CN113060962B - Oil well cement corrosion-resistant early strength agent suitable for salt-gypsum layer well cementation and preparation method thereof - Google Patents
Oil well cement corrosion-resistant early strength agent suitable for salt-gypsum layer well cementation and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 79
- 239000004568 cement Substances 0.000 title claims abstract description 77
- 239000003129 oil well Substances 0.000 title claims abstract description 28
- 238000005260 corrosion Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 17
- 239000010440 gypsum Substances 0.000 title claims abstract description 17
- 230000007797 corrosion Effects 0.000 title abstract description 20
- 239000011707 mineral Substances 0.000 claims abstract description 67
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 66
- 239000010410 layer Substances 0.000 claims abstract description 40
- 150000003384 small molecules Chemical class 0.000 claims abstract description 13
- 239000011229 interlayer Substances 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 claims 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 claims 1
- 230000007423 decrease Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 238000002156 mixing Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000004108 freeze drying Methods 0.000 description 12
- 230000008719 thickening Effects 0.000 description 11
- 239000007790 solid phase Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229940044172 calcium formate Drugs 0.000 description 2
- 239000004281 calcium formate Substances 0.000 description 2
- 235000019255 calcium formate Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002343 natural gas well Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- -1 aluminate salts Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Classifications
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- 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
- 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
- C04B2103/10—Accelerators; Activators
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明公开了一种适用于盐膏层固井的油井水泥防腐型早强剂及其制备方法，该早强剂包含以下重量份数的组分：25～40份层状矿物A、40～50份层状矿物B、10～40份纳米SiO2；其中，所述层状矿物A的层间含有NO3 ‑；所述层状矿物B的层间含有机小分子早强剂。本发明的油井水泥防腐型早强剂不含有Cl‑、SO4 2‑，从根本上降低了早强剂导致的水泥环腐蚀和后期力学性能下降的问题。The invention discloses an oil well cement anti-corrosion type early strength agent suitable for cementing in a salt-gypsum layer and a preparation method thereof. The early strength agent comprises the following components in parts by weight: 25-40 parts of layered mineral A, 40- 50 parts of layered mineral B and 10 to 40 parts of nano-SiO 2 ; wherein, the interlayer of the layered mineral A contains NO 3 ‑ ; the interlayer of the layered mineral B contains an organic small molecule early strength agent. The anti-corrosion early-strength agent for oil well cement of the invention does not contain Cl- and SO 4 2- , which fundamentally reduces the problems of cement sheath corrosion and later mechanical property decline caused by the early-strength agent.
Description
Technical Field
The invention relates to an oil well cement anticorrosion early strength agent, in particular to an oil well cement anticorrosion early strength agent suitable for salt-gypsum layer cementing and a preparation method thereof.
Background
In the process of oil exploitation, well cementation is a key link for connecting well drilling and later-stage oil exploitation. In the well cementation process, cement slurry is injected from a ground wellhead, pumped to an annular space between the casing and the stratum through the casing, and forms a cement sheath after being solidified, so that the cement sheath plays a role in supporting and protecting the casing and sealing and isolating oil, gas and water layers.
Currently, the exploration of oil and gas resources is mainly gradually shifted from conventional oil and gas resources which are easy to exploit to deep/ultra-deep layers which are complex and difficult to exploit, the formation conditions are complex, and well cementation is often confronted with the problems that the sealing section is ultra-long, the temperature difference between the top and the bottom of a cement sheath is large, and salt-containing formations, paste salt layers or brine layers are easy to leak and the like. Most natural gas wells face the difficult problem of long-seal-section well cementation operation under the condition of a huge thick salt layer, a paste salt layer or a composite salt layer. The ultra-long sealing section and the large top-bottom temperature difference must require enough cement paste retarder to ensure the injection safety at high temperature. But after returning to the top, the strength of the cement sheath develops slowly at low temperature, and even an over-retarding phenomenon appears. Cl in salt or paste-salt formations-、SO4 2-Can diffuse into a cement sheath, leads to later-stage cement stone corrosion damage and mechanical property reduction, and seriously threatens the long-term sealing integrity of the natural gas well. Therefore, the corrosion resistance and the top strength of the cement ring under the long sealing section of the stratum with the salt layer and the paste-salt layer are ensured to be rapidly developedThe later sealing integrity of the high cement ring is of great significance.
