CN105112030A - Anti-permeation elastomer for oil well cement and preparation method of cement paste - Google Patents
Anti-permeation elastomer for oil well cement and preparation method of cement paste Download PDFInfo
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- 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
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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
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/487—Fluid loss control additives; Additives for reducing or preventing circulation loss
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/50—Defoamers, air detrainers
Abstract
The invention provides an anti-permeation elastomer for oil well cement and a preparation method of cement paste. The anti-permeation elastomer for oil well cement is composed of the following components in parts by weight: 20-80 parts of acrylonitrile-butadiene-styrene copolymer powder, 20-80 parts of alkene vinyl acetate copolymer powder and 0.4-16 parts of organosilane or polysilane hydrophobic material. The acrylonitrile-butadiene-styrene copolymer powder (ABS for short) is used as the main body material of the elastomer. The ABS has excellent impact resistance, heat resistance, low temperature resistance and chemical resistance. The ABS added into the cement is combined with the cement particle and cement hydration product to fill up the pores and disperse the internal stress of hardened cement, thereby improving the toughness of the hardened cement. The alkene vinyl acetate copolymer powder, which is used as the auxiliary material of the elastomer, can easily form a film, thereby enhancing the water permeability and impact resistance of the hardened cement. The anti-permeation elastomer enhances the toughness of the hardened cement, lowers the permeability of the hardened cement, and ensures the completeness and sealability of the cement sheath.
Description
Technical field
The present invention relates to the impervious elastomerics of a kind of oil well cement and grout preparation method, belong to oil gas well cementing operation field.
Background technology
The Inter-zonal packing ability that in pit shaft, cement mantle is permanently effective is the prerequisite realizing oil-gas field development volume increase, it is the basis realizing layer mining, layer-management, zonal injection and separate zone stimulation, a bite well will reach due production capacity, depends primarily on the Inter-zonal packing degree reached in Completion Operations.But in general, well-cementing cement is the hard brittle material belonging to congenital microdefect, have that tensile strength is low, resistance to rupture is poor and the inherent defect such as impact resistance is low, in subsequent development and operation, cement mantle is under downhole temperature pressure environment, the effect being subject to external force makes internal stress change very easily to ftracture, the packing effect of cement mantle was lost efficacy, causes underground fluid (oil, gas, water) layer cross flow.
Current most domestic oil field has entered middle and later periods mining phase, and in order to improve the oil well life-span, ensure high and stable yields, cementing quality becomes the outstanding problem that oil gas casing and cementing faces.Simultaneously, unconventional petroleum resources exploitation has become important energy integral part, the fine and close exploratory development such as oil gas, shale gas generally adopts long horizontal sections horizontal well factory operation+staged fracturing or volume fracturing development scheme, need to carry out Large Scale Acidizing fracturing reform to reservoir, requirements at the higher level are proposed to cement mantle stopping property.Therefore, a kind of good with grout consistency in the urgent need to developing, improve the elastomer material of cement mechanical property, optimize Mechanical Behavior of Hardened Cement Paste, to resist the impact of drill string, the operation of the later stage such as perforation and pressure break destroys Behavior of Hardened Cement Paste, ensure the sealing integrity of cement mantle, prevent oil gas water breakthrough, improve the rate of oil and gas recovery and Oil/gas Well work-ing life, meet oil-gas exploration and development needs.
The conventional at present main latex of well cementation toughening material, rubber powder and fiber etc., at patent CN201210029067, CN20121022859 etc. have certain introduction and description.But generally have that dosage is large, ultimate compression strength loss, improve shock resistance difference, not easily disperse, the problems such as environmental pollution, and do not consider the impermeability of Behavior of Hardened Cement Paste.
Summary of the invention
In order to overcome, existing tensile strength is low, shock resistance is weak, and the invention provides the impervious elastomerics of a kind of oil well cement and grout preparation method, the present invention adds in cementing slurry, not only increases tensile strength and the shock resistance of Behavior of Hardened Cement Paste; And reduce the Young's modulus of Behavior of Hardened Cement Paste, change into plastic deformation by Brittle deformation underground cement ring is stressed, keep the integrity of cement mantle, simultaneously Behavior of Hardened Cement Paste has extremely low anti-gas, water oozes ability, for impermeable cement, ensure sealing, extend the work-ing life of Oil/gas Well.
