CN111138160A - H2S corrosion-resistant cement, preparation method and application thereof, and well cementation cement sheath - Google Patents
H2S corrosion-resistant cement, preparation method and application thereof, and well cementation cement sheath Download PDFInfo
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- CN111138160A CN111138160A CN202010000265.7A CN202010000265A CN111138160A CN 111138160 A CN111138160 A CN 111138160A CN 202010000265 A CN202010000265 A CN 202010000265A CN 111138160 A CN111138160 A CN 111138160A
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- cement
- corrosion
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- resistant
- phosphate
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- 239000004568 cement Substances 0.000 title claims abstract description 156
- 238000005260 corrosion Methods 0.000 title claims abstract description 71
- 230000007797 corrosion Effects 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 22
- 239000010452 phosphate Substances 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004645 aluminates Chemical class 0.000 claims abstract description 11
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 11
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 6
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 5
- 239000004137 magnesium phosphate Substances 0.000 claims description 5
- 229960002261 magnesium phosphate Drugs 0.000 claims description 5
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 5
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 5
- 239000004132 Calcium polyphosphate Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 4
- 229940009859 aluminum phosphate Drugs 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 235000001055 magnesium Nutrition 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 claims description 4
- 229940099402 potassium metaphosphate Drugs 0.000 claims description 4
- 235000019829 sodium calcium polyphosphate Nutrition 0.000 claims description 4
- 239000010959 steel Substances 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003129 oil well Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910001653 ettringite Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000845082 Panama Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- AGWMJKGGLUJAPB-UHFFFAOYSA-N aluminum;dicalcium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Ca+2].[Ca+2].[Fe+3] AGWMJKGGLUJAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 239000009096 changqing Substances 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- TWHXWYVOWJCXSI-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O TWHXWYVOWJCXSI-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/23—Acid resistance, e.g. against acid air or rain
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a H-resistant steel2S corrosion cement, preparation method and application thereof, and well cementation cement sheath, belonging to the technical field of sulfur-containing oil and gas well cementing and being H-resistant2S corrosion cement, by weight, the H corrosion resistant cement2The S corrosion cement comprises the following components: 100 parts of aluminate cement or sulphoaluminate cement, 5-50 parts of phosphate, 20-80 parts of alumina and 5-100 parts of filling material, wherein the filling material comprises at least one of the following components: kaolin, bauxite; the embodiment of the invention provides the H resistance2S corrosion cement having excellent H resistance2S corrosion ability, tested at 80 ℃ and H2The compression strength of the S partial pressure is not reduced but increased by 41 percent at the highest after 28 days of corrosion under the condition of 2MPa of S partial pressure.
Description
Technical Field
The invention belongs to the technical field of sulfur-containing oil and gas well cementing, and particularly relates to H2S corrosion-resistant cement, a preparation method and application thereof, and a well cementing cement sheath.
Background
At present, about 1/3 in oil and gas fields in the world contains H2And (4) S gas. Several oil and gas fields (such as Tarim, southwest, Changqing, China Central plains, North China, Panama in America, Alberta in Canada) in China all contain H with different degrees2S gas, Tarriwood oil field Tower Medium gas field, southwest oil gas field Puguang gas field and Rojiazhai gas field H2The highest value of S content is more than 10000 ppm.
H2S and oil well cement are subjected to chemical reaction to reduce the alkalinity of well cementation set cement, so that cementitious components in the set cement are reduced, a pore structure is damaged, the permeability is increased, and the well cementation set cement is resistant toThe pressure strength is reduced or even completely lost, the sealing integrity of the cement sheath is damaged, the packing fails, the annular pressure is easy to appear, the wellhead gas channeling occurs, and the severe challenge is brought to the safety production of the oil-gas well, and simultaneously, H2S is a highly toxic gas. Fleeing up to the ground can cause serious damage to surrounding life, property and environment. After the pore structure of the cement sheath is destroyed, H2S can directly corrode the underground pipe column, and the underground pipe column is usually brittle-broken when the stress of the underground pipe column is far lower than the yield strength of the underground pipe column due to the stress corrosion cracking effect of sulfide, so that oil, a casing pipe or the whole well is scrapped, and if the underground pipe column is highly toxic H2S leaks out, and people, ecological environment and equipment around the well bore can be greatly damaged. Therefore, to prevent the inclusion of H2The formation fluid of S corrodes the casing and accessories, and the problem to be solved firstly is the corrosion prevention problem of the cement sheath.
The prior art of silicate cement-based corrosion prevention mainly adopts superfine materials to reduce the permeability of set cement; the calcium-silicon ratio is changed to reduce the alkalinity of the cement and reduce the amount of substances capable of chemically reacting with acid gases; and (3) doping special corrosion-resistant materials to form a protective layer on the surface of the set cement. Various means have certain anticorrosion effect, but only retard the corrosion of cement stone from the aspect of dynamics, and as the fundamental improvement on materials is not carried out, the long-term anticorrosion performance is not ideal and is not solved fundamentally.