The long sealing section well is generally fixed under the condition of large temperature difference by adopting an early strength agent to improve the strength of cement slurry after returning to the top. At present, the commonly used oil well cement early strength agents are mainly inorganic salts and organic compounds, and related early strength agent patents also mainly adopt different inorganic salt compounding or inorganic salt and organic compound compounding, for example, Chinese patent CN105347716A, a dispersive chlorine-free oil well cement low-temperature early strength agent and cement paste containing the same; chinese patent CN106830744B, an early strength agent for well cementation and a preparation method thereof; chinese patent CN109943303A, a chlorine-free coagulation accelerator early strength agent for oil well cement, a preparation method and application thereof; chinese patent CN109943304A, an oil well cement coagulation accelerator early strength agent and a preparation method and application thereof; chinese patent CN110317589A, early strength agent and preparation method thereof, cement slurry for well cementation; chinese patent CN106746848B, a composite low-density cement early strength agent, a preparation method and application; chinese patent CN104194752A, a low-temperature early strength agent for coal bed gas well cementing and cement slurry for cementing containing the same.
The inorganic salt early strength agent mainly comprises chloride salts, aluminate salts, sulfate salts, lithium salts and nitrate salts, such as calcium chloride, lithium carbonate, sodium silicate, calcium sulfate, sodium nitrate, sodium aluminate and the like; the organic early strength agent comprises formamide, triethanolamine, calcium formate, sodium acetate and the like. However, these early strength agents all have certain disadvantages:
(1) the chloride and sulfate early strength agents can improve the early strength of the set cement, but can cause the corrosion of the set cement and a sleeve, increase the permeability of the set cement, aggravate the damage of a later-stage cement sheath and influence the long-term packing durability of the cement sheath;
(2) the lithium salt early strength agent has high cost and high reaction speed, and releases large amount of heat in a short time, if the heat is not consumed or released in time, microcracks are generated in the cement, so that the later strength is reduced;
(3) after the mixing amount of the inorganic salt early strength agent is larger, the slurry has strong thixotropy and high consistency, and the annular pressure loss is increased and the leakage risk is increased easily caused by cementing in a formation which is easy to leak;
(4) the addition of organic triethanolamine is sensitive when used alone, is extremely small and is not easy to control, and the excessive triethanolamine is easy to generate ultra-retardation;
(5) the addition of calcium formate and sodium acetate easily causes the loss of the later strength of the set cement;
(6) the early strength agent has the coagulation promoting effect, and the thickening time is shortened due to excessive addition, so that the operation safety is influenced; the addition amount is too small to exert the effect, which is also the deficiency of the prior early strength agent.
Disclosure of Invention
The invention aims to provide an oil well cement corrosion-resistant early strength agent suitable for cementing a salt-gypsum layer and a preparation method thereof, which solve the problem that chloride and sulfate early strength agents are easy to corrode and reduce the problems of cement sheath corrosion and later-stage mechanical property reduction caused by the existing early strength agent.
In order to achieve the purpose, the invention provides an oil well cement anticorrosion type early strength agent suitable for salt-gypsum layer cementing, which comprises the following components in parts by weight: 25-40 parts of layered mineral A, 40-50 parts of layered mineral B and 10-40 parts of nano SiO2(ii) a Wherein the lamellar mineral A contains NO between layers3 -(ii) a The interlayer of the layered mineral B contains an organic micromolecule early strength agent.
Preferably, the lamellar mineral a is prepared by the following method: mixing a high-valence metal nitrate more than trivalent and a low-valence metal nitrate less than divalent according to a molar ratio of 2: 1-4: 1 to form a mixed metal nitrate, putting the mixed metal nitrate in water, and adjusting the pH of the solution to 9-12; reacting at 70-90 ℃ in an inert gas atmosphere; after the reaction is finished, carrying out suction filtration, and freeze-drying or drying the solid at 50-70 ℃ to obtain the product containing NO between layers3 -The layered mineral A of (1).
The lamellar mineral B is prepared by the following method: mixing an organic small-molecule early strength agent and the layered mineral A according to the mass ratio of 0.3: 1-0.6: 1, and reacting the mixture in an organic solvent at 60-90 ℃ in an inert gas atmosphere; and after the reaction is finished, carrying out suction filtration, and carrying out freeze drying or drying at 50-70 ℃ on the solid to obtain the layered mineral B containing the organic small-molecule early strength agent between layers.
Preferably, the organic small-molecule early strength agent is selected from triethanolamine and/or triisopropanolamine.
Preferably, the high-valence metal nitrate is selected from Al (NO)3)3·9H2O and/or Fe (NO)3)3·9H2O。
Preferably, the low-valent metal nitrate is selected from Mg (NO)3)2·6H2O、Zn(NO3)2·6H2O、Zn(NO3)2·4H2O and Ca (NO)3)2·4H2And (4) in O.
Preferably, the organic solvent is ethylene glycol or a mixture of ethanol and water.
