CN105505350A - Elastic and flexible oil well cement slurry system based on temperature sensitive shape memory polymer and preparation method thereof - Google Patents
Elastic and flexible oil well cement slurry system based on temperature sensitive shape memory polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an elastic and flexible oil well cement slurry system based on a temperature sensitive shape memory polymer. The system comprises the following components in parts by weight: 100 parts of cement, 1 to 5 parts of elastic particle material of temperature sensitive shape memory polymer powder, 0.1 to 0.5 part of temperature sensitive shape memory polymer fiber, 3 to 6 parts of 2-acrylamido-methyl propane sulfonic acid/acrylic acid/acrylamide ternary polymer (fluid loss agent), 0.5 to 1.5 parts of aldehyde-ketone condensation polymer dispersant, 0.1 to 0.5 part of polypropylene fiber with a length of 3 to 5 mm, 0 to 5 parts of micro silicon, 0.05 to 0.1 part of tributyl phosphate, 0.01 to 1.5 parts of delayed coagulant, and 37 to 44 parts of water. The provided oil well cement slurry system can prominently reduce the elastic module of cured cement and improve the flexural strength of cured cement, and thus the cement ring has a strong impact resistant performance and high toughness.
Description
Technical field
The present invention relates to grout preparation field in drilling well, furtherly, relate to a kind of malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer and preparation method.
Background technology
Common cement paste for well cementation is generally made up of water, cement, admixture (water retaining, dispersion agent, retardant etc.) and extra material (fiber, micro-silicon etc.).
The cement mantle elasticity that common cement paste for well cementation is formed is little, fragility is large, the perforation bearing high energy-gathering jetting in down-hole impacts, the impact of big-frac treatment and staged fracturing and running casing and when continuing to creep into during collision impact to cement mantle of sleeve pipe and drill bit, cement mantle overall integrity can be destroyed, cause later stage interlayer seal performance failure, to Oil/gas Well, particularly high acid gas-containing well later stage well stimulation and Development and Production have potential potential safety hazard, cannot ensure that Oil/gas Well is kept the safety in production, cause huge financial loss.Therefore ensure that the integrity of oil well cement ring has great importance.
Summary of the invention
For solving produced problem in prior art, the invention provides a kind of malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer and preparation method.Can solve little, the fragility of cement mantle elasticity that common cement paste for well cementation formed large, under the impact loading produced in perforation exploitation and fracturing reform operation, cement mantle overall integrity is destroyed, and causes hydrocarbon zone to alter the problem of groove.
An object of the present invention is to provide a kind of malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer.
Comprise the following component counted by weight:
Cement 100 weight part;
Temperature sensitive shape-memory polymer powdered. elastomer particulate material 1 ~ 5 weight part; Preferably 2 ~ 5 weight parts;
Temperature sensitive shape memory polymer fibers 0.1 ~ 0.5 weight part; Preferably 0.1 ~ 0.2 weight part;
2-acrylamide-2-methylpro panesulfonic acid/acrylic acid/acrylamide ter-polymers water retaining 3 ~ 6 weight part;
Condensation polymeric dispersant 0.5 ~ 1.5 weight part;
Polypropylene fibre 0.1 ~ 0.5 weight part;
Micro-silicon 0 ~ 5 weight part;
Tributyl phosphate 0.05 ~ 0.1 weight part;
Retardant 0.01 ~ 1.5 weight part,
Water 37 ~ 44 weight part;
Described temperature sensitive shape-memory polymer is: polynorbornene, trans Isosorbide-5-Nitrae-polyisoprene, styrene-butadiene copolymer, Styrene And Butyl-acrylate multipolymer, urethane, crosslinked polyethylene, polyvinyl acetal gel, ethylene-vinyl acetate copolymer, polycaprolactone, polymeric amide or poly-fluoroolefins; Temperature sensitive shape-memory polymer shape memory transition temperature is between 50 ~ 80 DEG C;
The particle diameter of described temperature sensitive shape-memory polymer powdered. elastomer particulate material is between 4 ~ 400 orders;
The monfil diameter of described temperature sensitive shape memory polymer fibers is between 5 ~ 300 μm, and length is between 0.05 ~ 10cm.
