CN106947447A - Thermo-sensitive expanding microcapsules agent for anti gassing-out and channeling control cement slurry system - Google Patents
Thermo-sensitive expanding microcapsules agent for anti gassing-out and channeling control cement slurry system Download PDFInfo
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- CN106947447A CN106947447A CN201710164944.6A CN201710164944A CN106947447A CN 106947447 A CN106947447 A CN 106947447A CN 201710164944 A CN201710164944 A CN 201710164944A CN 106947447 A CN106947447 A CN 106947447A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- 239000003094 microcapsule Substances 0.000 title claims abstract description 37
- 239000004568 cement Substances 0.000 title claims abstract description 36
- 230000005465 channeling Effects 0.000 title claims abstract description 23
- 239000002002 slurry Substances 0.000 title claims abstract description 18
- 239000003129 oil well Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000013530 defoamer Substances 0.000 claims abstract description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003643 water by type Substances 0.000 claims abstract description 5
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 6
- 235000013847 iso-butane Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- -1 BDO dimethylacrylates Chemical class 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000010428 baryte Substances 0.000 claims description 2
- 229910052601 baryte Inorganic materials 0.000 claims description 2
- 229940008099 dimethicone Drugs 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019082 Osmanthus Nutrition 0.000 claims 1
- 241000333181 Osmanthus Species 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 230000008602 contraction Effects 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 9
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical class CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract description 4
- 238000012856 packing Methods 0.000 abstract description 2
- MBVUXDRWRMDPDB-UHFFFAOYSA-N CC(=CC(=O)OC(CCC)O)C Chemical class CC(=CC(=O)OC(CCC)O)C MBVUXDRWRMDPDB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 239000011083 cement mortar Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 7
- 208000005156 Dehydration Diseases 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000005360 mashing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/493—Additives for reducing or preventing gas migration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1033—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
Abstract
The invention discloses Thermo-sensitive expanding microcapsules agent for anti gassing-out and channeling control cement slurry system, the microcapsules agent for anti gassing-out prepares as follows：34 parts of acrylonitrile, 0.4 0.5 parts of methyl acrylates, 23 parts of methyl methacrylates are added in beaker; 12 parts of lauroyl peroxides are added as initiator; 10 30 parts of low boiling point solvents are used as foaming agent; 0.1 0.2 part 1; 4 butanediol dimethylacrylates are used as crosslinking agent; stirring and dissolving; it is transferred to glass reaction kettle; 20 25 parts of nano silicons are added as dispersant; add 300 350 parts of deionized waters; 20 24h are reacted in 60 70 DEG C of waters bath with thermostatic control under nitrogen protection, cool, wash, dry.The channeling control cement slurry system includes：100 parts of oil-well cement, 1.5 2 parts of fluid loss agent, 23 parts of dispersant, 0.1 1 parts of agent for anti gassing-out, 03 parts of retarder, 0.2 part of defoamer, 0 50 parts of density adjuster, 44 parts of water.The present invention can effectively make up Behavior of Hardened Cement Paste volume contraction, and packing formation fluid prevents channelling, and prevention annular space phenomenon with pressure occurs, and extends oil well service life.
Description
Technical field
The present invention relates to a kind of Thermo-sensitive expanding microcapsules agent for anti gassing-out in cementing slurry field and its preparing anti-gas channeling
Application in mortar architecture.
Background technology
Volume contraction in oil-well cement hydration process, be cause cement sheath interface agglutination it is of poor quality, induce OIH,
Annular space main cause with pressure after gas and water channelling and oil layer pollution, operation, this is that the cementing technology not yet solved very well is difficult
Topic.Volume contraction can make the pore pressure of cement mortar post reduce (gelling is weightless), volume after solidification to cement mortar in the plastic state
Shrink make between cement sheath and stratum and sleeve pipe cementing to go wrong, form microgap, more than the 95% of amount of contraction occurs in water
After mud final set, volume shrinkage mass is the 2.6%-5.0% of cement mortar cumulative volume, and the volume contraction of cement mortar both influences well cementation
Quality, forms potential risk, petroleum resources can be caused largely to be lost in again.