The invention also aims to provide a preparation method of the oil well cement anti-corrosion early strength agent suitable for cementing a salt-gypsum layer, which comprises the following steps: mixing the layered mineral A, the layered mineral B and the nano SiO2And (3) uniformly mixing to obtain the oil well cement corrosion-resistant early strength agent suitable for salt-gypsum layer cementing.
The preparation method of the layered mineral A comprises the following steps: mixing a high-valence metal nitrate with more than three valence and a low-valence metal nitrate with less than two valence according to a molar ratio of 2: 1-4: 1 to form mixed metal nitrate, adding 15-40 parts by weight of the mixed metal nitrate into 100 parts by weight of water, and adjusting the pH of the solution to 9-12; reacting at 70-90 ℃ in an inert gas atmosphere; after the reaction is finished, carrying out suction filtration, and freeze-drying or drying the solid at 50-70 ℃ to obtain the product containing NO between layers3 -The layered mineral A of (1).
The preparation method of the layered mineral B comprises the following steps: mixing an organic small-molecule early strength agent and the layered mineral A according to the mass ratio of 0.3: 1-0.6: 1, and reacting 15-35 parts by weight of the mixture in 100 parts by weight of an organic solvent at 60-90 ℃ in an inert gas atmosphere; and after the reaction is finished, carrying out suction filtration, and carrying out freeze drying or drying at 50-70 ℃ on the solid to obtain the layered mineral B containing the organic small-molecule early strength agent between layers.
Preferably, the high-valence metal nitrate is selected from Al (NO)3)3·9H2O and/or Fe (NO)3)3·9H2O; the low-valence metal nitrate is selected from Mg (NO)3)2·6H2O、Zn(NO3)2·6H2O、Zn(NO3)2·4H2O and Ca (NO)3)2·4H2And (4) in O.
Preferably, the organic small-molecule early strength agent is selected from triethanolamine and/or triisopropanolamine.
Preferably, the organic solvent is a mixture of ethylene glycol or ethanol and water, and the volume ratio of the ethylene glycol or the ethanol to the water is 1: 1.
The oil well cement corrosion-resistant early strength agent suitable for salt-gypsum layer cementing and the preparation method thereof solve the problem that chloride and sulfate early strength agents are easy to corrode, and have the following advantages:
(1) the oil well cement anticorrosive early strength agent does not contain Cl-、SO4 2-The problems of cement sheath corrosion and later-period mechanical property reduction caused by the early strength agent are fundamentally reduced;
(2) the oil well cement anticorrosive early strength agent utilizes the formation temperature and Cl in a salt-gypsum layer-、SO4 2-NO with early strengthening effect on layered minerals3 -And organic early strength agent molecules are released and replaced, so that the slow release effect of the early strength agent is realized, the environmental response and slow release characteristics avoid the shortening of thickening time caused by the early reaction of the early strength agent, and the contradiction between the long thickening time required by the safety of the injection cement at high temperature and the fast development requirement of the early strength at low temperature is overcome. Meanwhile, Cl which originally has corrosion effect can be replaced by interlayer anions-、SO4 2-Is inserted into the interlayer of the layered mineral to prevent diffusion and migration and reaction with set cement, and reduce Cl-、SO4 2-The ability to corrode set cement;
(3) the oil well cement anticorrosive early strength agent has nanometer level solid phase grains and may be used in producing cementThe crystal nucleus of the growth of the substance increases the compactness of the cement and further reduces Cl-、SO4 2-The diffusion capacity improves the corrosion resistance and the mechanical property of the set cement, and realizes the effect of one agent with multiple effects.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An oil well cement anticorrosion early strength agent suitable for salt-gypsum layer cementing is prepared by the following steps:
(1) preparation of the layered mineral a:
mixing Al (NO)3)3·9H2O and Mg (NO)3)2·6H2Mixing O in a molar ratio of 3:1 to obtain mixed metal salt, adding 35 parts by weight of the mixed metal salt into a reactor filled with 100 parts by weight of deionized water, rapidly stirring, and adjusting the pH value of the solution to 9 by adopting NaOH. Then, N was introduced into the reactor2(prevention of CO in air)2Dissolved in the solution, carbonized), and reacted at 70 ℃ for 24 hours. After the reaction is finished, cooling the solution to room temperature, washing the solution by deionized water under the condition of suction filtration until the pH of the solution is neutral, and then freeze-drying the prepared solid phase for 24 hours to obtain the product containing NO between layers3 -The layered mineral A of (1).