Temperature sensitive shape-memory polymer is the one of shape-memory polymer.Shape-memory polymer (ShapeMemoryPolymer, be called for short SMP) be a class novel intelligent material, this material is endowed certain initial intrinsic shape in molding process, deform under certain conditions and be fixed, as long as when needs it time to it apply certain means (as heating, illumination, energising, chemical treatment etc.), it just can be made to return to original shape rapidly.The characteristic of this " the first type-deformation-fixing-reply just type " of particular polymers is called as the shape-memory properties of polymkeric substance, and shape-memory polymer (SMP) belongs to the one of shape-memory material.SMP can be divided into temperature (heat) quick type SMP, Photosensitive SMP, electric quick type SMP, chemical co-ordination type SMP etc.Wherein temperature sensitive type SMP shape memory effect is caused by temperature change, performance relative maturity own, workable, is widely applied.
Oil well cement elastic particle based on temperature sensitive shape-memory polymer pulverizes preparation by the temperature sensitive shape-memory polymer of one through cryogenic freezing, and particle diameter is between 4 ~ 400 orders; Oil well cement toughened fiber based on temperature sensitive shape-memory polymer is prepared by the temperature sensitive shape-memory polymer of one, and its monfil diameter is between 5 ~ 300 μm, and length is between 0.05 ~ 10cm.
Condensation polymeric dispersant is dispersion agent the most frequently used in auxiliary agent of cementing the well at present.
Polypropylene fibre is that in current common commercially available fiber, heatproof is best, conventional in well cementation.Staple length between 3 ~ 5mm,
Retardant adopts retardant conventional in well cementation in prior art, as: citric acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Sunmorl N 60S etc.
Can also add according to practical situation other auxiliary agents that this area adopts usually in well cementing mortar architecture of the present invention, as: swelling agent, flow pattern regulator, agent for anti gassing-out etc., its consumption is conventional amount used, and those skilled in the art suitably can adjust according to practical situation.
Two of object of the present invention is to provide a kind of preparation method of the malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer.
Comprise:
Solid in component and liquid are mixed by described consumption respectively, obtain mixing split and mixing liquid, then join in mixing liquid by mixed powder, stir the obtained described malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer.
Particularly,
Cement, micro-silicon, temperature sensitive shape-memory polymer powdered. elastomer particulate material, temperature sensitive shape memory polymer fibers, polypropylene fibre are mixed to obtain mixed powder by described consumption;
Then ter-polymers water retaining, condensation polymeric dispersant, tributyl phosphate, retardant are mixed to obtain mixing liquid with water by described consumption;
Finally join in mixing liquid by mixed powder, stir the malleable well cementing mortar architecture namely obtained based on temperature sensitive shape-memory polymer.
Malleable well cementing mortar architecture of the present invention, have employed the elastic particle of temperature sensitive shape-memory polymer and temperature sensitive shape memory polymer fibers, effectively add elasticity and the toughness of Behavior of Hardened Cement Paste, reduce Behavior of Hardened Cement Paste Young's modulus, make cement mantle have higher shock resistance and toughness.System can be reduced in the destruction that in perforation exploitation and fracturing reform operation process, the shock load that produces is suffered cement mantle, has good promotion and application value.
Meanwhile, temperature sensitive shape-memory polymer is hard before reaching deformation temperature, is convenient to mixture and the pumping of on-the-spot grout.During well cementation, along with pumping into of grout raises gradually with downhole temperature, causing its elasticity when reaching deformation temperature, playing a role.Grout poor compatibility when which solving the mixed slurry that ordinary rubber elastic granule causes due to soft elasticity, the problem of not easily pumping.
Embodiment
One, embodiment
Below in conjunction with embodiment, further illustrate the present invention.
In embodiment raw materials used be commercially available.
Embodiment 1
(1) 500g oil well cement is taken, 2-acrylamide-2-methylpro panesulfonic acid/acrylic acid/acrylamide ter-polymers water retaining 15g, temperature sensitive shape-memory polymer powdered. elastomer particulate material (Styrene And Butyl-acrylate multipolymer, between particle diameter 4 ~ 400 order, shape memory transition temperature 50 ~ 60 DEG C) 5g, condensation polymeric dispersant 2.5g, polypropylene fibre 0.5g, temperature sensitive shape memory polymer fibers (urethane, monfil diameter is between 5 ~ 300 μm, length is between 0.05 ~ 10cm) 0.5g, tributyl phosphate 0.25g, retardant Sunmorl N 60S 0.05g, fresh water 220g.