The technical solution used in the present invention:
The impervious elastomerics of a kind of oil well cement, impervious elastomeric component and mass ratio are: 20 ~ 80 parts, acrylonitrile-butadiene-styrene copolymer powder, 20 ~ 80 parts, alkene class vinyl acetate copolymer powder, organosilane or polysilane hydrophobic material 0.4 ~ 16 part.
Described acrylonitrile-butadiene-styrene copolymer be with elastomerics be main chain graft copolymer and with the uniform mixture of the hard AS resin graft copolymer that is main chain, particle fineness 325 order.
Described acrylonitrile-butadiene-styrene copolymer powder powder concentration be 5% acid of hydrochloric acid and nitric acid composite solution carry out immersion treatment, treatment temp 50 DEG C, soak time 3 ~ 4 hours.
Described alkene class vinyl acetate copolymer powder is dispersion rubber powder, and dispersion rubber powder is ethylene vinyl acetate copolymer powder, is called for short EVA.
The SEAL80 of described organosilane for providing for National Starch company, polysilane powder hydrophobic material is DOW CORNING SPH50 or Wa Ke company BSPOWDERA.
A kind of as the impervious method for producing elastomers of the oil well cement in claim 1-5 as described in any one claim, the acrylonitrile-butadiene-styrene copolymer powder of 20 ~ 80 and the organosilane of 0.4 ~ 16 or polysilane hydrophobic material is added in Horizontal type helical ribbon mixer, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 20 ~ 80 is added in batch mixing stir 30 minutes again.
Comprise the impervious elastomeric grout of oil well cement in claim 1-5 described in any one claim, it consists of: 5 ~ 15 parts, impervious elastomerics, fluid loss agent 1 ~ 4 part, dispersion agent 0 ~ 2 part, retardant 0 ~ 5 part, 44 ~ 53 parts, water, defoamer 0.2 part, cement 100 parts.
Described cement is silicate G level oil well cement; Dispersion agent is sulfonation tannin, sulfonated ketone aldehyde condensate, poly-how sulfonic acid or its mixture; Water retaining is 2-acrylamide-2-methyl propane sulfonic multipolymer or PVA water retaining; Retardant is organophosphate, poly-hydroxy organic acid, AMPS copolymers of unsaturated carboxylic acids or their compound; Defoamer is dimethyl silicone oil or tributyl phosphate.
A kind of grout preparation method as claimed in claim 7, concrete steps are:
1) impervious elastomerics is prepared, the acrylonitrile-butadiene-styrene copolymer powder of 20 ~ 80 and the organosilane of 0.4 ~ 16 or polysilane hydrophobic material is added in Horizontal type helical ribbon mixer, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 20 ~ 80 is added in batch mixing stir 30 minutes again;
2) prepare impervious elastomerics grout, by step 1) in preparation impervious elastomerics choose 5 ~ 15 parts, 1 ~ 4 portion of fluid loss agent, 0 ~ 2 part of dispersion agent, 0 ~ 5 part of retardant, 44 ~ 53 parts of water, 0.2 part of defoamer, 100 parts of cement; All powders are dry mixed, liquid material wet mixing, are then prepared by GB/T19139-2012 oil-well cement test method regulation step.
Beneficial effect of the present invention:
1, the present invention is using acrylonitrile-butadiene-styrene copolymer (ABS) resin of industry one of five large synthetic resins as impervious elastomer material, and introduces alkene class vinyl acetate copolymer and organosilane or polysilane powder hydrophobic material.
2, the impervious elastomerics cement prepared by the present invention has impermeable and toughening effect, cement strength loss is very little, Young's modulus reduces by 30%, Behavior of Hardened Cement Paste impact work improves 10 ~ 15%, and tensile strength increases by 5 ~ 10%, and Behavior of Hardened Cement Paste rate of permeation is less than 0.001 × 10
-3μm
2.
