs to oilfield exploitation technical field, be specifically related to a kind of polymer particles wrapping up inorganic core
And its preparation method and application.
Background technology
After deep profile controlling refers to blocking agent solidification or expands, reduce the permeability of high permeability formation, it is achieved the water blockoff displacement of reservoir oil
Effect.From eighties of last century sixties so far, deep profile controlling always improves the important hands of oil recovery
Section.Along with the carrying out of oil exploitation, reservoir geology structure also changes ceaselessly occurring, this geology
Change require used by profile control means change the most accordingly.Current existing profile control blocking agent, such as water
Though mud, oil based cement, lime cream, resin, activity viscous crude, water-soluble polymer gel etc. serve
Certain effect, but have that free settling, viscosity is big, poor fluidity, high in cost of production defect.
Notification number is that the patent documentation of CN102485830A discloses a kind of hud typed microgranule profile adjustment and oil displacement
Agent, after specifically the silane coupled dressing agent of the nanoparticle band double bond of 10-600nm being modified,
Form polymer shell by polyreaction on its surface again, finally give inorganic and organic component with chemistry
Hud typed inorganic/organic polymer composite particles profile control reservoir oil displacing agent that bond is closed, although this oil displacement agent exists
80 DEG C, salinity is to place 15 days under conditions of 1000mg/L, and Stability Analysis of Structures is decomposed not yet, but
Being the requirement to inorganic material high (need to be through chemical modification), operation complexity, use cost is high.
Summary of the invention
The present invention provides a kind of polymer particles wrapping up inorganic core and its preparation method and application, purpose to exist
In realizing the profile control agent that a kind of stable in properties, good fluidity, easily dispersion and plugging strength are big, and energy
Enough effective closure carrying out corresponding size according to different size type fractured reservoir, and technological process letter
Single, production cost is low, less demanding to raw material.
The preparation method of a kind of polymer particles wrapping up inorganic core of the present invention, comprises the steps:
1) stir after the continuous phase of 20-35 weight portion being mixed with the emulsifying agent of 6-15 weight portion, prepare the
One solution；
2) in the first solution, add the inorganic material of 0.5-5 weight portion and be allowed to disperse, preparing first and mix
Close liquid；
3) by after the acrylamide of the 10-20 weight portion deionized water dissolving with 15-30 weight portion, add
The acrylic acid of 3-15 weight portion and the N,N methylene bis acrylamide of 0.01-0.08 weight portion, agitated also
After regulation degree of neutralization, add the first initiator of 0.1～0.2 weight portion, prepare the second solution；
4) the second solution is added in the first mixed liquor, agitated, prepare the second mixed liquor；
5) the second initiator being dividedly in some parts 0.01-0.08 weight portion in the second mixed liquor carries out reaction system
Obtain the polymer particles of described parcel inorganic core.
The preparation method is that employing reversed emulsion polymerization, oiliness will be dispersed in by acrylamide
In solvent, and make it be scattered in oil phase by emulsifying agent further, formed " Water-In-Oil " type emulsion and
The polymerization carried out.Owing to adding mineral-type materials, the reaction meeting of polymer in the preparation process of polymer
Occur at inorganic material surface and then be covered in outside inorganic material formation with the form of physically encapsulation to wrap up inorganic
The polymer particles of core, can be used for oil reservoir passage is carried out plugging and profile con-trol, improves oil displacement efficiency.The present invention
Above-mentioned each component of the polymer particles of parcel inorganic core is the most commercially available.
" polymer particles of parcel inorganic core " of the present invention refers to comprise in polymerization reaction system nothing
Machine material, makes polymerizate attachment or covers at least part of surface of inorganic material.
According to embodiment of the present invention, prepared polymer particles has and is distributed than more uniform particle diameter,
Use as profile control agent and there is good suspension (being difficult to deposition), the most also there is good mobility.