(2) cement, micro-silicon, temperature sensitive shape-memory polymer powdered. elastomer particulate material, temperature sensitive shape memory polymer fibers, polypropylene fibre are mixed to obtain mixed powder;
(3) mixing liquid is obtained by even to ter-polymers water retaining, polyvinyl alcohol water retaining, condensation polymeric dispersant, tributyl phosphate, retardant and mixing of fresh water;
(4) in the mixing container, add mixing liquid, agitator rotates with low speed (4000 ± 200 revs/min), and added in 15 seconds and mix to obtain mixed powder, cover the lid of agitator, and stirring is continued 35 seconds under high speed (12000 ± 500 revs/min), stir the malleable well cementing mortar architecture namely obtained based on temperature sensitive shape-memory polymer, density 1.86g/cm
3.
Embodiment 2
(1) 500g oil well cement is taken, micro-silicon 15g, 2-acrylamide-2-methylpro panesulfonic acid/acrylic acid/acrylamide ter-polymers water retaining 25g, temperature sensitive shape-memory polymer powdered. elastomer particulate material (urethane, between particle diameter 4 ~ 400 order, shape memory transition temperature 60 ~ 70 DEG C) 15g, condensation polymeric dispersant 5g, polypropylene fibre 1.5g, temperature sensitive shape memory polymer fibers (polyvinyl acetal gel, monfil diameter is between 5 ~ 300 μm, length is between 0.05 ~ 10cm) 1.5g, tributyl phosphate 0.4g, retardant citric acid 5g, fresh water 185g.
According to the working method of (2) ~ (4) in embodiment 1, obtain the malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer, density 1.90g/cm
3.
Embodiment 3
(1) 500g oil well cement is taken, micro-silicon 25g, 2-acrylamide-2-methylpro panesulfonic acid/acrylic acid/acrylamide ter-polymers water retaining 30g, temperature sensitive shape-memory polymer powdered. elastomer particulate material (ethylene-vinyl acetate copolymer, between particle diameter 4 ~ 400 order, shape memory transition temperature 70 ~ 80 DEG C) 25g, condensation polymeric dispersant 7.5g, polypropylene fibre 2.5g, temperature sensitive shape memory polymer fibers (trans 1, 4-polyisoprene, monfil diameter is between 5 ~ 300 μm, length is between 0.05 ~ 10cm) 2.5g, tributyl phosphate 0.5g, retardant 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 7.5g, fresh water 200g.
According to the working method of (2) ~ (4) in embodiment 1, obtain the malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer, density 1.89g/cm
3.
Comparative example: blank grout and Behavior of Hardened Cement Paste preparation
Take 500g oil well cement, tributyl phosphate 0.5g, 2-acrylamide-2-methylpro panesulfonic acid/acrylic acid/acrylamide ter-polymers water retaining 20g, condensation polymeric dispersant 5g, retardant 5g, fresh water 190g.
According to the working method of (2) ~ (4) in embodiment 1, obtain blank grout, density 1.90g/cm
3.
By above-described embodiment 1 ~ 3 and comparative example grout, pour into respectively in the maintenance module of 4cm × 4cm × 16cm, put into the water-bath maintenance 24 hours of 50 DEG C, take out the cement solidified, obtain Behavior of Hardened Cement Paste module.
Two, Behavior of Hardened Cement Paste Young's modulus and intensity test
Adopt German Toni pressure-proof and snap-resistent tester, when room temperature 25 DEG C, test water mudstone module Young's modulus and folding strength.Test result is as table 1.
Table 1
Sample | Young's modulus (GPa) | Folding strength (MPa) |
Comparative example-blank Behavior of Hardened Cement Paste module | 13.6 | 0.21 |
Embodiment 1 Behavior of Hardened Cement Paste module | 9.4 | 0.27 |
Embodiment 2 Behavior of Hardened Cement Paste module | 8.3 | 0.35 |
Embodiment 3 Behavior of Hardened Cement Paste module | 6.1 | 0.40 |
Can find out, have employed the elastic particle of temperature sensitive shape-memory polymer and the malleable well cementing mortar architecture of temperature sensitive shape memory polymer fibers, significantly can reduce Behavior of Hardened Cement Paste Young's modulus (adding the elasticity of Behavior of Hardened Cement Paste), refinforced cement stone folding strength (improve the toughness of Behavior of Hardened Cement Paste).System can be reduced in the destruction that in perforation exploitation and fracturing reform operation process, the shock load that produces is suffered cement mantle, and after advantageously ensuring oil gas well cementing operation, frscturing is on the impact of cementing quality, provides favourable support for realizing wellbore integrity.