Embodiment:
Embodiment 1:
In order to overcome, existing tensile strength is low, shock resistance is weak, and the invention provides the impervious elastomerics of a kind of oil well cement and grout preparation method, the present invention adds in cementing slurry, not only increases tensile strength and the shock resistance of Behavior of Hardened Cement Paste; And reduce the Young's modulus of Behavior of Hardened Cement Paste, change into plastic deformation by Brittle deformation underground cement ring is stressed, keep the integrity of cement mantle, simultaneously Behavior of Hardened Cement Paste has extremely low anti-gas, water oozes ability, for impermeable cement, ensure sealing, extend the work-ing life of Oil/gas Well.
The impervious elastomerics of a kind of oil well cement, impervious elastomeric component and mass ratio are: 20 parts, acrylonitrile-butadiene-styrene copolymer powder, 20 parts, alkene class vinyl acetate copolymer powder, organosilane or polysilane hydrophobic material 0.4 part.
In the present invention, adopt acrylonitrile-butadiene-styrene copolymer (being called for short ABS) powder as elastomer body material.ABS has excellent impact resistance, thermotolerance, lower temperature resistance and chemical proofing, adds ABS and cement granules, hydrolysis product of cement in cement and combines by filling hole and disperse water mudstone internal stress, improve Toughness of Harden Cement performance.
Adopt alkene class vinyl acetate copolymer powder as elastomerics subsidiary material, the easy film forming of alkene class vinyl acetate copolymer, improve the impervious and shock resistance of Behavior of Hardened Cement Paste.
Add organosilane or polysilane powder hydrophobic material, in grout, the silane that hydrophobizing agent discharges parcel makes its redispersion in mixing water, organo-functional group hydrolysis hydrophilic in silane under high alkalinity environment after hydrated cementitious forms the silanol of high reaction activity, silanol continues to carry out irreversible reaction with the oh group in hydrolysis product of cement and forms Chemical bond, thus make the silane linked together by commissure effect be securely fixed in the surface of Behavior of Hardened Cement Paste hole wall, because hydrophobic organo-functional group is towards the outside of hole wall, the surface of hole is made to obtain hydrophobicity, improve the overall water resistant of Behavior of Hardened Cement Paste and ooze ability.
Embodiment 2:
Impervious elastomeric component is chosen and mass ratio is: 80 parts, acrylonitrile-butadiene-styrene copolymer powder, 80 parts, alkene class vinyl acetate copolymer powder, organosilane or polysilane hydrophobic material 16 parts in the present embodiment.
In the present invention, adopt acrylonitrile-butadiene-styrene copolymer (being called for short ABS) powder as elastomer body material.ABS has excellent impact resistance, thermotolerance, lower temperature resistance and chemical proofing, adds ABS and cement granules, hydrolysis product of cement in cement and combines by filling hole and disperse water mudstone internal stress, improve Toughness of Harden Cement performance.
Adopt alkene class vinyl acetate copolymer powder as elastomerics subsidiary material, the easy film forming of alkene class vinyl acetate copolymer, improve the impervious and shock resistance of Behavior of Hardened Cement Paste.
Add organosilane or polysilane powder hydrophobic material, in grout, the silane that hydrophobizing agent discharges parcel makes its redispersion in mixing water, organo-functional group hydrolysis hydrophilic in silane under high alkalinity environment after hydrated cementitious forms the silanol of high reaction activity, silanol continues to carry out irreversible reaction with the oh group in hydrolysis product of cement and forms Chemical bond, thus make the silane linked together by commissure effect be securely fixed in the surface of Behavior of Hardened Cement Paste hole wall, because hydrophobic organo-functional group is towards the outside of hole wall, the surface of hole is made to obtain hydrophobicity, improve the overall water resistant of Behavior of Hardened Cement Paste and ooze ability.
Embodiment 3:
In the present embodiment, choose impervious elastomeric component and mass ratio is: 50 parts, acrylonitrile-butadiene-styrene copolymer powder, 50 parts, alkene class vinyl acetate copolymer powder, organosilane or polysilane hydrophobic material 8 parts.