(2) Preparation of layered mineral B:
mixing triethanolamine and the lamellar mineral A according to the mass ratio of 0.4:1, weighing 20 parts by weight of the mixture, adding the mixture into a reactor filled with 100 parts by weight of mixed solution of glycol and water according to the volume ratio of 1:1, and introducing N2After that, the reaction was stirred rapidly at 90 ℃ for 48 h. After the reaction is finished, cooling the solution to room temperature, washing for 3-5 times by using deionized water under the suction filtration condition, and freeze-drying the prepared solid phase for 24 hours to obtain the productTo obtain the layered mineral B containing triethanolamine between layers.
(3) Preparing an anticorrosive early strength agent:
25 parts of layered mineral A, 50 parts of layered mineral B and 25 parts of nano SiO2And (4) uniformly mixing to obtain the anticorrosive early strength agent.
Example 2
An oil well cement anticorrosion early strength agent suitable for salt-gypsum layer cementing is prepared by the following steps:
(1) preparation of the layered mineral a:
mixing Al (NO)3)3·9H2O and Zn (NO)3)2·6H2Mixing O in a molar ratio of 3:1 to obtain mixed metal salt, adding 30 parts by weight of the mixed metal salt into a reactor filled with 100 parts by weight of deionized water, rapidly stirring, and adjusting the pH value of the solution to 10 by adopting NaOH. Then introducing N into the reactor2The reaction was carried out at 85 ℃ for 15 h. After the reaction is finished, cooling the solution to room temperature, washing the solution by deionized water under the condition of suction filtration until the pH of the solution is neutral, and then freeze-drying the prepared solid phase for 24 hours to obtain the product containing NO between layers3 -The layered mineral A of (1).
(2) Preparation of layered mineral B:
mixing triethanolamine and the lamellar mineral A according to the mass ratio of 0.5:1, weighing 20 parts by weight of the mixture, adding the mixture into a reactor filled with 100 parts by weight of mixed solution of glycol and water according to the volume ratio of 1:1, and introducing N2After that, the reaction was stirred rapidly at 70 ℃ for 30 h. And after the reaction is finished, cooling the solution to room temperature, washing for 3-5 times by using deionized water under the suction filtration condition, and freeze-drying the prepared solid phase for 24 hours to obtain the layered mineral B containing triethanolamine between layers.
(3) Preparing an anticorrosive early strength agent:
32 parts of lamellar mineral A, 48 parts of lamellar mineral B and 20 parts of nano SiO2And (4) uniformly mixing to obtain the anticorrosive early strength agent.
Example 3
An oil well cement anticorrosion early strength agent suitable for salt-gypsum layer cementing is prepared by the following steps:
(1) preparation of the layered mineral a:
mixing Al (NO)3)3·9H2O and Mg (NO)3)2·6H2Mixing O in a molar ratio of 4:1 to obtain mixed metal salt, adding 25 parts by weight of the mixed metal salt into a reactor containing 100 parts by weight of deionized water, rapidly stirring, and adjusting the pH value of the solution to 11 by using NaOH. Then introducing N into the reactor2And reacting at 70 ℃ for 24 h. After the reaction is finished, cooling the solution to room temperature, washing the solution by deionized water under the condition of suction filtration until the pH of the solution is neutral, and then freeze-drying the prepared solid phase for 24 hours to obtain the product containing NO between layers3 -The layered mineral A of (1).
(2) Preparation of layered mineral B:
mixing triethanolamine and the lamellar mineral A according to the mass ratio of 0.35:1, weighing 30 parts by weight of the mixture, adding the mixture into a reactor filled with 100 parts by weight of mixed solution of glycol and water according to the volume ratio of 1:1, and introducing N2After that, the reaction was stirred rapidly at 80 ℃ for 24 h. And after the reaction is finished, cooling the solution to room temperature, washing for 3-5 times by using deionized water under the suction filtration condition, and freeze-drying the prepared solid phase for 24 hours to obtain the layered mineral B containing triethanolamine between layers.
(3) Preparing an anticorrosive early strength agent:
30 parts of a layered mineral A, 45 parts of a layered mineral B and 25 parts of nano SiO2Mixing uniformly to obtain the anti-corrosion early strength agent
Example 4
An oil well cement anticorrosion early strength agent suitable for salt-gypsum layer cementing is prepared by the following steps:
(1) preparation of the layered mineral a:
mixing Al (NO)3)3·9H2O and Ca (NO)3)2·6H2Mixing O in a molar ratio of 3:1 to obtain mixed metal salt, adding 30 parts by weight of the mixed metal salt into a reactor filled with 100 parts by weight of deionized water, rapidly stirring, and adjusting the pH value of the solution to 10 by adopting NaOH. However, the device is not suitable for use in a kitchenThen introducing N into the reactor2And reacting at 80 ℃ for 24 h. After the reaction is finished, cooling the solution to room temperature, washing the solution by deionized water under the condition of suction filtration until the pH of the solution is neutral, and then freeze-drying the prepared solid phase for 24 hours to obtain the product containing NO between layers3 -The layered mineral A of (1).