Swelling agent is added in cement to be closing micro-loop empty gap to improve the effective of the interface cementing quality of Behavior of Hardened Cement Paste two
One of measure.The swelling agent species used both at home and abroad is a lot, and the mode of action of swelling agent mainly has aeration, method of getting angry, solid phase
Plavini etc., traditional agent for anti gassing-out is mainly metallic aluminium and its oxygenate, latex class, polyvinyl alcohol and calcium sulfate.But it is existing
There is problems with agent for anti gassing-out：Class of getting angry agent for anti gassing-out (such as KQ series), with the uncontrollable defect of gas forming amount；Latex class is prevented
Has channeling agent (oil field deep well well cementation multiple-effect latex agent for anti gassing-out and preparation method thereof CN103834374A) addition is larger, when depositing
Demulsification is also occurred that when storing temperature is relatively low, anti-gas channeling effect is influenceed；Polyvinyl alcohol can not be used in high temperature and high salt environment；Solid phase
Expansion class agent for anti gassing-out (such as Zheng Guosheng plastic expansion channeling control cement slurry architectural studies and application [J] oil drilling technologies,
2013,35(5):Main component 52-55) is calcium sulfate, and major defect is that expansion character is not enough, Bulking Time, expansion well depth
It is uncontrollable.
The content of the invention
It is an object of the invention to provide Thermo-sensitive expanding microcapsules agent for anti gassing-out, the agent for anti gassing-out is a kind of heat volume
The microcapsules changed, its gas forming amount is controllable, and fixed point constant temperature plays a role and is coated alkaline-resisting, ground performance stabilization, does not influence
Normal mashing with slurry, construction technology is simply easily promoted, with wide market prospects.
Another object of the present invention also resides in the gas-tight for providing and being prepared using above-mentioned Thermo-sensitive expanding microcapsules agent for anti gassing-out
Channeling water mud system, the channeling control cement slurry system can start expansion in predeterminated position, effectively make up Behavior of Hardened Cement Paste volume contraction, seal
Channelling is prevented every formation fluid, prevention annular space phenomenon with pressure occurs, and improves oil well productivity, extends oil well service life.
To reach above technical purpose, the present invention provides following technical scheme.
Thermo-sensitive expanding microcapsules agent for anti gassing-out, is prepared by following components using suspension polymerization, and process is as follows：Burning
3-4 parts of acrylonitrile (AN), 0.4-0.5 parts of methyl acrylates (MA), 2-3 parts of methyl methacrylates (MMA) are added in cup, then are added
Enter 1-2 parts of lauroyl peroxides (LPO) as initiator, 10-30 parts of low boiling point solvents as foaming agent, 0.1-0.2 parts of Isosorbide-5-Nitraes-
Butanediol dimethylacrylate (BDDMA) is transferred to glass reaction kettle, then adds 20- as crosslinking agent, electromagnetic agitation dissolving
25 parts of nano silicons add 300-350 parts of deionized waters as dispersant, and 8- is stirred with 1200r/min speed
10min, under nitrogen protection after 60-70 DEG C of water bath with thermostatic control reaction 20-24h, cools, washs, dries, produce microcapsules anti-gas channeling
Agent, above-mentioned substance is parts by weight.
Acrylonitrile (AN), methyl acrylate (MA), methyl methacrylate under lauroyl peroxide (LPO) initiation
(MMA) it is copolymerized to form long-chain linear molecule, the line in the presence of BDO dimethylacrylate (BDDMA)
Type molecule, which is mutually bonded, is cross-linked into network molecular structure, and low boiling point solvent is gradually by netted point in the presence of nano silicon
Attached bag is wrapped up in, and forms Thermo-sensitive expanding microcapsules.
The low boiling point solvent is organic solvent of the gasification temperature in the range of -40-40 DEG C, such as propane, normal butane, isobutyl
Alkane, pentane, isopentane etc..
The Thermo-sensitive expanding microcapsules agent for anti gassing-out is the microcapsules that a kind of heat volume changes, with thermoplasticity
Shell, interior bag low boiling point organic solvent, according to different purposes, its diameter is generally 5-500 μm.
The wall material of the microcapsules is acrylonitrile (AN), methyl acrylate (MA), methyl methacrylate (MMA) three's copolymerization
Thing, core is stable in properties under low boiling point solvent, ground normal temperature and pressure, individually with not influenceing with slurry, mashing after cement mortar blending,
When microcapsules with temperature raise and during higher than solvent boiling point, solvent evaporation and make microcapsules little by little, uniform vaporization expansion, more
Wall material is not shunk and had compared with high-air-tightness so as to maintain the state after expansion after the volume contraction of moisturizing mud, temperature drop,
Ensure that cement mortar temperature reduction after be not in volume retraction phenomenon, it is ensured that the security of construction.
The channeling control cement slurry system prepared using above-mentioned Thermo-sensitive expanding microcapsules agent for anti gassing-out, is pressed by following each component
Weight is constituted：100 parts of oil-well cement, 1.5-2 parts of fluid loss agent, 2-3 parts of dispersant, 0.1-1 parts of agent for anti gassing-out, slow setting
0-3 parts of agent, 0.2 part of defoamer, 0-50 parts of density adjuster, 44 parts of water.
