CN108300436A - A kind of fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agent, preparation method and its application - Google Patents
A kind of fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agent, preparation method and its application Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000005060 rubber Substances 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002981 blocking agent Substances 0.000 title claims abstract description 38
- 239000011148 porous material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 17
- 239000004902 Softening Agent Substances 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002390 adhesive tape Substances 0.000 claims description 11
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- 238000004073 vulcanization Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 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 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229920002351 sodium apolate Polymers 0.000 claims description 4
- 229960003968 sodium apolate Drugs 0.000 claims description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 235000005128 Sapium sebiferum Nutrition 0.000 claims 1
- 244000057114 Sapium sebiferum Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 11
- 230000033558 biomineral tissue development Effects 0.000 abstract description 3
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- 239000003292 glue Substances 0.000 description 4
- 229940059939 kayexalate Drugs 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
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- 239000004519 grease Substances 0.000 description 3
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- 238000012546 transfer Methods 0.000 description 3
- 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 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 238000010334 sieve classification Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MQVMJSWYKLYFIG-UHFFFAOYSA-N propane-1-sulfonic acid;sodium Chemical compound [Na].CCCS(O)(=O)=O MQVMJSWYKLYFIG-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
A kind of fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agent of present invention proposition, preparation method and its application, belong to functional polymer material field, which has that mechanical strength is high, resistance to salinity ability is strong, high tenacity, high volume expansion ratio, is not precipitated and the performance characteristics such as tack.The technical solution includes the raw material of following parts by weight：Nitrile rubber is 100 parts, 50 110 parts of water-absorbing resin, 5 15 parts of oil swell resin, 15 30 parts of reinforcing agent, softening agent are 0.5 2 parts, accelerating agent is 25 parts, zinc oxide is 36 parts and vulcanizing agent is 0.5 3.5 parts.The present invention can be applied in the fractured-cavernous carbonate reservoir indepth plugging of high temperature and high salt high mineralization.
Description
Technical field
The invention belongs to functional polymer material field more particularly to a kind of fracture-pore reservoir oil-water selectivity self-expanding rubbers
Glue blocking agent, preparation method and its application.
Background technology
The oil and gas reserves of carbonate rock hydrocarbon reservoir is huge, wherein 30% or more is fracture hole type oil-gas reservoir.Such oil-gas reservoir by
Solution cavity, crack and dissolution pore composition, by more synergistic effects such as tectonic diastrophism, karst superimposed structure and multi-stage accumulation, oil reservoir storage
Layer forms the spatial distribution of discontinuity, and reservoir heterogeneity is extremely strong, and matrix does not have storage and oozes ability, and grease system is extremely multiple
Miscellaneous, exploitation carbonate reservoir has higher technical difficulty.
Carbonate Rocks In Tahe Oilfield fracture-pore reservoir majority is high temperature (100 DEG C or more), (100000mg/L or more) with high salt
Oil reservoir, anisotropism is strong, underground oil water relation is complicated and water exit interval is not easy determination etc., leads to conventional water-plugging technology adaptability
Difference；Fractured-vuggy reservoir circulation passage flow conductivity is strong, formation pressure gradient is low, oil reservoir ultra-deep and high temperature and high salt (buried depth 5400-
6600m, temperature be 120-140 DEG C, salinity 210-240g/L) etc. characteristics seriously constrain conventional High Intensity or selective blocking
Effective application of agent.
With the deep development of oil reservoir, oil reservoir rises in the middle and later periods of exploitation, moisture content, some local even superelevation contain
Water rate, reservoir pressure decaying, waterflood efficiency present variation trend, water drive " short circuit " problem is increasingly severe, flow mutually alter with unidirectionally
Become main development contradiction, the recovery ratio only 14.8% of system in Tahe Oilfield by effect, oil recovery technique improves recovery ratio as can get a promotion
Also larger space.
