CN109534774A - A kind of medium temperature magnesium oxysulfide thermosetting resin gelling system and preparation method thereof - Google Patents
A kind of medium temperature magnesium oxysulfide thermosetting resin gelling system and preparation method thereof Download PDFInfo
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- CN109534774A CN109534774A CN201710856159.7A CN201710856159A CN109534774A CN 109534774 A CN109534774 A CN 109534774A CN 201710856159 A CN201710856159 A CN 201710856159A CN 109534774 A CN109534774 A CN 109534774A
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- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 239000011347 resin Substances 0.000 title claims abstract description 73
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OLZDXDPSDUSGIS-UHFFFAOYSA-N sulfinylmagnesium Chemical compound [Mg].S=O OLZDXDPSDUSGIS-UHFFFAOYSA-N 0.000 title abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 32
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 16
- 239000013505 freshwater Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 38
- 239000011777 magnesium Substances 0.000 claims description 38
- 229910052749 magnesium Inorganic materials 0.000 claims description 38
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims description 38
- 239000000395 magnesium oxide Substances 0.000 claims description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound 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 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 239000007849 furan resin Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 4
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 239000011398 Portland cement Substances 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 8
- 239000003469 silicate cement Substances 0.000 description 8
- 239000004575 stone Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 238000007596 consolidation process Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000003129 oil well Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical group [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000009466 transformation 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
- 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
- C04B28/30—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 magnesium cements or similar cements
-
- 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
- C04B2111/00482—Coating or impregnation 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
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a kind of medium temperature magnesium oxysulfide thermosetting resin gelling systems in oil gas well cementing operation field and preparation method thereof.The medium temperature magnesium oxysulfide thermosetting resin gelling system, the following components comprising parts by weight meter: 100 parts of light calcined magnesia；5~30 parts of thermosetting resin；0.5~15 part of resin curing agent；50~200 parts of magnesium sulfate；5~20 parts of retarder；0.5~8 part of fluid loss agent；35~150 parts of fresh water；0~200 part of density adjuster.The medium temperature magnesium oxysulfide thermosetting resin gelling system, can be after injecting pit shaft, itself is gelled, is frozen into the induration with advantages of higher compressive strength and durability under temperature in wellbore, pressure, so that effective fixed sleeving, completely cuts off on fluid and alter.In 45~90 DEG C, be gelled by flow regime to the solid time to adjust the thermosetting resin gelling system according to demand, guarantee scene injection construction safety, can partially or completely substitute currently used Portland cement paste system.
Description
Technical Field
The invention relates to a working fluid for the field of oil and gas well cementation, in particular to a medium-temperature magnesium oxysulfate thermosetting resin gelling system and a preparation method thereof.
Background
At present, Portland oil well cement is a common cementing material for oil and gas well cementing, the main component of the Portland oil well cement is a calcium silicate-based material, the calcium silicate-based material can be subjected to self-hydration reaction with water, and solid set cement can be self-hardened under certain temperature and pressure conditions. Owing to the hydraulic activity of silicate material, the silicate oil well cement is well compatible with various water-based additives (fluid loss additive, retarder and the like) to form slurry with certain fluidity, and the slurry can be lightened or weighted by mixing various inorganic materials. The silicate cement stone basically meets the operation requirements of oil and gas wells due to higher compressive strength, lower permeability and better durability, so the silicate cement stone is very commonly applied to the operations of well cementation, well completion and the like of conventional oil and gas wells. However, the silicate cement stone also has the defects of the silicate cement stone, and one is that the silicate cement stone is hard and brittle under higher compressive strength, so that the silicate cement stone is damaged when receiving larger external force; and secondly, the silicate material has self-contractibility, and the whole volume of the set cement is reduced due to the crystal transformation of a hydration product in the self-hydration process of the silicate material. The defects on the cement sheath lead to the easy breakage of the cement sheath of the shaft, and the cement sheath and the casing as well as the cement sheath and the well wall form micro annular gaps, so that the effective sealing of the cement sheath on the annular space is seriously influenced, stratum fluid is led to flee to a well mouth, and the production safety is influenced. Therefore, improving the hardness and brittleness of the silicate cement stone and compensating the self shrinkage are urgent problems facing oil and gas well cementing in recent years.
The resin is a solid, semi-solid or liquid organic polymer with a certain molecular weight at normal temperature. And the crosslinking reaction is carried out under the action of the self-crosslinking agent or the curing agent to form a certain structure. Thermosetting resin refers to a resin which is heated, pressurized or subjected to chemical reaction under the action of a curing agent and ultraviolet light, and is crosslinked and cured into insoluble infusible substances. The thermoplastic resin is a resin which is softened after heating, hardened after cooling and can be repeatedly performed, and has no chemical reaction in the soft-hard conversion process. Various resins are widely applied in the industrial field, but are rarely applied in the field of oil and gas well cementing and only used as partial additives.