In embodiment of the present invention, it is 10%～20% that the second initiator can be formulated as mass content
Aqueous solution uses, and employing is added in batches, is typically equally divided into by the aqueous solution volume of the second initiator
It is added for 2-3 time.
Further, described continuous phase is white oil, and described emulsifying agent is sorbitan fatty acid ester, i.e.
Span series.White oil of the present invention generally refers to through purifying, being hydrogenated with saturated positive structure narrow fraction
The mixing-in fat hydrocarbon of (300-305 DEG C), is generally divided into industrial grade white oil, cosmetics-stage white oil, medical grade
White oil, food-level white oil, the present invention uses industrial grade white oil.
The concrete application type of Span series emulsifying agent used in the present invention does not limits, and can be a kind of,
Can also be more than one mixture, and to mixed proportion also indefinite, can be such as Arlacel-40,
One or more in Arlacel-60, Arlacel-80 and Arlacel-85.
Further, described inorganic material can be hydrophilic fumed silica, Vermiculitum and dumb light powder
A kind of.Inorganic material without mesh number requirement, is not required to be processed by the present invention, can directly use,
Polymer can be realized according to the method for the present invention to be wrapped in outside inorganic material with physical form, and have
Higher stability.
Further, described first initiator is sodium sulfite, and described second initiator is Ammonium persulfate..
Further, described step 3) in regulation degree of neutralization to 50-80%.Degree of neutralization refers to neutralize reaction
The degree carried out, is to represent with the mol ratio of two kinds of reactants, the most in the present invention, just with hydroxide
Sodium and acrylic acid mol ratio represent degree of neutralization.The water absorption of polymer is affected relatively big by degree of neutralization, if
Degree of neutralization is too low, and polymerization speed can increase, and is easily generated secondary cross-linking reaction, and making strand and network is contraction
State therefore water absorption is relatively low.Along with the increase of degree of neutralization, polymerization speed reduces, and water absorption can increase therewith
Height, but degree of neutralization is too high, can consume a large amount of reactant, and the productivity that will also result in polyreaction reduces,
So controlling degree of neutralization between 50-80%.
It is possible to further the sodium hydrate aqueous solution regulation degree of neutralization using mass content to be 10～20%.
Acrylic acid in polyreaction is neutralized by the sodium hydrate aqueous solution for example with 10～20%.
Further, described reaction temperature is 37～43 DEG C, and the time is 3-5h.This temperature not only facilitates
Inorganic material is carried out fully wrapped around by continuous phase with emulsifying agent with monomer, makes inorganic material, monomer continuously
With the system of emulsifying agent has good dispersibility, and contribute to the carrying out of polyreaction.Temperature
The too low initiation to polyreaction causes obstacle, and the too high meeting of temperature causes chain tra nsfer, affects molecular weight distribution,
Thus affect properties of product.
Further, the present invention also provides for a kind of polymer particles wrapping up inorganic core, uses any of the above-described
Described preparation method prepares.
Further, a kind of polymer particles wrapping up inorganic core of the present invention can be applied at oilfield exploitation
The plugging and profile con-trol in crack.
The enforcement of the present invention, at least has the advantage that
1, raw material be need not too much limit by the polymer particles of the parcel inorganic core of the present invention, especially without
Inorganic material need to be modified, it is also ensured that the stability of nucleocapsid parcel, operate simply, use into
This is low.
2, the polymer particles dispersion of the parcel inorganic core of the present invention is high, viscosity is low, good fluidity, easily
Inject in oil reservoir.
3, the polymer particles dilatancy of the parcel inorganic core of the present invention is strong, for the crack sealing ratiod of oil reservoir
High.
4, the polymer particles of the parcel inorganic core of the present invention can adapt to difference by changing inorganic core particle diameter
Type fractured reservoir, oil reservoir conformability is good.