In the present invention, adopt acrylonitrile-butadiene-styrene copolymer (being called for short ABS) powder as elastomer body material.ABS has excellent impact resistance, thermotolerance, lower temperature resistance and chemical proofing, adds ABS and cement granules, hydrolysis product of cement in cement and combines by filling hole and disperse water mudstone internal stress, improve Toughness of Harden Cement performance.
Adopt alkene class vinyl acetate copolymer powder as elastomerics subsidiary material, the easy film forming of alkene class vinyl acetate copolymer, improve the impervious and shock resistance of Behavior of Hardened Cement Paste.
Add organosilane or polysilane powder hydrophobic material, in grout, the silane that hydrophobizing agent discharges parcel makes its redispersion in mixing water, organo-functional group hydrolysis hydrophilic in silane under high alkalinity environment after hydrated cementitious forms the silanol of high reaction activity, silanol continues to carry out irreversible reaction with the oh group in hydrolysis product of cement and forms Chemical bond, thus make the silane linked together by commissure effect be securely fixed in the surface of Behavior of Hardened Cement Paste hole wall, because hydrophobic organo-functional group is towards the outside of hole wall, the surface of hole is made to obtain hydrophobicity, improve the overall water resistant of Behavior of Hardened Cement Paste and ooze ability.
Embodiment 4:
Based on the basis of above-described embodiment, in the present embodiment, described acrylonitrile-butadiene-styrene copolymer be with elastomerics be main chain graft copolymer and with the uniform mixture of the hard AS resin graft copolymer that is main chain, particle fineness 325 order.
Described acrylonitrile-butadiene-styrene copolymer powder powder concentration be 5% acid of hydrochloric acid and nitric acid composite solution carry out immersion treatment, treatment temp 50 DEG C, soak time 3 ~ 4 hours.
Described alkene class vinyl acetate copolymer powder is dispersion rubber powder, and dispersion rubber powder is ethylene vinyl acetate copolymer powder, is called for short EVA.
The SEAL80 of described organosilane for providing for National Starch company, polysilane powder hydrophobic material is DOW CORNING SPH50 or Wa Ke company BSPOWDERA, organosilane and polysilane powder hydrophobic material commercially all available.
Embodiment 5:
Based on the basis of above-described embodiment, in the present embodiment, a kind of as the impervious method for producing elastomers of the oil well cement in claim 1-5 as described in any one claim, the acrylonitrile-butadiene-styrene copolymer powder of 20 ~ 80 and the organosilane of 0.4 ~ 16 or polysilane hydrophobic material is added in Horizontal type helical ribbon mixer, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 20 ~ 80 is added in batch mixing stir 30 minutes again.
In the present embodiment, the acrylonitrile-butadiene-styrene copolymer powder of 80 and the organosilane of 16 or polysilane hydrophobic material is added in Horizontal type helical ribbon mixer, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 80 is added in batch mixing stir 30 minutes again.
Prepare the impervious elastomerics of oil well cement, the impervious elastomerics of oil well cement prepared by the present invention, adopt acrylonitrile-butadiene-styrene copolymer (being called for short ABS) powder as elastomer body material, to improve Toughness of Harden Cement performance; Adopt alkene class vinyl acetate copolymer powder as elastomerics subsidiary material, the easy film forming of alkene class vinyl acetate copolymer, improve the impervious and shock resistance of Behavior of Hardened Cement Paste, add organosilane or polysilane powder hydrophobic material, improve the overall water resistant of Behavior of Hardened Cement Paste and ooze ability.
Embodiment 6:
On basis based on embodiment 1, in the present embodiment, a kind of impervious elastomeric grout of oil well cement comprised in claim 1-5 described in any one claim, it consists of: 5 parts, impervious elastomerics, fluid loss agent 1 part, 44 parts, water, defoamer 0.2 part, cement 100 parts.When above-mentioned substance mixes, dispersion agent and retardant can not be added, mixture is fully uniformly mixed.