The magnesium oxysulfate cementing material is an air-hardening cementing material formed by active magnesium oxide and magnesium sulfate solution, has excellent performances of rapid solidification, rapid strength development, high compressive strength and the like, has good stability under dry conditions, and is widely applied to the field of buildings due to the characteristics; but the solidification is too fast, so the safe construction time requirement in well cementation construction can not be met, and the method has no research and application in the field of oil and gas well cementation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a medium-temperature magnesium oxysulfate thermosetting resin gelling system. In particular to a medium-temperature magnesium oxysulfate thermosetting resin gelling system and a preparation method thereof.
One of the purposes of the invention is to provide a medium-temperature magnesium oxysulfate thermosetting resin gelling system which can be self-gelled and solidified into a consolidated body with higher compressive strength and durability at the temperature and pressure of a shaft after being injected into the shaft, so that a sleeve can be effectively fixed and fluid channeling is isolated. The invention makes full use of the self-hardening characteristic of the magnesium oxysulfate cement in a dry environment, and utilizes the high-temperature resistant thermosetting resin to improve the water resistance of the magnesium oxysulfate cement and assist in enhancing the acid corrosion resistance of the magnesium oxysulfate cement. The thermosetting resin gelling system is at 45-90 ℃, the time from the gelling of a flowing state to the solid state can be adjusted according to requirements, the safety of on-site injection construction is ensured, and the thermosetting resin gelling system can partially or completely replace the existing common silicate cement slurry system. In the well casing tieback cementing of an oil-gas well, the cementing system is cured into a high-strength low-elasticity-modulus consolidation body in a dry environment in the annular space of two layers of casings, so that the annular space of the well casing is effectively sealed.
The medium-temperature magnesium oxysulfate thermosetting resin gelling system comprises thermosetting resin and a matched resin curing agent, magnesium oxysulfate cement and a matched retarder, a fluid loss agent, a density regulator and the like. The thermosetting resin and the magnesium oxysulfate cement contained in the cement can be cured in a shaft environment to form a set cement with high compressive strength, low elastic modulus and low permeability, and the set cement has good corrosion resistance.
The magnesium oxysulfate cement is prepared by mixing light-burned magnesium oxide and magnesium sulfate, and the proportion of the magnesium oxysulfate cement can be properly adjusted according to requirements.
Specifically, the medium-temperature magnesium oxysulfate thermosetting resin gelling system can comprise the following components in parts by weight:
100 parts of light-burned magnesium oxide;
5-30 parts of thermosetting resin; preferably 10-20 parts;
0.5-15 parts of a resin curing agent; preferably 0.5 to 10 parts, more preferably 2.5 to 10 parts;
50-200 parts of magnesium sulfate; preferably 50-100 parts;
5-20 parts of a retarder; preferably 10-20 parts;
0.5-8 parts of a fluid loss agent; preferably 0.5-6 parts; more preferably 2-4 parts;
35-150 parts of fresh water;
0-200 parts of density regulator.
It is further preferred that the first and second liquid crystal compositions,
100 parts of light-burned magnesium oxide;
10-20 parts of thermosetting resin;
0.5-10 parts of resin curing agent, more preferably 2.5-10 parts;
50-100 parts of magnesium sulfate;
10-20 parts of a retarder;
0.5-6 parts of fluid loss agent, preferably 2-4 parts;
35-150 parts of fresh water;
0-200 parts of density regulator.
Wherein,
the thermosetting resin can be at least one selected from melamine formaldehyde resin, furan resin and epoxy resin.
The resin curing agent can be selected from at least one of aliphatic amine, potassium carbonate or hydroxide of other alkaline earth metal.
The retarder is selected from at least one or a mixture of several of phosphoric acid and salt thereof, salicylic acid, tartaric acid and salt thereof.
The fluid loss agent can be at least one of a polyvinyl alcohol fluid loss agent or an AMPS multipolymer fluid loss agent.
The density regulator is a light-reducing or heavy-weight material, can be an electrodeless material, and can also be an organic material, and specifically can be one or more of glass beads, silicon powder, micro-silicon, fly ash, iron ore powder and the like.
The invention provides a well cementation working fluid system for an oil and gas well at the temperature of 45-90 ℃, wherein the medium-temperature magnesium oxysulfate thermosetting resin gelling system has stronger wall cementation capability, the system can form a consolidation body with certain compressive strength under the conditions of the temperature and the pressure of a shaft, and the consolidation body has good elastic deformation capability. The resin in the gelling system can be crosslinked and consolidated by itself to form a three-dimensional grid structure, the magnesium oxysulfate cement can be consolidated into magnesium oxysulfate set cement, and the magnesium oxysulfate set cement are organically interpenetrated to form a consolidated body with excellent mechanical properties, so that the effective sealing of an annular space is realized, and the sealing effectiveness is maintained for a long time.
