CN117247246A - CO-resistant for well cementation cement 2 Corrosion thermal insulation material and preparation method thereof - Google Patents
CO-resistant for well cementation cement 2 Corrosion thermal insulation material and preparation method thereof Download PDFInfo
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- CN117247246A CN117247246A CN202310931204.6A CN202310931204A CN117247246A CN 117247246 A CN117247246 A CN 117247246A CN 202310931204 A CN202310931204 A CN 202310931204A CN 117247246 A CN117247246 A CN 117247246A
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- cement
- powder
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- corrosion
- insulation material
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- 239000004568 cement Substances 0.000 title claims abstract description 116
- 230000007797 corrosion Effects 0.000 title claims abstract description 60
- 238000005260 corrosion Methods 0.000 title claims abstract description 60
- 239000012774 insulation material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 239000010878 waste rock Substances 0.000 claims abstract description 31
- 210000002268 wool Anatomy 0.000 claims abstract description 31
- 239000000919 ceramic Substances 0.000 claims abstract description 29
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims abstract description 27
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims abstract description 27
- XGRSAFKZAGGXJV-UHFFFAOYSA-N 3-azaniumyl-3-cyclohexylpropanoate Chemical compound OC(=O)CC(N)C1CCCCC1 XGRSAFKZAGGXJV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229960004711 sodium monofluorophosphate Drugs 0.000 claims abstract description 25
- 239000011325 microbead Substances 0.000 claims abstract description 24
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 22
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000004417 polycarbonate Substances 0.000 claims abstract description 20
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 20
- IYZSDQIECHWXMQ-UHFFFAOYSA-N P1(OC(CCO1)N)=O.[K] Chemical compound P1(OC(CCO1)N)=O.[K] IYZSDQIECHWXMQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004321 preservation Methods 0.000 claims abstract description 14
- 239000011810 insulating material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011435 rock Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 150000002910 rare earth metals Chemical class 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 claims description 10
- 229910021355 zirconium silicide Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- FEMRXDWBWXQOGV-UHFFFAOYSA-N potassium amide Chemical compound [NH2-].[K+] FEMRXDWBWXQOGV-UHFFFAOYSA-N 0.000 claims 2
- 239000011490 mineral wool Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 abstract description 12
- 230000002829 reductive effect Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- 230000036571 hydration Effects 0.000 description 9
- 238000006703 hydration reaction Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 239000003129 oil well Substances 0.000 description 7
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002641 lithium Chemical class 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical group [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052849 andalusite Inorganic materials 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052637 diopside Inorganic materials 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 potassium trimethylene phosphonate Chemical compound 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical group C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 239000005819 Potassium phosphonate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/30—Oxides other than silica
- C04B14/305—Titanium oxide, e.g. titanates
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/027—Lightweight materials
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/003—Phosphorus-containing compounds
-
- 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
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention discloses a CO-resistant cement for well cementation 2 Corrosion thermal insulation material and preparation method thereof, solving the problem of the prior solidWell cement is easy to be corroded by acid, and has low heat collection and utilization efficiency and serious heat loss. CO-resistant for well cementing cement 2 The corrosion heat-insulating material comprises 40-65 wt.% of heat-insulating matrix, 5-10 wt.% of aluminum titanate, 15-25 wt.% of sodium monofluorophosphate and 15-25 wt.% of potassium aminotrimethylene phosphonate, wherein the heat-insulating matrix is obtained by mixing hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate. The invention not only can improve the high-temperature stability, the early strength, the toughness and the CO resistance of the well cementation cement system 2 Ability to corrode; the filter loss can be reduced, the heat conductivity coefficient of the well cementation cement stone is reduced while the construction performance requirement is met, the heat preservation capability of the cement stone is improved, the heat loss in the geothermal resource exploitation process is effectively reduced, and the geothermal resource utilization rate is improved.
Description
Technical Field
The invention belongs to the technical field of geothermal resource development, and particularly relates to a CO-resistant cement for well cementation 2 Corrosion thermal insulation material and its preparation method.