The impervious elastomerics grout prepared by the present invention has impermeable and toughening effect, cement strength loss is very little, Young's modulus reduces by 30%, Behavior of Hardened Cement Paste impact work improves 10 ~ 15%, and tensile strength increases by 5 ~ 10%, and Behavior of Hardened Cement Paste rate of permeation is less than 0.001 × 10
-3μm
2.
The impervious elastomerics in embodiment 1 is chosen in the present embodiment, impervious elastomeric component and mass ratio are: 20 parts, acrylonitrile-butadiene-styrene copolymer powder, 20 parts, alkene class vinyl acetate copolymer powder, organosilane or polysilane hydrophobic material 0.4 part, such preparation draw grout, water resistant ability is strong, shock resistance grow, and toughness strengthens.
Embodiment 7:
On basis based on embodiment 1, in the present embodiment, choose 15 parts, impervious elastomerics, fluid loss agent 4 parts, dispersion agent 2 parts, retardant 5 parts, 53 parts, water, defoamer 0.2 part, cement 100 parts.
The impervious elastomerics grout prepared by the present invention has impermeable and toughening effect, cement strength loss is very little, Young's modulus reduces by 30%, Behavior of Hardened Cement Paste impact work improves 10 ~ 15%, and tensile strength increases by 5 ~ 10%, and Behavior of Hardened Cement Paste rate of permeation is less than 0.001 × 10
-3μm
2.
Choose the impervious elastomerics in embodiment 1, preparation draw grout, water resistant ability is strong, shock resistance grow, and toughness strengthens.
Embodiment 8:
On basis based on embodiment 1, in the present embodiment, choose 10 parts, impervious elastomerics, fluid loss agent 2 parts, dispersion agent 1 part, retardant 3 parts, 48 parts, water, defoamer 0.2 part, cement 100 parts.Choose the impervious elastomerics in embodiment 1, prepare the grout drawn, water resistant ability is strong, shock resistance grow, and toughness strengthens.
The impervious elastomerics grout prepared by the present invention has impermeable and toughening effect, cement strength loss is very little, Young's modulus reduces by 30%, Behavior of Hardened Cement Paste impact work improves 10 ~ 15%, and tensile strength increases by 5 ~ 10%, and Behavior of Hardened Cement Paste rate of permeation is less than 0.001 × 10
-3μm
2.
Embodiment 9:
In the present embodiment, described cement is silicate G level oil well cement; Dispersion agent is sulfonation tannin, sulfonated ketone aldehyde condensate, poly-how sulfonic acid or its mixture; Water retaining is 2-acrylamide-2-methyl propane sulfonic multipolymer or PVA water retaining; Retardant is organophosphate, poly-hydroxy organic acid, AMPS copolymers of unsaturated carboxylic acids or their compound; Defoamer is dimethyl silicone oil or tributyl phosphate.
In the present embodiment, dispersion agent is sulfonation tannin, and dispersion agent improves the dispersive ability of composite grain and again condenses ability.Water retaining is PVA water retaining, and the effect of PVA water retaining is the temperature resistance ability that improve grout.Retardant is organophosphate, and the effect of retardant is, when ensureing to stir, do not have solid to lump soon, retardant is effectively guaranteed to stir; Defoamer is dimethyl silicone oil, and defoamer Main Function is in the process stirred, and occurs the froth breaking after bubble and presses down bubble.
Embodiment 10:
On basis based on embodiment 6, in the present embodiment, a kind of grout preparation method as claimed in claim 7, concrete steps are:
1) impervious elastomerics is prepared, the acrylonitrile-butadiene-styrene copolymer powder of 20 ~ 80 and the organosilane of 0.4 ~ 16 or polysilane hydrophobic material is added in Horizontal type helical ribbon mixer, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 20 ~ 80 is added in batch mixing stir 30 minutes again;
2) prepare impervious elastomerics grout, by step 1) in preparation impervious elastomerics choose 5 ~ 15 parts, 1 ~ 4 portion of fluid loss agent, 0 ~ 2 part of dispersion agent, 0 ~ 5 part of retardant, 44 ~ 53 parts of water, 0.2 part of defoamer, 100 parts of cement; All powders are dry mixed, liquid material wet mixing, are then prepared by GB/T19139-2012 oil-well cement test method regulation step.