The invention also aims to provide a preparation method of the medium-temperature magnesium oxysulfate thermosetting resin gelling system, which comprises the following steps:
firstly, weighing the components according to the using amount for later use; secondly, uniformly mixing and stirring the light-burned magnesium oxide and the density regulator to obtain a mixed solid; dissolving magnesium sulfate, thermosetting resin, a resin curing agent, a retarder and a fluid loss agent in fresh water and uniformly stirring to obtain a mixed liquid; and finally, adding the mixed solid into the mixed liquid under stirring, and uniformly stirring to obtain the medium-temperature magnesium oxysulfate thermosetting resin gelling system.
Effects of the invention
① the moderate temperature magnesium oxysulfate thermosetting resin gel system can keep longer flowing ability at normal temperature, the slurry pumpability is good, ② the gel system density can be 1.20-2.50 g/cm by adding lightening or weighting material3The curing time of the system can be adjusted within 30-400 min by adjusting the addition of the retarder, the slurry sedimentation stability is good, the consolidation time of the thermosetting resin material in the ③ gelling system can be adjusted and controlled within the temperature range of 45-90 ℃ under the action of the curing agent, the magnesium oxysulfate cement in the ④ gelling system can also be cured by itself, the curing time can be effectively prolonged by matching the retarder within the temperature range of 45-90 ℃, the on-site pumping requirement is met, the thermosetting resin and the magnesium oxysulfate cement in the ⑤ gelling system are structurally interpenetrated, the strength and the compactness of the consolidated body are synergistically enhanced, the compressive strength of the ⑥ magnesium oxysulfate thermosetting resin consolidated body is higher, the elastic modulus is lower, the consolidation strength with the well wall is high, the migration of well bore fluid can be effectively isolated, and the invention provides a new gelling system for preventing the migration of annular fluid of an oil-gas well, and has better application prospect.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
The reagents used in the examples are all commercially available.
Example 1
(1) 300g of light-burned magnesium oxide, 150g of magnesium sulfate, 8g of polyvinyl alcohol fluid loss additive FSAM (Dezhou continental shelf company), 30g of matched retarder tartaric acid, 40g of GE epoxy resin (Shanghai Fulang chemical technology development Co., Ltd.), 20g of matched resin curing agent tetraethylenepentamine and 150g of fresh water are weighed.
(2) Uniformly mixing magnesium sulfate, thermosetting resin, a resin curing agent, a matched retarder, a polyvinyl alcohol fluid loss agent and fresh water to obtain a mixed liquid for later use;
(3) adding the mixed liquid into a mixing container, rotating a stirrer at a low speed (4000 +/-200 revolutions per minute), adding the light-burned magnesium oxide within 15 seconds, covering a cover of the stirrer, continuously stirring at a high speed (12000 +/-500 revolutions per minute) for 35 seconds, and uniformly stirring to obtain the medium-temperature magnesium oxysulfate thermosetting resin gelling system. The gelled system was tested according to the test method of GB-T19139-3Thickening time at 45 ℃ is 260min, compressive strength of the consolidated body is 17.8MPa, and elastic modulus is 6.3 GPa.
Example 2
(1) Weighing 200g of light-burned magnesium oxide, 150g of magnesium sulfate, 200g of light-reducing agent glass beads, 8g of polyvinyl alcohol fluid loss agent FSAM, 20g of matched retarder tartaric acid, 10g of matched retarder salicylic acid, 40g of GE epoxy resin, 15g of matched resin curing agent tetraethylenepentamine and 200g of fresh water.
(2) Mixing the light-burned magnesium oxide and the glass beads uniformly for later use;
(3) uniformly mixing magnesium sulfate, thermosetting resin, a resin curing agent, a matched retarder, a polyvinyl alcohol fluid loss agent and fresh water for later use;
(4) adding the mixed liquid into a mixing container, rotating a stirrer at a low speed (4000 +/-200 revolutions per minute), adding the mixture of light-burned magnesium oxide and glass beads within 15 seconds, covering a cover of the stirrer, continuously stirring at a high speed (6000 +/-500 revolutions per minute) for 35 seconds, and uniformly stirring to obtain a medium-temperature magnesium oxysulfate thermosetting resin gelling system with the density of 1.30g/cm3Thickening time at 70 ℃ is 200min, compressive strength of the consolidated body is 14.9MPa, and elastic modulus is 5.6 GPa.
Example 3
(1) 200g of light-burned magnesium oxide, 200g of magnesium sulfate, 400g of iron ore powder weighting agent, 12g of polyvinyl alcohol fluid loss additive FSAM, 30g of matched retarder tartaric acid, 10g of matched retarder sodium tartrate, 40g of GE epoxy resin, 1g of matched resin curing agent tetraethylenepentamine and 250g of fresh water are weighed.