Background
Geothermal energy is a green, environment-friendly, low-carbon and high-efficiency renewable resource, and has been widely paid attention to the society. Two heat-taking media commonly used for exploiting geothermal resources at present are water and CO 2 When water is used as a heat-taking medium, the water can perform physical and chemical reaction with rock minerals in the stratum to damage the stability of the reservoir and reduce the purity of working fluid; meanwhile, mineral components dissolved in water can cause scaling of a shaft, ground equipment and various pipelines, and the service life of the equipment is influenced; in addition, low recovery of working fluid is also a problem. Supercritical CO 2 When the geothermal resource is mined, various properties of the geothermal resource are superior to those of water, so that the geothermal resource can improve the heat-mining efficiency, increase the economic benefit and have important significance for the development of dry-hot rock. But using supercritical CO 2 When exploitation is carried out, the cement sheath for well cementation can be subjected to the action of acid corrosion to cause the performance degradation of cement stones, and in order to solve the problem, the corrosion resistance of the cement sheath for well cementation needs to be improved; in addition, in the geothermal resource exploitation process, the wellhead water temperature is obviously reduced compared with the reservoir temperature, and the resource waste is serious, so that the geothermal resource exploitation method is simple and convenientThe water temperature of the wellhead and the geothermal resource utilization efficiency can be increased, and a cement slurry system with low heat conductivity and good heat preservation effect can be introduced to perform well cementation operation.
In summary, in order to improve the heat collection efficiency and the utilization efficiency, reduce the heat loss, avoid the resource waste and increase the economic benefit, a CO-resistant cement for well cementation is developed 2 Corrosion of the insulation material is particularly important.
Disclosure of Invention
The invention aims to solve the technical problems that: the CO2 corrosion resistant heat insulation material for the well cementation cement and the preparation method thereof are provided to at least solve the technical problems of the part.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
CO-resistant for well cementation cement 2 The corrosion heat-insulating material consists of the following raw materials in percentage by weight:
heat preservation matrix: 40-65 wt.%;
aluminum titanate: 5-10 wt.%;
sodium monofluorophosphate: 15-25 wt.%
Potassium aminotrimethylene phosphonate: 15-25 wt.%;
the heat-insulating matrix is prepared by mixing (11-15)/(1-3)/(3-5)/(1-2) by weight ratio of hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate.
In some embodiments of the invention, the cementing cement is resistant to CO 2 The corrosion heat-insulating material comprises the following raw materials in percentage by weight:
heat preservation matrix: 50-65 wt.%;
aluminum titanate: 8-10 wt.%;
sodium monofluorophosphate: 20 to 25wt.%
Potassium aminotrimethylene phosphonate: 15-20 wt.%;
preferably, the heat-insulating matrix is prepared by mixing (11-12): 1-2): 3-4): 1 by weight ratio of hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate.
Further, the aluminum titanate is in a powder shape, and the particle size of the aluminum titanate is more than or equal to 800 meshes.
Further, the sodium monofluorophosphate is in the form of a powder having a particle size of > 325 mesh and a purity of > 99wt.%.
Further, the potassium aminotrimethylene phosphonate is a crystalline powder with a particle size > 160 mesh and a purity > 98wt.%.
Further, the hollow ceramic microbeads are prepared from lithium slag, zirconium silicide, molybdenum tailings, rare earth tailings and saw dust serving as raw materials by adopting a flame spray gun meltallizing method; preferably, the hollow ceramic microbeads have a particle size of 10-30 μm and a thermal conductivity of 0.09-0.11W/(mK).
The hollow ceramic microbeads disclosed by the invention are light in weight, high in strength, high in volcanic ash activity, good in heat preservation effect, good in cementing property with other inorganic cementing materials, and capable of promoting early hydration and strength development of geothermal well cementation cement. The waste rock wool board powder has good heat preservation performance due to low heat conductivity coefficient, can form a good three-dimensional network structure with a well cementation cement hydration product, and can provide support for hollow ceramic microbeads, protein shale powder and modified polycarbonate. The main component of the protein shale is SiO 2 The volcanic ash has volcanic ash activity and a large number of micropore structures, and the volcanic ash activity can be further enhanced after the volcanic ash is ground into powder; the microporous structure and the volcanic ash activity can be used as filling materials to fill gaps among hollow ceramic microspheres, waste rock wool boards, well cementation cement particles and hydration products, and can also be used as heat preservation materials and active materials to strengthen the performance of the heat preservation materials for well cementation. The modified polycarbonate has good hydrophilicity and temperature resistance, can form good cementation with other matrix materials, and can act together with a reticular structure formed by waste rock wool board powder, thereby having the effects of toughening and reducing brittleness. In addition, the lithium slag, molybdenum tailings, rare earth tailings, waste rock wool boards and other solid wastes are fully utilized, the environmental protection pressure caused by solid wastes can be greatly reduced, and the method is green and environment-friendly and has low cost.