Currently, water blockoff transfer drive mostly is carried out using polymer microballoon, but its problem is that the polymer of 1. water blockoff transfer drive is micro-
Ball stock size is smaller (being calculated with nm), and Microspheres Technique is not suitable for macropore and blocks, such as the oil field of northwest China
Fracture-pore reservoir is not good enough in high permeability formation band adaptability；2. previous microballoon in aqueous oil reservoir using gel as core, to oil reservoir
Long-time stability have an impact；3. the raw material of microballoon come from organic chemical industry's monomer, cost is higher, the synthetic technology of microballoon and application
Cost it is higher.Also, show polymer microballoon performance in heatproof, stability, high mineralization in conjunction with the field application of oil field transfer drive
The requirement at scene cannot be met in terms of the lower expansion character of degree and cost.For western part reservoir characteristics, inorganic gel blocking layer technology
It researches and develops successfully, but the technology application aspect is not mature enough, it cannot be from solving the problems, such as at all.
In addition, phenolic resin is widely applied in terms of Water in Water Shutoff in Oil Field.It, first will be hot when resin implementing process operates
The preshrunk liquid of curable type phenolic resin is mixed with curing agent, then squeezes into water layer, can under the action of curing agent and formation temperature
It is cross-linked to form the insoluble resin structure not melted whithin a period of time, to block water layer.The advantages of resinae plugging agent is can be with
Formation pore is injected, and generates enough plugging strengths, the different types geological conditions such as crack, hole, hole can be blocked
Stratum.After resin chemical solidification, plugging agent forms chemical bond with sand face influences the fuel-displaced of oil duct, shadow to block stratum
Ring recovery ratio.Therefore, exploitation new type high temperature deep profile controlling blocking agent be solve high temperature, formation stimulation augmented injection with high salt necessary means.
Invention content
A kind of fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agent of present invention proposition, preparation method and its application,
The rubber blocking agent has that mechanical strength is high, resistance to salinity ability is strong, high tenacity, high volume expansion ratio, is not precipitated and tack
Etc. performance characteristics, can be effectively used for the fractured-cavernous carbonate reservoir indepth plugging of high temperature and high salt.
In order to achieve the above object, an aspect of of the present present invention provides a kind of fracture-pore reservoir oil-water selectivity self-expanding rubber
Glue blocking agent includes the raw material of following parts by weight：Nitrile rubber be 100 parts, 50-110 parts of water-absorbing resin, oil swell resin 5-15
Part, 15-30 parts of reinforcing agent, softening agent are 0.5-2 parts, accelerating agent is 2-5 parts, zinc oxide is 3-6 parts and vulcanizing agent is 0.5-3.5
Part.
Preferably, including the raw material of following parts by weight：Nitrile rubber be 100 parts, 70-90 parts of water-absorbing resin, oil-soluble
8-10 parts of resin, 20-30 parts of reinforcing agent, softening agent are 1.0-2 parts, accelerating agent is 3-5 parts, zinc oxide is 4-6 parts and vulcanizing agent
It is 1.0-2.5 parts.
Preferably, the water-absorbing resin is in kayexalate, sodium apolate or polyallyl sodium sulfonate
Or mixtures thereof one kind.
Preferably, the oil swell resin is in hydrogenated petroleum resin, phenolic resin, butadiene-styrene rubber or polyvinyl resin
Or mixtures thereof one kind.
Preferably, the vulcanizing agent is or mixtures thereof benzoyl peroxide, cumyl peroxide.
Preferably, the reinforcing agent is or mixtures thereof carbon black 550, white carbon.
Preferably, the softening agent is stearic acid, the accelerating agent is zinc oxide.
The fracture-pore reservoir grease choosing that another aspect provides a kind of as described in any of the above-described technical solution
The preparation method of selecting property self-expanding rubber blocking agent, includes the following steps：
1) the nitrile rubber mill that parts by weight are 100 parts is plasticated, after being slowly added into 15-30 parts of reinforcing agent, adds suction
50-110 parts of water-resin, is then kneaded 5-10min；
2) 0.5-2 parts of softening agent is sequentially added into above-mentioned system, accelerating agent is 2-5 parts, is kneaded 10-30min；
3) and then zinc oxide is added as 3-6 parts, 5-15 parts of oil swell resin, is kneaded 20-40min；
4) 0.5-3.5 parts of vulcanizing agent is added, after being kneaded 3-5min, uniform bottom sheet obtains rubber compound, cooling；
5) rubber compound after cooling is squeezed out with thin adhesive tape, press cure is carried out to adhesive tape at 170 DEG C, obtains vulcanizate
Item；
6) by the vulcanization adhesive tape mechanical crushing of gained, particle is classified by screening, obtains the different self-expanding rubber of grain size
Glue blocking agent.