Disclosure of Invention
In view of the above problems, the present invention has been made in order to provide an H2S corrosion resistant cement, a method of preparing the same, applications thereof, and a well cementation cement sheath that overcome the above problems.
The embodiment of the invention provides an H-resistant cable2S corrosion cement, by weight, the H corrosion resistant cement2The S corrosion cement comprises the following components:
aluminate cement or sulphoaluminate cement 100 parts
5-50 parts of phosphate
20-80 parts of alumina
5-100 parts of a filling material,
the filling material comprises at least one of the following: kaolin and bauxite.
Further, the H resistance is calculated according to the weight portion2The S corrosion cement comprises the following components:
aluminate cement or sulphoaluminate cement 100 parts
15 portions of phosphate
50 portions of alumina
48 parts of filling materials.
Further, the phosphate comprises at least one of: magnesium phosphate, aluminum phosphate, potassium metaphosphate, sodium polyphosphate, calcium polyphosphate and magnesium polyphosphate.
Based on the same invention concept, the embodiment of the invention also provides an H-resistant cable2The preparation method of the S corrosion cement comprises the following steps:
preparing for H resistance according to the weight parts2S corrosion of said components of the cement;
the components are mixed evenly to prepare the H-resistant material2S corrodes the cement.
Based on the same invention concept, the embodiment of the invention also provides an H-resistant cable2Application of S corrosion cement in H-containing environment2S environment.
Based on the same invention concept, the embodiment of the invention also provides an H-resistant cable2S corrosion of cement sheath for cementing well2S is formed after cement slurry is corroded for well cementation.
Further, the H resistance2The water cement ratio of the S corrosion cement to the water is 0.40-0.60.
Further, the H resistance2The water cement ratio of the S corrosion cement to the water is 0.44.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
1 the invention provides an embodiment of the invention with H resistance2The S-corrosion cement is non-silicate-base chemical bonding cement, acid-base reaction of acid-base component in the cement occurs after the cement is mixed with slurry to form a gelled material, and the gelled material cannot be mixed with H2And S corrosion.
2 the invention provides the H-resistant2S corrosion cement and toolHas excellent H resistance2S corrosion ability, tested at 80 ℃ and H2The compression strength of the S partial pressure is not reduced but increased by 41 percent at the highest after 28 days of corrosion under the condition of 2MPa of S partial pressure.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The reasons for cement ring corrosion in oil wells are:
H2s, dissolved in water, penetrates into the cement and CaOH2Reaction to produce CaSO4·2H2O gypsum. Cement stone CSH gel and H2The S solution can also react to generate CaSO4·2H2O gypsum. The sulfate radical dissolved in water can also react with tricalcium aluminate and tetracalcium aluminoferrite in the cement to produce ettringite AFT, and ettringite crystals cause the internal stress of a system and are also the main reason for generating cracks by the expansion of a cement hardened body. The main reason is that the gypsum and AFT ettringite expand to cause cracks on the set cement, so that the permeability of the corroded set cement is greatly increased, and the compressive strength of the set cement is rapidly reduced.
In this embodiment, an H-tolerant is provided2S corrosion cement, by weight, the H corrosion resistant cement2The S corrosion cement comprises the following components:
aluminate cement or sulphoaluminate cement 100 parts
5-50 parts of phosphate
20-80 parts of alumina
5-100 parts of a filling material,
the filling material comprises at least one of the following: kaolin and bauxite.
By adopting the technical scheme, the alloy has high H resistance2When S corrosion cement is added into the slurry preparation water to prepare cement slurry, phosphate ions contact with the surfaces of cement particles to accelerate the hydration rate and form phosphate hydrate. With the continuous formation of phosphate hydration products, a large amount of phosphate ions are contacted with cement particles due to volume expansion, and a large amount of phosphate hydration products are rapidly formed; as phosphate hydration products grow and grow outward, the particles and other fillers such as alumina, filler material, surface-coated hydration products are integrated with each other to harden the phosphate cement and produce a chemically bonded cement sheath that is not silicate-based, due to the absence of the CaOH of oil well cement2And a CSH gel component, and the phosphoric acid is more acidic than the hydrogen sulfuric acid, so that the cement is not coated with H2And (4) S reaction. Since the phosphate reacts with the cement very rapidly, which may lead to an excessively rapid development of strength, and structural defects occur after the cement is cured, which may affect the integrity of the cement, it is necessary to add alumina and other filler materials to reduce the concentrations of the cement and phosphate, in order to slow down the reaction rate.