The lithium slag mainly comprises a quartz phase, andalusite, corundum, and a small amount of glass phase, kaolinite and lithium carbonate; wherein SiO is 2 Content >60wt.%,Al 2 O 3 Content > 20wt.%, na 2 The content of O is 0.2 to 0.8 weight percent, K 2 The O content is 0.1 to 4wt.%.
The content of the zirconium silicide active substances is more than 99.9wt.%
The molybdenum tailings mainly comprise diopside, albite and dolomite; wherein SiO is 2 The content is more than 52wt.% of Al 2 O 3 Content > 14wt.%.
The main chemical composition (SiO) of the rare earth tailings 2 、Fe 2 O 3 、Al 2 O 3 And CaO, etc.) of > 82%, where SiO 2 The content is more than 55wt.% of Al 2 O 3 Content > 14wt.%, caF 2 The content is 0.25 to 0.30wt.%.
The sawdust is formed by crushing dry sawdust, and the average particle size of the sawdust is less than 20 meshes.
According to the invention, lithium slag, zirconium silicide, molybdenum tailings, rare earth tailings and saw dust are adopted to prepare the hollow ceramic microspheres, and a large amount of air is arranged in the hollow ceramic microspheres, so that the heat conduction capacity of the heat insulation material can be reduced, and the heat insulation performance is improved; at the same time, siO necessary for providing ceramics 2 、Al 2 O 3 In addition, the lithium slag, molybdenum tailings and rare earth tailings are alkali metal oxides (K 2 O、Na 2 O), wherein rare earth oxide in the rare earth tailings can be used as a stabilizer and a sintering aid, so that the strength and the toughness of the ceramic microbeads are greatly improved; the dolomite in the molybdenum tailings forms a diopside phase staggered net structure along with the increase of the sintering temperature, so that the strength of the ceramic microbeads is improved; the zirconium silicide further improves the density and strength of the ceramic microbeads; sawdust generates a large amount of gas at high temperature, which provides basic conditions for forming a hollow structure.
The preparation method of the hollow ceramic microbeads comprises the following steps:
step A, drying and calcining the lithium slag at a high temperature to obtain activated lithium slag;
step B, weighing activated lithium slag, zirconium silicide, molybdenum tailings and rare earth tailings with the mass ratio of (60-74), (13-15), (10-20) and (1-5), performing wet ball milling and drying to form a mixture A; preferably, the mass ratio of the activated lithium slag, the zirconium silicide, the molybdenum tailings and the rare earth tailings is 70:15:10:5;
step C, weighing the mixture A and sawdust with the mass ratio of (90-95) to (5-10), uniformly mixing to form a mixture B, and adopting a flame spray gun to spray the mixture B, and cooling and solidifying to obtain a spray product; preferably, the mass ratio of the mixture A to the sawdust is 90:10;
and D, collecting a fused product, and drying in vacuum to obtain the hollow ceramic microspheres.
The invention adopts the flame spray gun meltallizing method to form the hollow ceramic microbeads, and has simple process flow, convenient equipment operation and low energy consumption.
Preferably, in the step A, the baking is carried out by adopting a baking oven, wherein the baking temperature is 50-70 ℃ and the baking time is 7-8 hours; the calcination temperature is 680-700 ℃ and the calcination time is 1-1.5 h;
preferably, in the step B, a wet ball mill is adopted for wet ball milling, the liquid medium is absolute ethyl alcohol, the liquid-solid ratio is 2:1, the ball milling rotating speed is 30r/min, and the time is 1.5-2 h; oven drying at 50-70 deg.c for 1.5-2 hr;
preferably, in the step C, the powder feeding gas of the mixture B is oxygen, the powder feeding speed is 15g/s, the gas introduced by the flame spray gun is oxygen-acetylene, the oxygen pressure is 0.5-0.7 MPa, the acetylene pressure is 0.12-0.15 MPa, the spray flame temperature is 2500-2600 ℃, and the quenching distance is 450-500 mm; adopting distilled water as a cooling medium, spraying the molten product into the distilled water for rapid cooling and solidification;
preferably, in the step D, the drying is performed by using a vacuum drying oven, wherein the vacuum degree of the vacuum drying is 0.05-0.08 MPa, the baking temperature is 70-85 ℃ and the time is 6-7 h.
Further, the waste rock wool board powder is obtained by drying, crushing and grinding waste rock wool boards or waste rock wool boards, and the average grain diameter of the waste rock wool board powder is more than or equal to 325 meshes.