Preferably, the particle size range of the self-expanding rubber blocking agent is 0.5-1.5mm.
Another aspect of the invention provides a kind of fracture-pore reservoir grease choosing as described in any of the above-described technical solution
Selecting property self-expanding rubber blocking agent is in 120 DEG C -140 DEG C of temperature, salinity≤20 × 104The fractured-cavernous carbonate reservoir of mg/L is deep
Application in portion.
Compared with the prior art, advantage is the present invention：
1, the fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agent provided by the invention that is suitable for is using nitrile rubber as base
Body material is prepared into after being aided with reinforcing agent, water-absorbing resin, oil swell resin etc. and beginning to pratise mixing through vulcanization, have mechanical strength it is high,
Resistance to salinity ability is strong, high tenacity, high volume expansion ratio, is not precipitated and the performance characteristics such as tack.
2, rubber blocking agent provided by the invention is met water and is slowly expanded, and oil swell resin is sustained molten under the action of a small amount of oil product
Swollen precipitation gradually forms at high temperature between particle surface, particle to be effectively adhered, and high temperature resistant salt resistance is formed after water swelling
High intensity expanded elastomers, effectively block large fracture, block exhalant canal, can be effectively used for temperature at 130 DEG C, salinity≤
20×104The fractured-cavernous carbonate reservoir indepth plugging of mg/L.
3, rubber blocking agent provided by the invention is to reduce water outlet, steady oil control water, the best measure for improving recovery ratio, is had wide
Wealthy application prospect and preferable economic benefit and actual application value.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
An embodiment of the present invention provides a kind of fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agents, including following weight
The raw material of part：Nitrile rubber is 100 parts, 50-110 parts of water-absorbing resin, 5-15 parts of oil swell resin, 15-30 parts of reinforcing agent, softens
Agent is 0.5-2 parts, accelerating agent is 2-5 parts, zinc oxide is 3-6 parts and vulcanizing agent is 0.5-3.5 parts.
The formula of fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agent that above-described embodiment provides is with nitrile rubber
Basis material, be aided with water-absorbing resin, oil swell resin, reinforcing agent, softening agent, crosslinking agent, accelerating agent begin to pratise mixing after through vulcanization
Reaction is prepared into, and has that mechanical strength is high, resistance to salinity ability is strong, high tenacity, high volume expansion ratio, is not precipitated and tack
Etc. performance characteristics.After the rubber blocking agent meets water, hydrone and the hydrophilic radical of hydrophilic agent in rubber in conjunction with and slowly expand, moisture
Son is gradually infiltrated by the surface of rubber inside rubber until expansion balance is fully achieved in rubber.In the expansion process of rubber,
Oil swell resin inside rubber is precipitated along the channel of expansion to the surface of rubber particles, is sustained under the action of a small amount of oil product
Swelling, when temperature be higher than macromolecule resin glass transition temperature, when close to flow temperature, between the rubber particles of expansion by
It is gradually formed and is effectively adhered, the population for forming bigger blocks system, reaches the plugging effect of water blockoff, forms high temperature resistant salt resistance
High intensity expanded elastomers effectively block large fracture, block exhalant canal, can be effectively used for the fracture hole of high temperature and high salt high salinity
In type Carbonate Reservoir indepth plugging.
In a preferred embodiment, oil reservoir oil-water selectivity self-expanding rubber blocking agent may also include the original of following parts by weight
Material：Nitrile rubber is 100 parts, 70-90 parts of water-absorbing resin, 8-10 parts of oil-soluble resin, 20-30 parts of reinforcing agent, softening agent are
1.0-2 parts, accelerating agent be 3-5 parts, zinc oxide is 4-6 parts and vulcanizing agent is 1.0-2.5 parts.The rubber being prepared by the formula
Blocking agent advantageously, can more effectively be applied to height in terms of mechanical strength, resistance to salinity ability, toughness and volume expansion ratio
In the fractured-cavernous carbonate reservoir indepth plugging of temperature high salinity with high salt.