Claims (5)
1., based on a malleable well cementing mortar architecture for temperature sensitive shape-memory polymer, it is characterized in that:
Described mortar architecture comprises the following component counted by weight:
Cement 100 weight part;
Temperature sensitive shape-memory polymer powdered. elastomer particulate material 1 ~ 5 weight part;
Temperature sensitive shape memory polymer fibers 0.1 ~ 0.5 weight part;
2-acrylamide-2-methylpro panesulfonic acid/acrylic acid/acrylamide ter-polymers water retaining
3 ~ 6 weight parts;
Condensation polymeric dispersant 0.5 ~ 1.5 weight part;
Polypropylene fibre 0.1 ~ 0.5 weight part;
Micro-silicon 0 ~ 5 weight part;
Tributyl phosphate 0.05 ~ 0.1 weight part;
Retardant 0.01 ~ 1.5 weight part,
Water 37 ~ 44 weight part;
Described temperature sensitive shape-memory polymer is: polynorbornene, trans Isosorbide-5-Nitrae-polyisoprene, styrene-butadiene copolymer, Styrene And Butyl-acrylate multipolymer, urethane, crosslinked polyethylene, polyvinyl acetal gel, ethylene-vinyl acetate copolymer, polycaprolactone, polymeric amide or poly-fluoroolefins; Temperature sensitive shape-memory polymer shape memory transition temperature is between 50 ~ 80 DEG C;
The particle diameter of described temperature sensitive shape-memory polymer powdered. elastomer particulate material is between 4 ~ 400 orders;
The monfil diameter of described temperature sensitive shape memory polymer fibers is between 5 ~ 300 μm, and length is between 0.05 ~ 10cm;
The length of described polypropylene fibre is between 3 ~ 5mm.
2. well cementing mortar architecture as claimed in claim 1, is characterized in that:
Described temperature sensitive shape-memory polymer is: styrene-butadiene copolymer, Styrene And Butyl-acrylate multipolymer, urethane, polyvinyl acetal gel or ethylene-vinyl acetate copolymer.
3. well cementing mortar architecture as claimed in claim 1, is characterized in that:
Temperature sensitive shape-memory polymer powdered. elastomer particle 2 ~ 5 weight part;
Temperature sensitive shape memory polymer fibers 0.1 ~ 0.2 weight part.
4. a preparation method for the malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer as described in one of claims 1 to 3, is characterized in that described method comprises:
Solid in component and liquid are mixed by described consumption respectively, obtain mixing split and mixing liquid, then join in mixing liquid by mixed powder, stir the obtained described malleable well cementing mortar architecture based on temperature sensitive shape-memory polymer.
5. preparation method as claimed in claim 4, is characterized in that:
Cement, micro-silicon, temperature sensitive shape-memory polymer powdered. elastomer particulate material, temperature sensitive shape memory polymer fibers, polypropylene fibre are mixed to obtain mixed powder by described consumption;
Then ter-polymers water retaining, polyvinyl alcohol water retaining, condensation polymeric dispersant, tributyl phosphate, retardant are mixed to obtain mixing liquid with water by described consumption;
Finally join in mixing liquid by mixed powder, stir the malleable well cementing mortar architecture namely obtained based on temperature sensitive shape-memory polymer.
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WO2017184813A1 (en) * | 2016-04-21 | 2017-10-26 | Dahi-Taleghani Arash | Cement materials including shape memory polymer and methods of making cement materials |
CN108239531A (en) * | 2016-12-23 | 2018-07-03 | 中石化石油工程技术服务有限公司 | A kind of shape memory type sealing agent |
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CN112625663B (en) * | 2019-09-24 | 2022-09-09 | 中国石油化工股份有限公司 | Well cementation composite leaking stoppage isolation liquid system and application thereof |
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