Further, the protein shale powder is obtained by drying and grinding the protein shale, and the average grain diameter of the protein shale powder is more than or equal to 1200 meshes and SiO 2 The content is more than or equal to 90 wt%.
Further, the modified polycarbonate is formed by blending, granulating, cooling and crushing waste rock wool board powder and polycarbonate according to the mass ratio of (1-2) (9-10), preferably 1:9 in a melt blending mode, and then carrying out low-temperature plasma modification, wherein the average particle size is more than or equal to 325 meshes;
the invention also provides the CO-resistant cement for well cementation 2 The preparation method of the corrosion thermal insulation material comprises the following steps: weighing a heat-insulating matrix, aluminum titanate powder, sodium monofluorophosphate and potassium aminotrimethylene phosphonate, and fully mixing to obtain the CO-resistant cement for well cementation 2 And (5) corroding the heat insulation material.
Preferably, a powder mixer is used for mixing the heat-preserving matrix, the aluminum titanate powder, the sodium monofluorophosphate and the potassium aminotrimethylene phosphonate for 5-10 min.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines inorganic material sodium monofluorophosphate and organic material potassium aminotrimethylene phosphonate to synergistically enhance CO resistance 2 Corrosion performance. Wherein, the sodium monofluorophosphate reacts with calcium hydroxide which is a cement hydration product to generate apatite, and the apatite is coated on the surface of the rest hydration product to form a compact protective layer to prevent CO 2 Further invasion; the aqueous solution of the amino-trimethylene phosphonic acid potassium is weak acid and can be combined with Ca in cement hydration products 2+ Chelating to form complex, reducing substances easy to be carbonized in hydration products, inhibiting and interfering with formation and growth of calcium carbonate, and improving CO tolerance 2 Corrosiveness; the aluminum titanate has good heat resistance, and the microstructure of the aluminum titanate has a crystal phase and air holes, so that the aluminum titanate has the characteristics of low heat conductivity and corrosion resistance, on one hand, the aluminum titanate can enhance the heat resistance, and on the other hand, the aluminum titanate is cooperated with a heat-insulating matrix to enhance the heat-insulating property.
The invention adopts a heat-insulating matrix, the main component of which is SiO 2 And Al 2 O 3 The calcium-silicon ratio (Ca/Si ratio) is greatly reduced after the cement is added. The high-temperature strength of the cement stone is ensured by the reduction of the calcium-silicon ratio, the temperature resistance of the cement is improved, and the other handThe surface reduces the generation of alkaline hydration products, inhibits the generation of calcium carbonate, and further cooperates with the potassium aminotrimethylene phosphonate and the sodium monofluorophosphate to strengthen the corrosion resistance of the cement stone.
Under the synergistic effect of the components, the invention mixes the components according to a certain proportion to form the CO-resistant cement for well cementation 2 The corrosion heat-insulating material not only can improve the high-temperature stability, early strength, toughness and CO resistance of a well cementation cement system 2 Ability to corrode; the filter loss can be reduced, the heat conductivity coefficient of the well cementation cement stone is reduced while the construction performance requirement is met, the heat preservation capability of the cement stone is improved, the heat loss in the geothermal resource exploitation process is effectively reduced, and the geothermal resource utilization rate is improved.
Drawings
FIG. 1 is a graph of the weight loss of cement slurry systems 1# to 5# of the present invention versus corrosion 28d of the cement slurry system.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The particle size of the hollow ceramic microbeads in the embodiment of the invention is 5-40 mu m, and the heat conductivity coefficient is 0.09-0.11W/(m.K).
The lithium slag in the embodiment of the invention mainly comprises quartz phase, andalusite, corundum, and a small amount of glass phase, kaolinite and lithium carbonate; wherein SiO is 2 The content is more than 60wt.% of Al 2 O 3 Content > 20wt.%, na 2 The content of O is 0.2 to 0.8 weight percent, K 2 The O content is 0.1 to 4wt.%.
The zirconium silicide active material content in the examples of the present invention was > 99.9wt.%.
The molybdenum tailings in the embodiment of the invention mainly consist of diopsideSodium feldspar and dolomite; wherein SiO is 2 The content is more than 52wt.% of Al 2 O 3 Content > 14wt.%.
The main chemical composition (SiO) of the rare earth tailings in the embodiment of the invention 2 、Fe 2 O 3 、Al 2 O 3 And CaO, etc.) in a ratio of > 82wt.%, where SiO 2 The content is more than 55wt.% of Al 2 O 3 Content > 14wt.%, caF 2 The content is 0.25 to 0.30wt.%.