Accompanying drawing explanation
Fig. 1 is the microscope figure of the polymer particles of the embodiment of the present invention 1；
Fig. 2 is the microscope figure of the polymer particles of the embodiment of the present invention 2；
Fig. 3 is the microscope figure of the polymer particles of the embodiment of the present invention 3；
Fig. 4 is the microscope figure of the polymer particles of the embodiment of the present invention 4；
Fig. 5 is the initial particle figure of the polymer particles of the embodiment of the present invention 1；
Fig. 6 is the interfacial tension figure of the polymer particles of the embodiment of the present invention 1；
Fig. 7 is the swelling variation diagram of the polymer particles of the embodiment of the present invention 1.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the reality of the present invention
Execute example, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described
Embodiment be a part of embodiment of the present invention rather than whole embodiments.Based on the reality in the present invention
Executing example, it is every other that those of ordinary skill in the art are obtained under not making creative work premise
Embodiment, broadly falls into the scope of protection of the invention.
Embodiment 1
At 40 DEG C, mixing speed is under 1000r/min, by 27 weight portion white oils and 7 weight portion Arlacel-40s
Mix homogeneously, prepares the first solution.0.85 part by weight of hydrophilic gas phase titanium dioxide is added in the first solution
Silicon, stirs, and prepares the first mixed liquor.By 10 parts by weight propylene amide with 18 weight portion deionizations
Water dissolution, adds 5.5 parts by weight of acrylic acid, 0.05 weight portion N,N methylene bis acrylamide, stirs
Mix after making to be completely dissolved, with 20% sodium hydrate aqueous solution regulation degree of neutralization to 70%.Now, add
0.1 weight portion sodium sulfite stirring makes to be completely dissolved, and prepares the second solution.Second solution is added first
In mixture, stir 1h, prepare the second mixed liquor.15% over cure is added at twice in the second mixed liquor
(wherein, Ammonium persulfate. solid is 0.05 weight portion to acid aqueous ammonium, and controls the interval of twice addition
For 30min), it is cooled to 25 DEG C of dischargings after stirring 4h, prepares the polymer particles system of parcel inorganic core,
Corresponding microscope figure is shown in Fig. 1, and places 24h and have no appearance layering.
The present embodiment is wrapped up the polymer particles of hydrophilic fumed silica As time goes on
Interfacial tension is monitored, the results are shown in Table 1, and carried out curve according to the change of this interfacial tension and paint
System, is shown in Fig. 6.
The polymer particles that the present embodiment wraps up hydrophilic fumed silica carries out the inspection of initial particle
Survey, the detection of interfacial tension and swellbility monitoring, result is shown in Fig. 5, Fig. 6 and Fig. 7.
As shown in Figure 5: its particle diameter of polymer particles of parcel inorganic core prepared by the present embodiment the most all divides
Cloth is between 400-600nm, and mean diameter is about 500nm, and particle diameter distribution is homogeneous, there is no appearance grain
The situation that footpath is distributed in a jumble, it may thus be appreciated that the polymer particles dispersion of parcel inorganic core prepared by the method
Good.
As shown in Figure 6: the polymer particles of parcel inorganic core prepared by the present embodiment, its interfacial tension with
The prolongation of time to be gradually reduced, therefore there is good mobility and shear resistant, adjust for oil reservoir
It is capable of when cuing open oil reservoir is rapidly injected.
As shown in Figure 7: the polymer particles swellability of parcel inorganic core prepared by the present invention is good, its with
The passage of time, gradually imbibition, thus reservoir fractures is carried out the closure of maximum magnitude.