Specifically, the H resistance is calculated according to the weight portion2The S corrosion cement comprises the following components:
aluminate cement or sulphoaluminate cement 100 parts
15 portions of phosphate
50 portions of alumina
48 parts of filling materials.
By adopting the technical scheme and adopting the optimal weight part ratio, the composite material has high H resistance2The S-corrosion cement has optimal H resistance2S corrosion performance.
Specifically, the phosphate comprises at least one of the following: magnesium phosphate, aluminum phosphate, potassium metaphosphate, sodium polyphosphate, calcium polyphosphate and magnesium polyphosphate.
Based on the same invention concept, the embodiment of the invention also provides an H-resistant cable2The preparation method of the S corrosion cement comprises the following steps:
preparing for H resistance according to the weight parts2S corrosion of said components of the cement;
the components are mixed evenly to prepare the H-resistant material2S corrodes the cement.
The H-resistant alloy prepared by adopting the technical scheme2The S corrosion cement has excellent H resistance2S corrosion performance.
Based on the same invention concept, the embodiment of the invention also provides an H-resistant cable2Application of S corrosion cement in H-containing environment2S environment.
The embodiment of the invention provides the H resistance2S corrosion cement having excellent H resistance2S corrosion, and is therefore suitable for containing H2And S is applied in the environment.
Based on the same invention concept, the embodiment of the invention also provides an H-resistant cable2S corrosion well cementation cement sheath which is formed by H2S corrosion resistant cement slurry after well cementation.
H resistance obtained by adopting the technical scheme2S corrosion of cement sheath for well cementation, high H2The oil well with S content has excellent corrosion resistance and can prevent H2S-pipe fleeing causes damage to personnel, equipment and the environment.
In particular, the said H resistance2The water-cement ratio of S corrosion cement to water is 0.40-0.60, and the preferred H resistance2S the water-cement ratio of the corrosion cement to the proportioned water is 0.44.
By adopting the technical scheme, the density range of 1.35-1.90g/cm can be prepared3The phosphate cement slurry meets the requirements of well cementation of different stratums.
The cement with H2S corrosion resistance, the preparation method, the application and the well cementation cement sheath of the application are combined with the embodiment
A detailed description will be given.
The aluminate cement of the embodiment of the invention is produced by Zhengzhou aluminum all refractory material Co., Ltd, and has a trade name of A600; the sulphoaluminate cement is produced by Zhengzhou king building cement industry Co., Ltd, and has a trade name of ZWSA; the phosphate material was supplied by chemical reagents ltd, miuiou, department of tianjin; the kaolin is provided by Jade Biotechnology Limited of Dongying, and the particle size is 800 meshes; bauxite is supplied by Zibo excellence refractory Co., Ltd, with a particle size of 325 mesh.
Example 1
Adding 8 parts by weight of sodium phosphate, 8 parts by weight of sodium polyphosphate, 6 parts by weight of disodium hydrogen phosphate, 5 parts by weight of sodium hexametaphosphate, 30 parts by weight of alumina and 5 parts by weight of bauxite into 100 parts by weight of aluminate cement, taking municipal tap water as slurry preparation water, setting the water-cement ratio to be 0.40, preparing the cement slurry according to GB/T19139-3Curing in a curing box at 80 ℃ for 24h for forming, wherein the 24h compressive strength is 14.1 MPa. Coring cement stone, making into cylinder with diameter and height of 25mm, and placing into H-resistant container2Introducing H into the S-corrosion high-temperature and high-pressure reaction kettle according to a calculated proportion at room temperature2S and N2Heating to 80 ℃ to enable H2The S partial pressure is 2MPa, and the total pressure is 10 MPa. After the cement paste is cured for 28d under the condition, the compressive strength is tested to be 19.7MPa, the compressive strength is not reduced but increased after corrosion, and the cement paste has good H resistance2S corrosion performance.
Example 2
Adding 5 parts by weight of ammonium hydrogen phosphate, 9 parts by weight of ammonium dihydrogen phosphate, 7 parts by weight of magnesium phosphate, 2 parts by weight of sodium dihydrogen phosphate, 80 parts by weight of aluminum oxide, 3 parts by weight of kaolin and 45 parts by weight of bauxite into 100 parts by weight of sulphoaluminate cement, preparing cement paste according to GB/T19139-3Curing in a curing box at 80 ℃ for 24H for forming, wherein the 24H compressive strength is 12.8MPa, the temperature is 80 ℃ and the temperature is H2And the compressive strength of the cured cement paste is 15.0MPa after 28 days under the condition of S partial pressure of 2 MPa.