(2) Mixing the light-burned magnesium oxide and the iron ore powder uniformly for later use;
(3) uniformly mixing magnesium sulfate, thermosetting resin, a resin curing agent, a matched retarder, a polyvinyl alcohol fluid loss agent and fresh water to obtain a mixed liquid for later use;
(4) adding the mixed liquid into a mixing container, rotating a stirrer at a low speed (4000 +/-200 revolutions per minute), adding the mixture of the light-burned magnesium oxide and the iron ore powder within 15 seconds, covering a cover of the stirrer, continuously stirring at a high speed (12000 +/-500 revolutions per minute) for 35 seconds, and uniformly stirring to obtain a medium-temperature magnesium oxysulfate thermosetting resin gelling system with the density of 2.40g/cm3Thickening time at 90 ℃ is 220min, compressive strength of the consolidated body is 11.6MPa, and elastic modulus is 5.1 GPa.
Claims (9)
1. A medium-temperature magnesium oxysulfate thermosetting resin gelling system comprises the following components in parts by weight:
100 parts of light-burned magnesium oxide;
5-30 parts of thermosetting resin; preferably 10-20 parts;
0.5-15 parts of a resin curing agent; preferably 0.5 to 10 parts, more preferably 2.5 to 10 parts;
50-200 parts of magnesium sulfate; preferably 50-100 parts;
5-20 parts of a retarder; preferably 10-20 parts;
0.5-8 parts of a fluid loss agent; preferably 0.5-6 parts; more preferably 2-4 parts;
35-150 parts of fresh water;
0-200 parts of density regulator.
2. The medium-temperature magnesium oxysulfate thermosetting resin gelling system according to claim 1, characterized by comprising the following components in parts by weight:
100 parts of light-burned magnesium oxide;
10-20 parts of thermosetting resin;
0.5-10 parts of resin curing agent, more preferably 2.5-10 parts;
50-100 parts of magnesium sulfate;
10-20 parts of a retarder;
0.5-6 parts of fluid loss agent, preferably 2-4 parts;
35-150 parts of fresh water;
0-200 parts of density regulator.
3. The medium-temperature magnesium oxysulfate thermosetting resin gelling system according to claim 1, characterized by comprising the following components in parts by weight:
100 parts of light-burned magnesium oxide;
10-20 parts of thermosetting resin;
2.5-10 parts of a resin curing agent;
50-100 parts of magnesium sulfate;
10-20 parts of a retarder;
2-4 parts of a fluid loss agent;
35-150 parts of fresh water;
0-200 parts of density regulator.
4. An intermediate-temperature magnesium oxysulfate thermosetting resin gelling system according to any one of claims 1 to 3, wherein:
the thermosetting resin is at least one of melamine formaldehyde resin, furan resin and epoxy resin.
5. An intermediate-temperature magnesium oxysulfate thermosetting resin gelling system according to any one of claims 1 to 3, wherein:
the resin curing agent is selected from at least one of aliphatic amine, potassium carbonate or hydroxide of other alkaline earth metals.
6. An intermediate-temperature magnesium oxysulfate thermosetting resin gelling system according to any one of claims 1 to 3, wherein:
the retarder is at least one selected from phosphoric acid and salts thereof, salicylic acid, tartaric acid and salts thereof.
7. An intermediate-temperature magnesium oxysulfate thermosetting resin gelling system according to any one of claims 1 to 3, wherein:
the fluid loss agent is selected from at least one of polyvinyl alcohol fluid loss agents and AMPS multipolymer fluid loss agents.
8. An intermediate-temperature magnesium oxysulfate thermosetting resin gelling system according to any one of claims 1 to 3, wherein:
the density regulator is at least one selected from glass beads, silicon powder, micro-silicon, fly ash and iron ore powder.
9. A process for the preparation of a medium temperature magnesium oxysulfate thermosetting resin gelling system according to any one of claims 1 to 8, comprising the steps of:
firstly, weighing the components according to the using amount for later use; secondly, uniformly mixing and stirring the light-burned magnesium oxide and the density regulator to obtain a mixed solid; dissolving magnesium sulfate, thermosetting resin, a resin curing agent, a retarder and a fluid loss agent in fresh water and uniformly stirring to obtain a mixed liquid; and finally, adding the mixed solid into the mixed liquid under stirring, and uniformly stirring to obtain the medium-temperature magnesium oxysulfate thermosetting resin gelling system.
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| CN112457829A (en) * | 2020-12-08 | 2021-03-09 | 中国石油天然气集团有限公司 | Retarded thermosetting resin gelling composition and preparation method thereof |
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