In a preferred embodiment, the water-absorbing resin is kayexalate, sodium apolate or polyallyl
Or mixtures thereof one kind in sodium sulfonate.In the present embodiment, used kayexalate, sodium apolate, polyene
The hydrophilic functional groups of propyl sulfonic acid sodium are sulfonic group, it will not lose hydrophilic with calcium and magnesium bivalent cation formation chemical crossbond
Property, water swellability can be shown in 200,000 mineralized waters, salt tolerance is preferable.Meanwhile above-mentioned water-absorbing resin also with oil-soluble
Resin butadiene-styrene rubber has preferable compatibility.It is understood that the present embodiment is not limited to cited water-absorbing resin, also
It can be the resin well-known to those skilled in the art with identity function effect.
In a preferred embodiment, the oil swell resin is hydrogenated petroleum resin, phenolic resin, butadiene-styrene rubber or poly- second
Or mixtures thereof one kind in olefine resin.It is understood that the present embodiment is not limited to cited oil swell resin, also
It can be the resin well-known to those skilled in the art with identity function effect.
In a preferred embodiment, the vulcanizing agent is or mixtures thereof benzoyl peroxide, cumyl peroxide.
In one preferred embodiment, the reinforcing agent is or mixtures thereof carbon black 550, white carbon.In a preferred embodiment, the softening
Agent is stearic acid, and the accelerating agent is zinc oxide.It is understood that above-described embodiment is not limited to cited reinforcement
Agent, softening agent and accelerating agent can also be the compound well-known to those skilled in the art with identity function effect.
The embodiment of the present invention additionally provides a kind of oil reservoir oil-water selectivity self-expanding as described in any of the above-described embodiment
The preparation method of rubber blocking agent, includes the following steps：
1) the nitrile rubber mill that parts by weight are 100 parts is plasticated, after being slowly added into 15-30 parts of reinforcing agent, adds suction
50-110 parts of water-resin, is then kneaded 5-10min；
2) 0.5-2 parts of softening agent is sequentially added into above-mentioned system, accelerating agent is 2-5 parts, is kneaded 10-30min；
3) and then zinc oxide is added as 3-6 parts, 5-15 parts of oil swell resin, is kneaded 20-40min；
4) 0.5-3.5 parts of vulcanizing agent is added, after being kneaded 3-5min, uniform bottom sheet obtains rubber compound, cooling；
5) rubber compound after cooling is squeezed out with thin adhesive tape, press cure is carried out to adhesive tape at 170 DEG C, obtains vulcanizate
Item；
6) by the vulcanization adhesive tape mechanical crushing of gained, particle is classified by screening, obtains the different self-expanding rubber of grain size
Glue blocking agent.
A kind of preparation method of the rubber blocking agent mentioned by above-described embodiment is present embodiments provided, which uses
Conventional method is kneaded above-mentioned component, obtains required vulcanization adhesive tape by vulcanizing treatment, then uses machinery as required
Vibrosieve mode to after crushing particle be classified, obtain particle size range 0.5-1.5mm rubber blocking agent.Be prepared into for
The blocking agent of different-grain diameter, primarily to adapting to the need that fractured-cavernous carbonate reservoir deep different reservoir flaw size blocks
It wants, to achieve the purpose that reduce water outlet, steady oil control water, improve recovery ratio.