Example 3
To 100 parts by weight of sulphoaluminate cement, 3 parts by weight of potassium phosphate, 1 part by weight of calcium phosphatePhosphoric acid rate, 60 parts of alumina and 5 parts of bauxite by weight, municipal tap water is used as slurry preparation water, the water-cement ratio is 0.60, the cement slurry is prepared according to GB/T19139-3The 24-hour compressive strength of the material is 10.7MPa, 80 ℃ and H2And the compressive strength of the cured cement paste is 12.8MPa after 28 days under the condition of S partial pressure of 2 MPa.
Example 4
Adding 12 parts by weight of sodium polyphosphate, 15 parts by weight of sodium hexametaphosphate, 8 parts by weight of ammonium dihydrogen phosphate, 10 parts by weight of potassium phosphate, 5 parts by weight of aluminum tripolyphosphate, 20 parts by weight of alumina and 95 parts by weight of kaolin into 100 parts by weight of sulphoaluminate cement, preparing cement paste according to GB/T19139-3The 24-hour compressive strength of the steel is 14.0MPa, 80 ℃ and H2And the compressive strength of the cured cement paste is 19.8MPa after 28 days under the condition of the S partial pressure of 2 MPa.
Comparative example 1
The comparative example was the same as example 1 except that the following technical features were different from those of example 1. The difference lies in that:
by weight, H resistance2The corrosion cement comprises the following components:
aluminate cement or sulphoaluminate cement 90 parts
Phosphate 3 parts
16 portions of alumina
Bauxite 9 parts
The phosphate is magnesium phosphate, aluminum phosphate, potassium metaphosphate or sodium metaphosphate.
The density of the obtained cement paste is 1.90g/cm under the condition that the water-cement ratio is 0.443The 24-hour compressive strength of the steel is 18.8MPa, 80 ℃ and H2And the compressive strength of the cured cement paste is 8.7MPa after 28 days under the condition of S partial pressure of 2 MPa.
Comparative example 2
The comparative example was the same as example 1 except that the following technical features were different from those of example 1. The difference lies in that:
in parts by weightH resistance2The corrosion cement comprises the following components:
110 portions of aluminate cement or sulphoaluminate cement
55 portions of phosphate
90 portions of alumina
110 parts of bauxite,
the phosphate is sodium polyphosphate, calcium polyphosphate or magnesium polyphosphate.
The density of the obtained cement paste is 1.35g/cm under the condition that the water-cement ratio is 0.63The 24-hour compressive strength of the steel is 13.7MPa, 80 ℃ and H2And the compressive strength of the cured cement paste is 6.3MPa after 28 days under the condition of S partial pressure of 2 MPa.
Comparative example 3
The comparative example was the same as example 1 except that the bauxite filler material was not contained.
The density of the obtained cement slurry is 1.41g/cm3The 24-hour compressive strength of the material is 15.4MPa, 80 ℃ and H2And the compressive strength of the cured cement paste is 7.1MPa after 28 days under the condition of S partial pressure of 2 MPa.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. H-resistant cable2S corrosion cement is characterized in that the cement has H resistance in parts by weight2The S corrosion cement comprises the following components:
aluminate cement or sulphoaluminate cement 100 parts
5-50 parts of phosphate
20-80 parts of alumina
5-100 parts of a filling material,
the filling material comprises at least one of the following: kaolin and bauxite.
2. An H-tolerant composition according to claim 12S corrosion cement is characterized in that the cement has H resistance in parts by weight2The S corrosion cement comprises the following components:
aluminate cement or sulphoaluminate cement 100 parts
15 portions of phosphate
50 portions of alumina
48 parts of filling materials.
3. An H-tolerant composition according to claim 12S corrosion cement, characterized in that said phosphate comprises at least one of: magnesium phosphate, aluminum phosphate, potassium metaphosphate, sodium polyphosphate, calcium polyphosphate and magnesium polyphosphate.
4. H-resistant cable2Method for the preparation of S-corrosion cement, characterized in that it is used to prepare a H-resistant cement according to any one of claims 1 to 32S corrosion cement comprising:
preparing for H resistance according to the weight parts2S corrosion of said components of the cement;
the components are mixed evenly to prepare the H-resistant material2S corrodes the cement.
5. H-resistant cable2The application of S corrosion cement is characterized in that the S corrosion cement is applied to H-containing cement2S environment.
6. H-resistant cable2S-corrosion resistant cement sheath for well cementation, characterized in that it is made of a H-resistant material according to any one of claims 1 to 32And S, adding the corrosive cement into the prepared slurry, uniformly mixing, and cementing to obtain the cement.
7. An H-tolerant composition according to claim 62S corrosion well cementation cement sheath, characterized in that the H resistance2The water cement ratio of the S corrosion cement to the prepared slurry water is 0.40-0.60.
8. An H-tolerant composition according to claim 72S corrosion well cementation cement sheath, characterized in that the H resistance2The water-cement ratio of the S corrosion cement to the prepared slurry water is 0.44.
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