Embodiment 2
At 38 DEG C, mixing speed is under 1200r/min, by 20 weight portion white oils, 6 weight portion Arlacel-40s, 2
Weight portion Arlacel-80 mix homogeneously, prepares the first solution.1.5 weight portion Vermiculitums are added in the first solution
(800 mesh), stirs, and prepares the first mixed liquor.12 parts by weight propylene amide are gone with 16 weight portions
Ionized water dissolves, and adds 3.5 parts by weight of acrylic acid, 0.03 weight portion N,N methylene bis acrylamide,
After stirring makes to be completely dissolved, the sodium hydrate aqueous solution with 15% regulates degree of neutralization to 60%.Now, then add
Enter 0.1 weight portion sodium sulfite stirring to make to be completely dissolved, prepare the second solution.Second solution is added the
In one mixture, stir 1.5h, prepare the second mixed liquor.10% mistake is added at twice in the second mixed liquor
(wherein, Ammonium persulfate. solid is 0.02 weight portion to ammonium sulfate solution, controls being spaced apart of twice addition
20min), being cooled to 28 DEG C after stirring 5h, the mean diameter preparing above-mentioned parcel inorganic core is that 800nm gathers
Compound microparticle system, corresponding microscope figure is shown in Fig. 2, and places 24h and have no appearance layering.
As time goes on interfacial tension is entered by the polymer particles that the present embodiment wraps up Vermiculitum
Row monitoring, the results are shown in Table 1.
Embodiment 3
At 42 DEG C, mixing speed is under 1100r/min, by 20 weight portion white oils, 15 weight portion Arlacel-60s
Mix homogeneously, prepares the first solution.In the first solution, add 1 weight portion dumb light powder, stir, system
Obtain the first mixed liquor.20 parts by weight propylene amide are dissolved by 28.67 parts by weight of deionized water, adds 15
Parts by weight of acrylic acid, 0.08 weight portion N,N methylene bis acrylamide, after stirring makes to be completely dissolved, use
The sodium hydrate aqueous solution regulation degree of neutralization of 20% is to 80%.Now, 0.2 weight portion bisulfite is added
Sodium stirring makes to be completely dissolved, and prepares the second solution.Second solution is added in the first mixture, stirs 1.5h,
Prepare the second mixed liquor.Ammonium persulfate aqueous solution (wherein, over cure is added at twice in the second mixed liquor
Acid ammonium solid is 0.06 weight portion, and control twice addition be spaced apart 40min), cool down after stirring 5h
To 28 DEG C, prepare above-mentioned parcel inorganic core particle diameter be mean diameter be 1 μm polymer particles system, right
The microscope figure answered is shown in Fig. 3, and places 24h and have no appearance layering.
The present embodiment is wrapped up the polymer particles of dumb light powder As time goes on to interfacial tension
It is monitored, the results are shown in Table 1.
Embodiment 4
At 43 DEG C, mixing speed is under 1200r/min, by 35 weight portion white oils, 10 weight portion Arlacel-60s,
5 weight portion Arlacel-80 mix homogeneously, prepare the first solution.4.5 part by weight of hydrophilic are added in the first solution
Property aerosil, stir, prepare the first mixed liquor.By 18 parts by weight propylene amide with 24.87
Parts by weight of deionized water is dissolved, and adds 10.5 parts by weight of acrylic acid, 0.03 weight portion N, N-di-2-ethylhexylphosphine oxide third
Acrylamide, after stirring makes to be completely dissolved, the sodium hydrate aqueous solution with 10% regulates degree of neutralization to 50%.This
Time, add 0.1 weight portion sodium sulfite stirring and make to be completely dissolved, prepare the second solution.Molten by second
Liquid adds in the first mixture, stirs 2h, prepares the second mixed liquor.Add in the second mixed liquor at twice
(wherein, Ammonium persulfate. solid is 0.03 weight portion, and controls twice addition to enter ammonium persulfate aqueous solution
Be spaced apart 20min), stirring 4.5h after be cooled to 27 DEG C, prepare above-mentioned parcel inorganic core particle diameter be flat
All particle diameters are 5 μm polymer particles systems, and corresponding microscope figure is shown in Fig. 4 and places 24h and have no
Layering occurs.