In the present embodiment,
1) impervious elastomerics is prepared, the acrylonitrile-butadiene-styrene copolymer powder of 80 and the organosilane of 16 or polysilane hydrophobic material is added in Horizontal type helical ribbon mixer, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 0 is added in batch mixing stir 30 minutes again;
2) prepare impervious elastomerics grout, by step 1) in preparation impervious elastomerics choose 5 parts, 2 portions of fluid loss agents, 2 parts of dispersion agents, 5 parts of retardant, 53 parts of water, 0.2 part of defoamer, 100 parts of cement; All powders are dry mixed, liquid material wet mixing, are then prepared by GB/T19139-2012 oil-well cement test method regulation step.
The impervious elastomerics grout prepared by the present invention has impermeable and toughening effect, cement strength loss is very little, Young's modulus reduces by 30%, Behavior of Hardened Cement Paste impact work improves 10 ~ 15%, and tensile strength increases by 5 ~ 10%, and Behavior of Hardened Cement Paste rate of permeation is less than 0.001 × 10
-3μm
2.
Embodiment 11:
On basis based on upper 10 embodiments, choose three examples in the present embodiment and be described.
Example 1 impervious elastomerics compositing formula of the present invention
The impervious elastomerics compositing formula of table 1
Example 2 impervious elastomerics Behavior of Hardened Cement Paste mechanics modified formula
Table 2 impervious elastomerics Behavior of Hardened Cement Paste mechanics modified formula
Example 3 impervious elastomerics cementing concrete slurry formula
Table 3 impervious elastomerics cementing concrete slurry formula
Mechanical Behavior of Hardened Cement Paste is tested
Press the good grout of the given formulated of table 2 according to GB/T19139-2012 oil-well cement test method, according to GB/T19139-2012 oil-well cement test method curing water mudstone, curing condition is: normal pressure 70 DEG C × 7 days.
Mechanical property triaxial tester is tested, and test condition is: confined pressure 5MPa, constant speed (2kN/min)
Behavior of Hardened Cement Paste shock resistance and rate of permeation ballistic work tester and Permeability tester are tested
The impervious elastomerics Mechanical Behavior of Hardened Cement Paste of table 4
The present invention carrys out the toughness of comprehensive evaluation Behavior of Hardened Cement Paste from tensile strength, impact work, Young's modulus etc.As can be seen from Table 4, impervious elastomeric adding affects very little on Behavior of Hardened Cement Paste ultimate compression strength, but improve Behavior of Hardened Cement Paste tensile strength and impact resistance, reduce Behavior of Hardened Cement Paste Young's modulus, impervious elastomerics carries out matrix plastification transformation to Behavior of Hardened Cement Paste, improves Mechanical Behavior of Hardened Cement Paste, prevents later stage operation from destroying Behavior of Hardened Cement Paste mechanical integrity, significantly reduce Behavior of Hardened Cement Paste rate of permeation, improve cement mantle stopping property.
The performance test of impervious elastomerics cementing slurry
Press the good grout of the given formulated of table 3 according to GB/T19139-2012 oil-well cement test method, carry out the performance tests such as grout multiviscosisty, dehydration, stream change, free liquid according to GB/T19139-2012 oil-well cement test method
The impervious elastomerics cement slurry property of table 5
After adding impervious elastomerics in the embodiment of the present invention as can be seen from Table 5, the main conventional project performance of grout is not had an impact substantially.When impervious elastomerics parts by weight are 5 parts ~ 15 parts, to grout stability (free liquid content), thickening time all without negative impact; According to rheological property data, when impervious elastomerics dosage is large, consistency index increases, and paste structure and thixotropy strengthen, and improve slurry sedimentation stability.
The impervious elastomerics cement prepared by the present invention has impermeable and toughening effect, cement strength loss is very little, Young's modulus reduces by 30%, Behavior of Hardened Cement Paste impact work improves 10 ~ 15%, and tensile strength increases by 5 ~ 10%, and Behavior of Hardened Cement Paste rate of permeation is less than 0.001 × 10-3 μm 2.