The hollow ceramic microbeads of the embodiment of the invention are prepared from lithium slag, zirconium silicide, molybdenum tailings, rare earth tailings and saw dust serving as raw materials by adopting a flame spray gun meltallizing method, and specifically comprise the following steps:
step A, drying the lithium slag in a baking oven at 60 ℃ for 8 hours, and calcining the dried lithium slag in a muffle furnace at 700 ℃ for 1.5 hours to obtain activated lithium slag;
step B, activated lithium slag, zirconium silicide, molybdenum tailings and rare earth tailings are mixed according to a proportion of 60:15:20:5, grinding for 1h in a wet ball mill, wherein the liquid medium is absolute ethyl alcohol, the ball milling liquid-solid ratio is 2:1, the ball milling rotating speed is 30r/min, and the ball milling time is 2h; drying in an oven at 60 ℃ for 2 hours after ball milling to form a mixture A;
step C, mixing the mixture A and sawdust according to the mass ratio of 95:5 to form a mixture B, using a flame spray gun to spray the mixture B, and spraying a spray product into a cooling medium to be distilled water for rapid cooling and solidification; wherein the powder feeding gas of the mixture B is oxygen and the powder feeding speed is 15g/s; the gas introduced by the flame spray gun is oxygen-acetylene, the oxygen pressure is 0.6MPa, the acetylene pressure is 0.12MPa, the spray flame temperature is 2600 ℃, and the quenching distance is 500mm;
and D, collecting a fused and irradiated product, and drying the product at 80 ℃ under 0.07MPa for 6 hours in vacuum to obtain the hollow ceramic microbeads.
The preparation method of the waste rock wool board powder in the embodiment of the invention comprises the following steps: and (3) drying the waste rock wool boards or the waste rock wool boards, coarsely crushing the waste rock wool boards by using a crusher, and grinding the waste rock wool boards by using an ultrafine grinding machine to obtain waste rock wool board powder.
The preparation method of the protein shale powder in the embodiment of the invention comprises the following steps: and (3) drying the protein shale in a baking oven, and then grinding the dried protein shale in a superfine grinding machine to obtain protein shale powder.
The preparation method of the modified polycarbonate in the embodiment of the invention comprises the following steps: and (3) mixing the waste rock wool board powder and polycarbonate according to the mass ratio of 1:9, granulating, cooling, crushing, and performing low-temperature plasma modification to form modified polycarbonate.
Example 1
As a preferred embodiment of the invention, the embodiment discloses a CO-resistant cement for well cementation 2 The specific composition of the corrosion insulation is shown in table 1.
TABLE 1
Component (A) | Weight percent (wt.%) |
Thermal insulation matrix | 40 |
Aluminum titanate powder | 10 |
Sodium monofluorophosphate | 25 |
Amino-trimethylene phosphonic acid potassium salt | 25 |
In the embodiment, the heat-insulating matrix is prepared by mixing hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate according to a weight ratio of 11:3:5:1.
In the present embodimentThe heat-insulating matrix, aluminum titanate powder, sodium monofluorophosphate and potassium aminotrimethylene phosphonate with the weight percentages of 40:10:25:25 are put into a powder mixer to be fully mixed for 5min, and then the CO-resistant cement for well cementation is obtained 2 Corrosion insulating material No. 1.
Example 2
As a preferred embodiment of the invention, the embodiment discloses a CO-resistant cement for well cementation 2 The specific composition of the corrosion insulation is shown in table 2.
TABLE 2
In the embodiment, the heat-insulating matrix is prepared by mixing hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate according to a weight ratio of 11:3:5:1.
In the embodiment, the heat-insulating matrix, aluminum titanate powder, sodium monofluorophosphate and potassium aminotrimethylene phosphonate with the weight percentages of 52:8:20:20 are put into a powder mixer to be fully mixed for 5min, and then the CO-resistant cement for well cementation is obtained 2 Corrosion insulating material No. 2.
Example 3
As a preferred embodiment of the invention, the embodiment discloses a CO-resistant cement for well cementation 2 The specific composition of the corrosion insulation is shown in table 3.
TABLE 3 Table 3
Component (A) | Weight percent (wt.%) |
Thermal insulation matrix | 65 |
Aluminum titanate powder | 5 |
Sodium monofluorophosphate | 15 |
Amino-trimethylene phosphonic acid potassium salt | 15 |
In the embodiment, the heat-insulating matrix is prepared by mixing hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate according to a weight ratio of 11:3:5:1.