The present embodiment is wrapped up the polymer particles of hydrophilic fumed silica As time goes on
Interfacial tension is monitored, the results are shown in Table 1.
From Fig. 1-Fig. 4: the polymer particles of the parcel inorganic core obtained by embodiment 1-4 is according to reactant
Different content and inorganic matter selected by variety classes, the parcel inorganic core of various particle diameter can be prepared
Polymer particles is used for blocking the duct of oil reservoir, therefore, it is possible to adapt to dissimilar Fractured oil
Hiding, oil reservoir conformability is good.
From Fig. 1 and Fig. 4: although embodiment 1,4 has selected identical inorganic material, but pass through
Control the content of reactant, still can prepare the polymer particles of parcel inorganic core of different-grain diameter to not
Block with type fractured reservoir.
Interfacial tension (mN/M) the monitoring table of the polymer particles of table 1 embodiment 1-4
As shown in Table 1: the polymer particles of parcel inorganic core prepared by the present invention, its interfacial tension along with
The prolongation of time is gradually reduced, and therefore has good mobility and shear resistant, adjusts for oil reservoir
It is capable of when cuing open oil reservoir is rapidly injected.
Reference examples
The polymer particles of the parcel inorganic core of this reference examples, uses 0.14kg azodiisobutyronitrile as drawing
Send out agent in step 4) middle addition, inorganic material elects surface as through 3-(methacryloxypropyl) propyl group front three
The silica dioxide granule 2.84kg that TMOS is modified, remaining operating process is same as in Example 1.
Test example 1
Prepared by the polymer particles of employing parcel inorganic core prepared by above-described embodiment 1-4 and reference examples
Polymer particles carries out the test of plugging strength in the way of fill out sand tube simulation.
Concrete operations are: be first that 400mD fill out sand tube formation water carries out saturated by 15 permeabilities, be divided into 5
Group (numbering 1-5), often 3 (numbered a-c) of group.All flows with 2ml/min are above-mentioned to group 1 injection
Brand-new embodiment 1 wraps up the polymer particles of inorganic core, wraps up nothing to the group 2 above-mentioned brand-new embodiment 2 of injection
The polymer particles of machine core, wraps up the polymer particles of inorganic core to the group 3 above-mentioned brand-new embodiment 3 of injection,
The polymer particles of inorganic core is wrapped up, to the group 5 above-mentioned brand-new pair of injection to the group 4 above-mentioned brand-new embodiment 4 of injection
Wrap up the polymer particles of inorganic core as usual, until stopping when concentration is 5000mg/L, subsequently by fill out sand tube
Closed at both ends.
Test example 1-1: after preserving 3 days under conditions of 130 DEG C, with 1ml/min flow to above-mentioned numbered a
Fill out sand tube inject formation water, until the fill out sand tube port of export flows out the first drop of liquid, and constantly have liquid later
Body flows out, and now the reading of port pressure table is the breakthrough pressure Pm, breakthrough pressure Pm of corresponding embodiment
The biggest, plugging strength is the highest.
Test example 1-2: after preserving 10 days under conditions of 130 DEG C, to the fill out sand tube of above-mentioned numbered b with examination
Test example 1-1 and carry out identical operation.
Test example 1-3: after preserving 20 days under conditions of 130 DEG C, to the fill out sand tube of above-mentioned numbered c with examination
Test example 1-1 and carry out identical operation.
Reference example: do not add any blocking agent carries out, with formation water, the back-up sand that saturated permeability is 400mD
Pipe, carries out identical operation with test example 1-1 and records breakthrough pressure Pm as 0.2MPa.
Concrete outcome is shown in Table 2.
The plugging strength test result of the polymer particles of table 2 embodiment 1-4 and reference examples 1
As seen from the results in Table 2:
The plugging strength of the polymer particles of the parcel inorganic core that 1, prepared by the present invention is big, and at 130 DEG C
Closure effect is still effectively played under high temperature.