Above 11 embodiments are one embodiment of the present invention, but embodiments of the present invention are not limited thereto, and should be understood that those skilled in the art's some improvement without departing from the principles of the present invention all belong to protection scope of the present invention.
Claims (9)
1. the impervious elastomerics of oil well cement, it is characterized in that: impervious elastomeric component and mass ratio are: 20 ~ 80 parts, acrylonitrile-butadiene-styrene copolymer powder, 20 ~ 80 parts, alkene class vinyl acetate copolymer powder, organosilane or polysilane hydrophobic material 0.4 ~ 16 part.
2. the impervious elastomerics of a kind of oil well cement according to claim 1, it is characterized in that: described acrylonitrile-butadiene-styrene copolymer be with elastomerics be main chain graft copolymer and with the uniform mixture of the hard AS resin graft copolymer that is main chain, particle fineness 325 order.
3. the impervious method for producing elastomers of a kind of oil well cement according to claim 1, it is characterized in that: described acrylonitrile-butadiene-styrene copolymer powder powder concentration be 5% acid of hydrochloric acid and nitric acid composite solution carry out immersion treatment, treatment temp 50 DEG C, soak time 3 ~ 4 hours.
4. the impervious elastomerics of a kind of oil well cement according to claim 1, is characterized in that: described alkene class vinyl acetate copolymer powder is dispersion rubber powder, and dispersion rubber powder is ethylene vinyl acetate copolymer powder, is called for short EVA.
5. the impervious elastomerics of a kind of oil well cement according to claim 1, is characterized in that: the SEAL80 of described organosilane for providing for National Starch company, and polysilane powder hydrophobic material is DOW CORNING SPH50 or Wa Ke company BSPOWDERA.
6. one kind as the impervious method for producing elastomers of the oil well cement in claim 1-5 as described in any one claim, it is characterized in that: in Horizontal type helical ribbon mixer, add the acrylonitrile-butadiene-styrene copolymer powder of 20 ~ 80 and the organosilane of 0.4 ~ 16 or polysilane hydrophobic material, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 20 ~ 80 is added in batch mixing stir 30 minutes again.
7. one kind comprises the impervious elastomeric grout of oil well cement in claim 1-5 described in any one claim, it is characterized in that: it consists of: 5 ~ 15 parts, impervious elastomerics, fluid loss agent 1 ~ 4 part, dispersion agent 0 ~ 2 part, retardant 0 ~ 5 part, 44 ~ 53 parts, water, defoamer 0.2 part, cement 100 parts.
8. the impervious elastomerics grout of one according to claim 7, is characterized in that: described cement is silicate G level oil well cement; Dispersion agent is sulfonation tannin, sulfonated ketone aldehyde condensate, poly-how sulfonic acid or its mixture; Water retaining is 2-acrylamide-2-methyl propane sulfonic multipolymer or PVA water retaining; Retardant is organophosphate, poly-hydroxy organic acid, AMPS copolymers of unsaturated carboxylic acids or their compound; Defoamer is dimethyl silicone oil or tributyl phosphate.
9. a grout preparation method as claimed in claim 7, is characterized in that:
1) impervious elastomerics is prepared, the acrylonitrile-butadiene-styrene copolymer powder of 20 ~ 80 and the organosilane of 0.4 ~ 16 or polysilane hydrophobic material is added in Horizontal type helical ribbon mixer, stir 30 minutes, and then the alkene class vinyl acetate copolymer powder of 20 ~ 80 is added in batch mixing stir 30 minutes again;
2) prepare impervious elastomerics grout, by step 1) in preparation impervious elastomerics choose 5 ~ 15 parts, 1 ~ 4 portion of fluid loss agent, 0 ~ 2 part of dispersion agent, 0 ~ 5 part of retardant, 44 ~ 53 parts of water, 0.2 part of defoamer, 100 parts of cement; All powders are dry mixed, liquid material wet mixing, are then prepared by GB/T19139-2012 oil-well cement test method regulation step.
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Application publication date: 20151202 |