The oil-well cement is the G level high sulfate-resistant oil well cements for meeting API specification.
The fluid loss agent is 2- acrylamide-2-methyl propane sulfonics or hydroxyethyl cellulose.
The dispersant is poly styrene sulfonate.
The agent for anti gassing-out is Thermo-sensitive expanding microcapsules.
The retarder is sodium lignin sulfonate or citric acid.
The defoamer is dimethicone or tributyl phosphate.
The density adjuster is Iron Ore Powder or barite.
Under the stirring condition of 4000 turns/min rotating speeds, above material is uniformly mixed, then turning with 12000 turns/min
Speed stirring and froth breaking, you can obtain Thermo-sensitive expanding microcapsules channeling control cement slurry system.
Thermo-sensitive expanding microcapsules channeling control cement slurry system makes up cement mortar by microcapsule expansion and shunk, and prevents because of water
Mud volume contraction causes the risk of formation fluid channelling, can effectively insulate oil-gas-water layer, with expansion rate height, cement strength
It is high, do not fail, the advantage of volume stability, overcome the defect and deficiency of prior art presence.
Compared with prior art, the invention has the advantages that：
(1) the Thermo-sensitive expanding microcapsules agent for anti gassing-out has gas forming amount controllable, and fixed point constant temperature plays a role and is coated resistance to
Alkali, ground performance is stable, and raw material is common and with low cost；
(2) Thermo-sensitive expanding microcapsules agent for anti gassing-out itself expansion multiplying power is blended at 50-70 times according to proper proportion
In cement mortar, the volume contraction during hardening of cement can be effectively made up；
(3) the expanding microcapsules channeling control cement slurry system, prepares simple, it is easy to promote, can start in predeterminated position swollen
It is swollen, Behavior of Hardened Cement Paste volume contraction is made up, packing formation fluid prevents channelling, and prevention annular space phenomenon with pressure occurs, and improves oil well productivity,
Extend oil well service life.
Embodiment
With reference to specific embodiment, the Thermo-sensitive expanding microcapsules agent for anti gassing-out and channeling control cement slurry system are carried out
Describe in detail.
Embodiment 1
The preparation (following material is parts by weight) of Thermo-sensitive expanding microcapsules agent for anti gassing-out, process is as follows：
Formula 1：3 parts of acrylonitrile, 0.4 part of methyl acrylate, 2 parts of methyl methacrylate, initiator lauroyl peroxide 1
Part, 10 parts of foaming agent iso-butane, 0.1 part of crosslinking agent BDO dimethylacrylate, electromagnetic agitation dissolving is transferred to reaction
Glass kettle, adds 20 parts of dispersant nano silicon, 300 parts of deionized water, 1200r/min stirring 8-10min, nitrogen protection
After lower 62 DEG C of waters bath with thermostatic control reaction 24h, cool, washing is drying to obtain.
Formula 2：15 parts of foaming agent iso-butane, other are identical with formula 1.
Formula 3：20 parts of foaming agent iso-butane, other are identical with formula 1.
Formula 4：25 parts of foaming agent iso-butane, other are identical with formula 1.
Formula 5：30 parts of foaming agent iso-butane, other are identical with formula 1.
Influence of the foaming agent consumption of table 1 to microcapsule expansion temperature
| Formula number | Optimum expansion temperature/DEG C | Bear maximum temperature/DEG C |
| 1 | 102 | 125 |
| 2 | 98 | 123 |
| 3 | 90 | 120 |
| 4 | 87 | 119 |
| 5 | 83 | 120 |
Embodiment 2 (following material is parts by weight)
Blank sample：100 parts of oil-well cement, 2 parts of dispersants, mixing and stirring produces dry-mixed material；1.5 parts of drop dehydrations
Agent, 1 part of retarder, 0.2 part of defoamer are dissolved in 44 parts of water and stirred, and produce wet mixing material；In 4000 turns/min rotating speeds
Under stirring condition, dry-mixed material is at the uniform velocity added in wet mixing material (used time 15s), then stirred with 12000 turns/min rotating speed
35s and froth breaking, that is, obtain contrast groups mortar architecture.