The embodiment of the present invention additionally provides a kind of oil reservoir oil-water selectivity self-expanding as described in any of the above-described embodiment
Rubber blocking agent is in 120 DEG C -140 DEG C of temperature, salinity≤20 × 104Answering in the fractured-cavernous carbonate reservoir deep of mg/L
With.The rubber blocking agent that above-described embodiment provides has strong mechanical strength height, resistance to salinity ability, high tenacity, high volume expansion times
Rate is not precipitated and the performance characteristics such as tack, and meeting water can slowly expand, and oil swell resin is sustained under the action of a small amount of oil product
Swelling is precipitated to gradually form at high temperature between particle surface, particle and effectively be adhered, and high temperature resistant can be formed after water swelling
The high-strength gel of salt resistance.Therefore, large fracture can be effectively blocked, exhalant canal is blocked, is used especially for high temperature and high salt high mineralization
In the fractured-cavernous carbonate reservoir indepth plugging of degree.
In order to become apparent from the oil reservoir oil-water selectivity self-expanding rubber blocking agent introduced the embodiment of the present invention in detail and provided,
Preparation method and its application, are described below in conjunction with specific embodiment.
Embodiment 1
100 parts of input open mills of nitrile rubber are subjected to plasticating for raw rubber, metering part in formula system is weighed by table 1
Number, then sequentially adds mill by the reinforcing agent of weighing, softening agent, accelerating agent, zinc oxide, oil swell resin, vulcanizing agent one by one
It carries out being kneaded in machine and be uniformly mixed, process rubber compound, it is cold to set for 24 hours.Rubber compound is put into mold, in 10Mpa, 170 DEG C of items
Rubber vulcanization is carried out with vulcanizing press under part, obtains vulcanizate.The vulcanizate of preparation is subjected to mechanical crushing with pulverizer, then
The different rubber particles of grain size are obtained after vibrating screen sieve classification.
Embodiment 2
The preparation method is the same as that of Example 1, and the parts by weight for differing only in each component be added are different.Each component specifically adds
The mass fraction entered is shown in Table 1.
Embodiment 3
The preparation method is the same as that of Example 1, and the parts by weight for differing only in each component be added are different.Each component specifically adds
The mass fraction entered is shown in Table 1.
Embodiment 4
The preparation method is the same as that of Example 1, and the parts by weight for differing only in each component be added are different.Each component specifically adds
The mass fraction entered is shown in Table 1.
Comparative example 1
100 parts of nitrile rubber is put into open mill and is plasticated, it is soft then by 60 parts of high hydroscopic resin Sodium Polyacrylate
Agent 0.5 divides, 3 parts of accelerating agent, and zinc oxide 3 divides, and 1 part of reinforcing agent 20, vulcanizing agent are sequentially added in open mill and are kneaded, added
Work goes out rubber compound, cold to set for 24 hours.Rubber compound is put into mold, sizing material is carried out with vulcanizing press under the conditions of 10Mpa, 170 DEG C
Vulcanization, obtains vulcanizate.The vulcanizate of preparation is subjected to mechanical crushing with pulverizer, then grain is obtained after vibrating screen sieve classification
The different rubber particles of diameter.
Comparative example 2
For preparation method with comparative example 1, the parts by weight for differing only in each component be added are different.Each component specifically adds
The mass fraction entered is shown in Table 1.
The addition statistical form of each component in table 1 embodiment 1-4 and comparative example 1-2
Performance test
Following performance test is carried out to the preparation-obtained rubber particles of above-described embodiment 1-4 and comparative example 1-2, and auxiliary
It is illustrated with relevant industries standard, test result is as shown in table 2.
The performance aggregation of rubber particles obtained by 2 each embodiment of table
By 2 data analysis of table it is found that the material processed in the rubber material and comparative example that the present invention processes is in room temperature mechanics
Aspect of performance difference is little, but just expansion and the functional aspect of adhesion have huge difference.In formulation examples provided by the invention
The hydrophilic agent used is kayexalate, has preferable salt tolerance, the volume expansion ratio in 200,000 mineralized water
Between 250-310%, the hydrophilic agent used in comparative example is polyacrylic acid sodium salt, hardly swollen in 200,000 mineralized water
Swollen, salt tolerance is poor.In addition, also using oil-soluble resin in inventive formulation so that in 130 DEG C of mines after rubber particles expansion
Change water in have can adhesive, and comparative example processing particle in 130 DEG C of water do not have adhesive.