2, the inorganic material of the present invention is without any chemical modification, single with physical form formation polymer pair
The parcel of inorganic material, preserves 20 days its character the most stable, additionally it is possible to enter hole under the high temperature conditions
The closure of row high intensity, therefore uses the polymer particles of the preparation method preparation parcel inorganic core of the present invention
Not only to raw material without processing, operation is simple, and use cost is low, and can obtain good plugging effect.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, rather than right
It limits；Although the present invention being described in detail with reference to foregoing embodiments, this area common
Skilled artisans appreciate that the technical scheme described in foregoing embodiments still can be modified by it,
Or the most some or all of technical characteristic is carried out equivalent；And these amendments or replacement, and
The essence not making appropriate technical solution departs from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the preparation method of the polymer particles wrapping up inorganic core, it is characterised in that include walking as follows
Rapid:
1) stir after the continuous phase of 20-35 weight portion being mixed with the emulsifying agent of 6-15 weight portion, prepare the
One solution；
2) in the first solution, add the inorganic material of 0.5-5 weight portion and be allowed to disperse, preparing first and mix
Close liquid；
3) by after the acrylamide of the 10-20 weight portion deionized water dissolving with 15-30 weight portion, add
The acrylic acid of 3-15 weight portion and the N,N methylene bis acrylamide of 0.01-0.08 weight portion, agitated also
After regulation degree of neutralization, add the first initiator of 0.1～0.2 weight portion, prepare the second solution；
4) the second solution is added in the first mixed liquor, prepare the second mixed liquor；
5) the second initiator being dividedly in some parts 0.01-0.08 weight portion in the second mixed liquor reacts,
Prepare the polymer particles of parcel inorganic core；
Wherein, described inorganic material is the inorganic material that surface free is modified.
Preparation method the most according to claim 1, it is characterised in that described first solution continuous
Being white oil mutually, described emulsifying agent is sorbitan fatty acid ester.
Preparation method the most according to claim 2, it is characterised in that described sorbitan fatty
Acid esters is one or more in Arlacel-40, Arlacel-60, Arlacel-80 and Arlacel-85.
Preparation method the most according to claim 1, it is characterised in that described inorganic material is hydrophilic
One in property aerosil, Vermiculitum and dumb light powder.
Preparation method the most according to claim 1, it is characterised in that described first initiator is sub-
Sodium bisulfate, described second initiator is Ammonium persulfate..
Preparation method the most according to claim 1, it is characterised in that described step 3) middle regulation
Degree of neutralization is to 50-80%.
Preparation method the most according to claim 6, it is characterised in that use mass content be 10～
The sodium hydroxide solution regulation degree of neutralization of 20%.
Preparation method the most according to claim 1, it is characterised in that the temperature of described reaction is
37～43 DEG C, the time is 3-5h.
9. the polymer particles wrapping up inorganic core, it is characterised in that according to claim 1～8 institute
The method stated prepares.
10. the polymer particles of the parcel inorganic core described in claim 9 be applied in oilfield exploitation right
The plugging and profile con-trol in crack.
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| CN110410047A (en) * | 2019-06-17 | 2019-11-05 | 中国石油天然气股份有限公司 | Oil displacement method for high-gas-content oil field and gas energy release oil displacement agent thereof |
| CN111704697A (en) * | 2020-05-29 | 2020-09-25 | 中国石油天然气股份有限公司 | Core-shell type hyperbranched nano-polymer and preparation method thereof |
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| CN110410047A (en) * | 2019-06-17 | 2019-11-05 | 中国石油天然气股份有限公司 | Oil displacement method for high-gas-content oil field and gas energy release oil displacement agent thereof |
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| CN111704697B (en) * | 2020-05-29 | 2022-06-03 | 中国石油天然气股份有限公司 | Core-shell type hyperbranched nano-polymer and preparation method thereof |
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Application publication date: 20161005 |