In the embodiment, the heat-insulating matrix, aluminum titanate powder, sodium monofluorophosphate and potassium aminotrimethylene phosphonate with the weight percentages of 65:5:15:15 are put into a powder mixer to be fully mixed for 5min, and then the CO-resistant cement for well cementation is obtained 2 Corrosion insulating material 3#.
Example 4
As a preferred embodiment of the invention, the embodiment discloses a CO-resistant cement for well cementation 2 The specific composition of the corrosion insulation is shown in table 4.
TABLE 4 Table 4
In the embodiment, the heat-insulating matrix is prepared by mixing hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate according to a weight ratio of 13:2:4:1.
In the embodiment, the heat-insulating matrix, aluminum titanate powder, sodium monofluorophosphate and potassium aminotrimethylene phosphonate with the weight percentages of 52:8:20:20 are put into a powder mixer to be fully mixed for 5min, and then the CO-resistant cement for well cementation is obtained 2 Corrosion insulation material # 4.
Example 5
As a preferred embodiment of the invention, the embodiment discloses a CO-resistant cement for well cementation 2 The specific composition of the corrosion insulation is shown in table 5.
TABLE 5
Component (A) | Weight percent (wt.%) |
Thermal insulation matrix | 52 |
Aluminum titanate powder | 8 |
Sodium monofluorophosphate | 20 |
Amino-trimethylene phosphonic acid potassium salt | 20 |
In the embodiment, the heat-insulating matrix is prepared by mixing hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate according to a weight ratio of 15:1:3:1.
In this example, an insulating matrix, aluminum titanate powder, sodium monofluorophosphate, and ammonia in weight percentages of 52:8:20:20, respectively, were usedFully mixing the potassium trimethylene phosphonate in a powder mixer for 5min to obtain the CO-resistant cement for well cementation 2 Corrosion insulating material No. 5.
Comparative example 1
Compared with the example 1, the comparative example does not contain sodium monofluorophosphate, namely, the raw materials comprise the following components in percentage by mass: heat preservation matrix: aluminum titanate powder: the potassium aminotrimethylene phosphonate was 40:10:25. the remaining conditions were the same. The material prepared in this comparative example was designated d1#.
Comparative example 2
Compared with the example 1, the comparative example does not contain the amino-trimethylene potassium phosphonate, namely the raw materials comprise the following components in mass ratio: heat preservation matrix: aluminum titanate powder: the potassium aminotrimethylene phosphonate was 40:10:25. the remaining conditions were the same. The material prepared in this comparative example was designated d2#.
Test examples
CO-resistant cement for well cementation prepared in examples 1 to 5 2 The corrosion heat insulation materials No. 1-No. 5 and the materials D1-D2 prepared by the comparative example are all prepared into cement paste according to the GB/T19139 standard, and the formula is as follows: CO-resistant for 80% G grade oil well cement+20% well cementing cement 2 Corrosion insulating material (mass ratio), and CO-resistant for G-grade oil well cement and well cementation cement 2 The corrosion heat insulation material is 1% high-temperature retarder and 2.5% high-temperature fluid loss agent calculated by 100%, the water cement ratio is 0.5, and well cementation cement slurry systems 1# to 5# and D1# to D2# are respectively obtained.
The cement paste is prepared according to the GB/T19139 standard, and the formula is as follows: 100% of G-grade oil well cement, 1% of high-temperature retarder and 2.5% of high-temperature fluid loss additive (calculated by mass ratio) calculated by 100% of G-grade oil well cement, and water cement ratio of 0.5, thereby obtaining a comparison well cementation cement slurry system.
The G-grade oil well cement is provided by Jiahua special cement Co., ltd, the high-temperature retarder and the high-temperature fluid loss agent are provided by Sichuan Xuan Ran Hong new material Co., ltd, and the high-temperature retarder is an AMPS polymer; high-temperature filtrate reducer 2-acrylamido-2-methylpropanesulfonic acid polymer.
Referring to GB/T19139 oil well cement test method, cement engineering properties of the well cementation cement slurry systems 1# to 5# and D1# to D2# are compared, and 150 ℃ test is carried out, and the results are shown in Table 6.