(2) Preparation of layered mineral B:
mixing triisopropanolamine and the lamellar mineral A according to the mass ratio of 0.55:1, weighing 25 parts by weight of the mixture, adding the mixture into a reactor filled with 100 parts by weight of ethanol and water mixed solution according to the volume ratio of 1:1, and introducing N2After that, the reaction was stirred rapidly at 85 ℃ for 20 h. And after the reaction is finished, cooling the solution to room temperature, washing for 3-5 times by using deionized water under the suction filtration condition, and freeze-drying the prepared solid phase for 24 hours to obtain the layered mineral B containing triisopropanolamine between layers.
(3) Preparing an anticorrosive early strength agent:
35 parts of lamellar mineral A, 45 parts of lamellar mineral B and 20 parts of nano SiO2And (4) uniformly mixing to obtain the anticorrosive early strength agent.
Experimental example 1 Performance test
1. Preparation of cement paste
Setting blank group cement paste, comparison group cement paste and embodiment cement paste, wherein the components of each cement paste are as follows:
the formula of the blank group cement slurry is as follows: 100 parts by weight of JH-G grade oil well cement, 20 parts by weight of silicon powder, 10 parts by weight of micro silicon, a density regulator, 6 parts by weight of a filtrate reducer, 5 parts by weight of a retarder and 1.0 part by weight of a dispersant
The formula of the cement paste of the control group is as follows: 100 parts by weight of JH-G grade oil well cement, 20 parts by weight of silicon powder, 10 parts by weight of micro-silicon, a density regulator and 3 parts by weight of CaCl2+6 parts by weight of fluid loss additive, 5 parts by weight of retarder and 1.0 part by weight of dispersant
The cement paste formula of the embodiment is as follows: 100 parts by weight of JH-G grade oil well cement, 20 parts by weight of silicon powder, 10 parts by weight of micro silicon, a density regulator and 4 parts by weight of anti-corrosive early strength agent, 6 parts by weight of filtrate reducer, 5 parts by weight of retarder and 1.0 part by weight of dispersing agent in the corresponding examples
2. Performance testing
The cement paste thickening time and compressive strength tests of the examples, the control group and the blank group are carried out according to GB/T19139-2012 oil well cement test method; in the corrosion resistance evaluation experiment, the prepared cement stone is preserved for 2 days at 100 ℃ and 20.7MPa in advance, and then is soaked in a medium containing corrosion (containing 5 mass percent of Na)2SO4NaCl with the mass fraction of 5 percent) is continuously maintained at 100 ℃ for 5 days under the condition of 20.7MPa, and then taken out to test the compressive strength; and curing the non-corroded sample at 100 ℃ and 20.7MPa for 7 days, and taking out the non-corroded sample to test the compressive strength.
Table 1 shows the effect of the corrosion-inhibiting early strength agent on the early strength and thickening time of the cement paste
Note: a: thickening time at 150 ℃ and 130 MPa; b: the compressive strength is under the conditions of 100 ℃, 20.7MPa and 24 h; c: the compressive strength is under the conditions of 90 ℃, 20.7MPa and 24 h; d is the compressive strength under the conditions of 80 ℃, 20.7MPa and 24 h;
table 2 shows the results of the experiment of corrosion resistance of the corrosion-resistant early strength agent to cement slurry
Note: compression strength at 100 ℃, 20.7MPa, 7 d.
As can be seen from the table, although the conventional calcium chloride early strength agent can improve the early strength of the cement paste, the effect on the thickening time of the cement paste is great, and the thickening time is shortened by 140-200 min. The corrosion-resistant early strength agent prepared by the invention is doped into cement paste, the thickening time influence is small, and compared with the thickening time in a blank group, the thickening time is shortThe shortening is only about 40 min. After high-temperature prefabrication at 150 ℃, the strength of the cement stone doped with the anticorrosive early strength agent develops rapidly under maintenance at different top temperatures. Meanwhile, compared with a control group sample, after the anti-corrosion early strength agent prepared by the invention is doped into cement slurry and soaked in a corrosive medium, the reduction of the compressive strength is inhibited, the strength reduction rate of 168 hours is only about 10 percent, which is obviously higher than that of the control group, and the set cement resists Cl-、SO4 2-The corrosion capability of the steel is obviously improved.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
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