A kind of preparation of Thermo-sensitive expanding microcapsules channeling control cement slurry system, process is as follows：
It is formulated A：100 parts of oil-well cement, 0.1 part of agent for anti gassing-out expanding microcapsules, 2 parts of dispersants, mixing and stirring is
Obtain dry-mixed material；1.5 parts of fluid loss agents, 1 part of retarder, 0.2 part of defoamer are dissolved in 44 parts of water and stirred, and produce wet mixing material
Material；Under the stirring condition of 4000 turns/min rotating speeds, dry-mixed material is at the uniform velocity added in wet mixing material (used time 15s), then with
12000 turns/min rotating speed stirring 35s and froth breaking, that is, obtain Thermo-sensitive expanding microcapsules channeling control cement slurry system.
It is formulated B：0.3 part of agent for anti gassing-out microcapsules, other are identical with formula A, with reference to GB/T 19139-2012 (oil wells
Cement testing method) and the SY/T 5504.5-2010 (parts of oil well cement additive evaluation method the 5th：Agent for anti gassing-out) to above-mentioned
The performance of cement mortar is evaluated, and the results are shown in Table 2, table 3.
The blank sample of table 2, formula A, the cement mortar combination properties of formula B at different temperatures
Note：API dehydrations condition is 90 DEG C × 7.1MPa × 30min
Thickening condition is 120 DEG C × 80MPa × 60min
The blank sample of table 3, formula A, the performance evaluation of gas channeling prevention for being formulated B
Understand that agent for anti gassing-out expanding microcapsules have no effect on the engineering property of cement mortar according to table 2, table 3, at 50 DEG C not
Has channeling can be prevented well, and the characteristics of this is due to Thermo-sensitive expanding microcapsules is that constant temperature fixed point plays a role, its Initial Dilatation
Temperature is 70 DEG C, reaches that anti-gas channeling is functional after its expansion temperature, and tool has made marked progress compared with prior art.
The above is for only for ease of it will be understood by those skilled in the art that technical scheme, can not be to limit
The present invention.Within the spirit and principles of the invention, any modifications, equivalent substitutions and improvements made etc., should be included in this
Within the protection domain of invention.
Claims (4)
1. Thermo-sensitive expanding microcapsules agent for anti gassing-out, is prepared by following components using suspension polymerization, process is as follows：In beaker
Middle 3-4 parts of acrylonitrile of addition, 0.4-0.5 parts of methyl acrylates, 2-3 parts of methyl methacrylates, add 1-2 parts of peroxidating month
Osmanthus acyl is used as foaming agent, 0.1-0.2 parts of BDO dimethylacrylates as initiator, 10-30 parts of low boiling point solvents
As crosslinking agent, electromagnetic agitation dissolving is transferred to glass reaction kettle, then adds 20-25 parts of nano silicons as dispersant,
300-350 parts of deionized waters are added, 8-10min are stirred with 1200r/min speed, under nitrogen protection 60-70 DEG C of thermostatted water
After bath reaction 20-24h, cool, wash, dry, produce microcapsules agent for anti gassing-out, above-mentioned substance is parts by weight.
2. Thermo-sensitive expanding microcapsules agent for anti gassing-out as claimed in claim 1, it is characterised in that the low boiling point solvent is gas
Change organic solvent of the temperature in the range of -40-40 DEG C, the organic solvent is propane, normal butane, iso-butane, pentane or isoamyl
Alkane.
3. the channeling control cement slurry system prepared using the Thermo-sensitive expanding microcapsules agent for anti gassing-out described in claim 1 or 2, by
Following each component is constituted by weight ratio：100 parts of oil-well cement, 1.5-2 parts of fluid loss agent, 2-3 parts of dispersant, agent for anti gassing-out
0.1-1 parts, 0-3 parts of retarder, 0.2 part of defoamer, 0-50 parts of density adjuster, 44 parts of water.
4. channeling control cement slurry system as claimed in claim 3, it is characterised in that the oil-well cement is G grades high sulfur resistive oil
Well cement, the fluid loss agent is 2- acrylamide-2-methyl propane sulfonics or hydroxyethyl cellulose, and the dispersant is polyphenyl second
Alkene sulfonate, the retarder be sodium lignin sulfonate or citric acid, the defoamer be dimethicone or tributyl phosphate,
The density adjuster is Iron Ore Powder or barite.
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| CN113045263A (en) * | 2021-03-18 | 2021-06-29 | 西南石油大学 | Hybrid fiber cement-based foam composite wave-absorbing material and preparation method thereof |
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| CN113444504A (en) * | 2020-03-24 | 2021-09-28 | 中国石油天然气股份有限公司 | Crystallization anti-channeling well cementation cement slurry and preparation method thereof |
| CN113045263A (en) * | 2021-03-18 | 2021-06-29 | 西南石油大学 | Hybrid fiber cement-based foam composite wave-absorbing material and preparation method thereof |
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