TABLE 6
According to experimental data in Table 6, the cement slurry systems 1# to 5# prepared in examples 1 to 5 have water loss of less than 50ml, fluidity and free liquid meeting construction requirements, good slurry stability, controllable thickening time, good engineering properties and far better CO resistance than those of cement without cementing 2 And (3) corroding a contrast well cementation cement slurry system of the heat insulation material. The invention relates to a CO-resistant cement for well cementation 2 The corrosion heat-insulating material and the additive have good compatibility, the thickening time is controllable, and the corrosion heat-insulating material and the additive are suitable for preparing the existing well cementation cement slurry system.
Putting the cement paste of the well cementation cement paste system 1# to 5#, the D1# to D2#, and the cement paste of the contrast well cementation cement paste system into a high-temperature high-pressure corrosion reaction kettle, and placing the cement paste into a high-temperature high-pressure gaseous supercritical CO containing water vapor 2 In the environment, the curing temperature is 150 ℃, and the CO 2 The pressure is 5MPa, the total pressure is 10MPa, N 2 Partial pressure; the curing period is 7d and 28d. Adopting a NYSQ-2017 pressure tester to test the compressive strength; and the permeability of each cement paste sample is measured according to the standard SY/T6466-2000 'evaluation method of the high temperature resistance of the oil well cement stone'. And (3) using a DRE-2C type thermal conductivity coefficient tester, and adopting a transient plane heat source method to perform thermal conductivity coefficient test of the well cementation cement. The results of each test are shown in Table 7.
TABLE 7
As can be seen from the experimental data in Table 7, after a certain period of corrosion, no CO resistance for well cementing cement was added 2 The comparative well cementation cement slurry system of the corrosion heat insulation material has low compressive strength and has a fading phenomenon, while the well cementation cement slurry systems 1# to 5# prepared in examples 1 to 5 have high compressive strength and have no fading phenomenon, and the compressive strength is slightly increased, thus indicating the CO resistance for the well cementation cement of the invention 2 The corrosion of the heat insulating material can improve the temperature resistance of the cement stone. Meanwhile, compared with the well cementation cement slurry system, the permeability of the well cementation cement slurry system 1# to 5# is greatly increased, but the total permeability is far smaller than that of the well cementation cement slurry system, which shows that the CO-resistant cement for well cementation is used in the invention 2 The corrosion heat insulation material can form a protective layer on the surface of the hydration product, increase the compactness of the cement matrix and protect the cement stone from CO 2 Corrosion and corrosion resistance are excellent; according to the analysis of the data of the well cementation cement slurry systems D1# and D2#, the compressive strength of the singly doped sodium monofluorophosphate or the amino trimethylene phosphonic acid potassium is reduced, the permeability is increased, and the heat conductivity coefficient is basically kept unchanged; the result shows that the synergistic effect of sodium monofluorophosphate and potassium aminotrimethylene phosphonate is favorable for enhancing the corrosion resistance of the invention. In addition, the heat conductivity coefficients of the well cementation cement slurry systems 1# to 5# are far lower than those of the contrast well cementation cement slurry system, which shows that the CO-resistant cement for well cementation is used in the invention 2 The corrosion heat insulation material has the characteristics of low heat conductivity and good heat insulation effect.
Putting the cement paste of the well cementation cement paste system 1# to 5# and the cement paste of the contrast well cementation cement paste system into a high-temperature high-pressure corrosion reaction kettle, wherein the cement paste is in the gaseous supercritical CO of high-temperature high-pressure and water vapor 2 In the environment. Curing temperature is 150 ℃, CO2 pressure is 5MPa, total pressure is 10MPa, N 2 Partial pressure; the curing period was 28d. Thermogravimetric analysis measurements were performed on the cured product of each well cementing slurry system, as shown in fig. 1.
The research shows that the cement corrosion product is calcium carbonate, the decomposition temperature range of the calcium carbonate is 600-770 ℃, the weight loss of the cement stone in the temperature range is measured by a thermogravimetric analysis method to represent the corrosion condition of the cement stone under the given condition, the greater the weight loss of the sample in the range is, the more easily the sample is corroded, and otherwise, the more the sample is corrosion-resistant. FIG. 1 is a weight loss curve comparing corrosion 28d of cement slurries 1# to 5# of a cement slurry. Sample thermogravimetry was tested on a thermal analysis instrument manufactured by Mettle Toledo company, at a heating rate of 10 ℃/min, under nitrogen protection.