Claims (10)
1. a kind of fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agent, which is characterized in that include the raw material of following parts by weight：
Nitrile rubber is 100 parts, 50-110 parts of water-absorbing resin, 5-15 parts of oil swell resin, 15-30 parts of reinforcing agent, softening agent 0.5-2
Part, accelerating agent are 2-5 parts, zinc oxide is 3-6 parts and vulcanizing agent is 0.5-3.5 parts.
2. self-expanding rubber blocking agent according to claim 1, which is characterized in that include the raw material of following parts by weight：Butyronitrile
Rubber is 100 parts, 70-90 parts of water-absorbing resin, 8-10 parts of oil-soluble resin, 20-30 parts of reinforcing agent, softening agent are 1.0-2 parts, promote
Into agent be 3-5 parts, zinc oxide is 4-6 parts and vulcanizing agent is 1.0-2.5 parts.
3. self-expanding rubber blocking agent according to claim 1, which is characterized in that the water-absorbing resin is polystyrolsulfon acid
Or mixtures thereof one kind in sodium, sodium apolate or polyallyl sodium sulfonate.
4. self-expanding rubber blocking agent according to claim 1, which is characterized in that the oil swell resin is non-hydrogenated petroleum tree
Or mixtures thereof one kind in fat, phenolic resin, butadiene-styrene rubber or polyvinyl resin.
5. self-expanding rubber blocking agent according to claim 1, which is characterized in that the vulcanizing agent be benzoyl peroxide,
Or mixtures thereof cumyl peroxide.
6. self-expanding rubber blocking agent according to claim 1, which is characterized in that the reinforcing agent is carbon black 550, white carbon
Or mixtures thereof.
7. self-expanding rubber blocking agent according to claim 1, which is characterized in that the softening agent is stearic acid, the rush
It is zinc oxide into agent.
8. a kind of preparation side of such as claim 1-7 any one of them fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agents
Method, which is characterized in that include the following steps：
1) the nitrile rubber mill that parts by weight are 100 parts is plasticated, after being slowly added into 15-30 parts of reinforcing agent, adds water suction tree
50-110 parts of fat, is then kneaded 5-10min；
2) 0.5-2 parts of softening agent is sequentially added into above-mentioned system, accelerating agent is 2-5 parts, is kneaded 10-30min；
3) and then zinc oxide is added as 3-6 parts, 5-15 parts of oil swell resin, is kneaded 20-40min；
4) 0.5-3.5 parts of vulcanizing agent is added, after being kneaded 3-5min, uniform bottom sheet obtains rubber compound, cooling；
5) rubber compound after cooling is squeezed out with thin adhesive tape, press cure is carried out to adhesive tape at 170 DEG C, obtain vulcanization adhesive tape；
6) by the vulcanization adhesive tape mechanical crushing of gained, particle is classified by screening, it is stifled to obtain the different self-expanding rubber of grain size
Agent.
9. preparation method according to claim 8, which is characterized in that the particle size range of the self-expanding rubber blocking agent is
0.5mm-1.5mm。
10. a kind of if claim 1-7 any one of them fracture-pore reservoir oil-water selectivity self-expanding rubber blocking agents are in temperature
120 DEG C -140 DEG C, salinity≤20 × 104Application in the fractured-cavernous carbonate reservoir deep of mg/L.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810035650.8A CN108300436B (en) | 2018-01-15 | 2018-01-15 | Oil-water selective self-expansion rubber plugging agent for fracture-cavity oil reservoir, and preparation method and application thereof |
| PCT/CN2018/082860 WO2018171812A1 (en) | 2018-01-15 | 2018-04-12 | Fracture cave-type reservoir oil/water selective self-expanding rubber plugging agent, preparation method therefor, and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810035650.8A CN108300436B (en) | 2018-01-15 | 2018-01-15 | Oil-water selective self-expansion rubber plugging agent for fracture-cavity oil reservoir, and preparation method and application thereof |
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| CN108300436B CN108300436B (en) | 2020-08-28 |
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| WO2018171812A1 (en) | 2018-09-27 |
| CN108300436B (en) | 2020-08-28 |
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