As can be seen from the experimental results of FIG. 1, in the temperature range of 600-770 ℃, the weight loss TG (%) of the well cementation cement paste 1# to 5# is smaller than that of the comparative well cementation cement paste, namely the corrosion resistance of the well cementation cement paste 1# to 5# is far greater than that of the comparative well cementation cement paste, which shows that the CO resistance for the well cementation cement of the invention 2 The corrosion insulation material has excellent corrosion resistance.
In conclusion, by adopting the technical scheme, the corrosion resistance and the heat preservation performance of the well cementation cement can be effectively improved.
Finally, it should be noted that: the above embodiments are merely preferred embodiments of the present invention for illustrating the technical solution of the present invention, but not limiting the scope of the present invention; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; that is, even though the main design concept and spirit of the present invention is modified or finished in an insubstantial manner, the technical problem solved by the present invention is still consistent with the present invention, and all the technical problems are included in the protection scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the scope of the invention.
Claims (10)
1. CO-resistant for well cementation cement 2 Corrosion thermal insulation material is characterized in thatThe material comprises the following raw materials in percentage by weight:
heat preservation matrix: 40-65 wt.%;
aluminum titanate: 5-10 wt.%;
sodium monofluorophosphate: 15-25 wt.%
Potassium aminotrimethylene phosphonate: 15-25 wt.%;
the heat-insulating matrix is prepared by mixing (11-15)/(1-3)/(3-5)/(1-2) by weight ratio of hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate.
2. A CO-resistant cement for cementing according to claim 1 2 The corrosion heat-insulating material is characterized by comprising the following raw materials in percentage by weight:
heat preservation matrix: 50-65 wt.%;
aluminum titanate: 8-10 wt.%;
sodium monofluorophosphate: 20 to 25wt.%
Potassium aminotrimethylene phosphonate: 15-20 wt.%;
preferably, the heat-insulating matrix is prepared by mixing (11-12): 1-2): 3-4): 1 by weight ratio of hollow ceramic microbeads, waste rock wool board powder, protein rock powder and modified polycarbonate.
3. A CO-resistant cement for cementing according to claim 1 or 2 2 The corrosion heat insulation material is characterized in that the aluminum titanate is in powder shape, and the particle size of the aluminum titanate is more than or equal to 800 meshes.
4. A CO-resistant cement for cementing according to claim 1 or 2 2 The corrosion heat insulation material is characterized in that the sodium monofluorophosphate is in a powder shape, and the particle size of the sodium monofluorophosphate is more than 325 meshes.
5. A CO-resistant cement for cementing according to claim 1 or 2 2 The corrosion heat insulation material is characterized in that the amino potassium trimethylenephosphonate is crystalline powder, and the particle size of the amino potassium trimethylenephosphonate is more than 160 meshes.
6. A CO-resistant cement for cementing according to claim 1 or 2 2 The corrosion thermal insulation material is characterized in that the hollow ceramic microbeads are prepared from lithium slag, zirconium silicide, molybdenum tailings, rare earth tailings and saw dust serving as raw materials by a flame spray gun meltallizing method; preferably, the hollow ceramic microbeads have a particle size of 10-30 μm and a thermal conductivity of 0.09-0.11W/(mK).
7. A CO-resistant cement for cementing according to claim 1 or 2 2 The corrosion heat insulation material is characterized in that the waste rock wool board powder is obtained by drying, crushing and grinding waste rock wool boards or rock wool board waste materials, and the average grain diameter of the waste rock wool board powder is more than or equal to 325 meshes.
8. A CO-resistant cement for cementing according to claim 1 or 2 2 The corrosion heat insulation material is characterized in that the protein shale powder is obtained by drying and grinding protein shale, and the average grain diameter of the protein shale powder is more than or equal to 1200 meshes and SiO 2 The content is more than or equal to 90 wt%.
9. A CO-resistant cement for cementing according to claim 1 or 2 2 The corrosion heat insulation material is characterized in that the modified polycarbonate is formed by blending, granulating, cooling and crushing waste rock wool board powder and polycarbonate according to the mass ratio of (1-2) to (9-10) in a melt blending mode, and then modifying the waste rock wool board powder and the polycarbonate by low-temperature plasma, wherein the average particle size is more than or equal to 325 meshes.
10. CO-resistant for use in a well cementing cement according to any one of claims 1 to 9 2 The preparation method of the corrosion thermal insulation material is characterized by comprising the following steps: weighing a heat-insulating matrix, aluminum titanate powder, sodium monofluorophosphate and potassium aminotrimethylene phosphonate, and fully mixing to obtain the CO-resistant cement for well cementation 2 And (5) corroding the heat insulation material.
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