CN105368411B - One kind is used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste - Google Patents

One kind is used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste Download PDF

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CN105368411B
CN105368411B CN201510925384.2A CN201510925384A CN105368411B CN 105368411 B CN105368411 B CN 105368411B CN 201510925384 A CN201510925384 A CN 201510925384A CN 105368411 B CN105368411 B CN 105368411B
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magnesium carbonate
carbonate whisker
sio
whisker
oil
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CN105368411A (en
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李明
靳建洲
袁进平
于永金
徐�明
齐奉忠
刘硕琼
张弛
郭小阳
郭子涵
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Southwest Petroleum University
CNPC Engineering Technology R&D Co Ltd
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Southwest Petroleum University
CNPC Drilling Research Institute Co Ltd
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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
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions

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  • Life Sciences & Earth Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

It is used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste the invention discloses one kind, is prepared by following steps：(1) magnesium carbonate whisker is added in deionized water, is moved to after being disperseed using ultrasonic wave in 80 DEG C of water bath with thermostatic control, Na is added dropwise2SiO3Aqueous solution, is constantly passed through CO2, when the pH value of suspension reaches 8~9, stop logical CO2, 2~3h is aged, then washing and filtering, drying, screening are carried out to suspension；(2) using silane coupling agent to SiO2Cladding magnesium carbonate whisker particle is modified；(3) coupling agent modified whisker particle is placed in spray drying device, drying temperature is 100~200 DEG C, and magnesium carbonate whisker toughener is obtained after handling 30min.The present invention maintains original performance of magnesium carbonate whisker, and can be combined well with cement material, does not influence the original engineering property of cement mortar, can significantly reduce the brittleness of oil/gas well Behavior of Hardened Cement Paste.

Description

One kind is used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste
Technical field
The present invention relates to a kind of toughener for being used for oil gas well cementing operation in petroleum natural gas exploration, this toughener can Reaching reduces the brittle effect of Behavior of Hardened Cement Paste, improves the mechanical property of Behavior of Hardened Cement Paste.
Background technology
Cement slurry sets form oil-well cement ring (stone) after well cementing operation, and the effect of cement sheath includes supporting sleeve and prevents Formation fluid is to realize resource hierarchy to burn into packing lost-circulation zone and slough formation etc. bad ground, the packing oil-gas-water layer of casing Exploitation lays the foundation.Good cement sheath should maintain long term seal integrality, this is most important to oil/gas well Production Life, and directly Connecing influences later stage oil-gas mining.Since Behavior of Hardened Cement Paste is fragile material, by the subsequent jobs such as perforation, pressure break, exploitation and subterranean strata The influence of complexing action power, is also easy to produce microcrack and microannulus, cause oil/gas well Inter-zonal packing fail, be unfavorable for oil-gas mining and Volume increase.Therefore, it is most important to oil-gas mining and volume increase can to reduce the brittle material of Behavior of Hardened Cement Paste for research acquisition.At present, in stone Oily field reduces the brittleness of cement sheath, but organic fibre such as common polyester fiber, polypropylene fibre, carbon fiber using fiber more Dimension bad dispersibility, of high cost and durability in Behavior of Hardened Cement Paste is poor, it is impossible to effectively improves the toughness of Behavior of Hardened Cement Paste, therefore, there is an urgent need for grind The brittle material of Behavior of Hardened Cement Paste can be reduced by studying carefully to obtain.
Whisker is a fibre-like monocrystal.The diameter very little of whisker, generally 0.1~10 μm, draw ratio for 10~ 100, since its diameter is small, it is difficult to be received into the gap of big crystal, therefore the structure of this high-sequential causes whisker Intensity be usually closer to the theoretical strength of chemical bond between lattice atoms.In one-dimensional, bidimensional known today, three-dimensional reinforcement In, whisker is the composite material activeness and quietness body of best performance.Magnesium carbonate whisker is the palpus shape that a kind of size is much smaller than staple fiber Monocrystal, has the characteristic of mineral micro powder and fiber concurrently, has excellent chemical stability, thermal insulation and wearability.But this crystalline substance Must be poor with the compatibility of Behavior of Hardened Cement Paste, if carrying out specially treated to this whisker, it is allowed to have good compatibility with Behavior of Hardened Cement Paste, So magnesium carbonate whisker will become a kind of preferable toughening material, not applied at present in cement mortar also.
To make magnesium carbonate whisker and Behavior of Hardened Cement Paste have good compatibility, precipitation method SiO can be first used2It is brilliant to coat magnesium carbonate Must, then again to the whisker after parcel with coupling agent modified.SiO2Cladding is to carry out " cladding " to material surface using inorganic matter It is modified to achieve the purpose that, carry out coating using simple deposited phenomenon.Coupling agent is the material for having both sexes structure, its molecule In a part of group can form strong chemical bonding, another part group with the various functional group reactions of powder surface Some chemical reactions or physical entanglement can occur with organic polymer, so that the widely different material of two kinds of materials be tied securely Altogether.Silane coupling agent is a kind of low molecule organo-silicon compound with special construction, its phase interaction between inorganic mineral With, material surface formed network structure film, make material surface performance change.
The content of the invention
It is an object of the invention to provide one kind can reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste, should Toughener maintains original performance of magnesium carbonate whisker, and can be combined well with cement material, does not influence cement mortar Original engineering property, and the friable structure of Behavior of Hardened Cement Paste is changed to a certain extent, oil/gas well Behavior of Hardened Cement Paste can be significantly reduced Brittleness.
To reach above-mentioned technical purpose, the present invention provides following technical scheme：
One kind is used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste, is prepared by following steps：
(1) precipitation method SiO is passed through2Coat magnesium carbonate whisker
Solution is prepared：Prepare the Na of 0.05~0.15mol/L2SiO3Aqueous solution 100mL.
Magnesium carbonate whisker processing：10~30g magnesium carbonate whiskers are added in 100mL deionized waters, utilize ultrasonic wavelength-division Dissipate 10~30min.
Precipitation cladding：Solution containing magnesium carbonate whisker is moved in 80 DEG C of water bath with thermostatic control, be added dropwise under fast stirring The Na configured2SiO3Solution, while with CO2For precipitating reagent, CO is constantly passed through2, and the pH value of suspension is observed, when pH reaches 8 When~9, stop logical CO2。
Particle disposal：2~3h of digestion time, then washing and filtering is carried out to suspension, dry 24h, sieve under the conditions of 120 DEG C Get the SiO that length is 40~80 μm2Coat magnesium carbonate whisker particle.
(2) using silane coupling agent to SiO2Cladding magnesium carbonate whisker particle is modified
Silane coupling agent is made into the dilution that concentration is 0.5~1.5 mass % with absolute ethyl alcohol, SiO2Coat carbonic acid After magnesium whisker particle immersion wherein 20~40min, cleaned repeatedly with clear water and remove excess surface coupling agent.
(3) it is spray-dried
Coupling agent modified whisker particle is placed in spray drying device, drying temperature is set to 100~200 DEG C, processing Taken out after 30min, up to being used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste.
Material described above is commercially available.
Compared with prior art, the invention has the advantages that：
(1) toughener passes through SiO2After cladding, the original performance structure of magnesium carbonate whisker, its draw ratio and height are saved The excellent performances such as intensity can play a role in cement material；
(2) coupling agent is in SiO2Cladding is modified again, and mutually association oligomerisation forms net to the silanol of each molecule of silane again The film of network structure is covered in whisker particle surface, makes its inorganization, is more advantageous to the combination of whisker particle and cement granules；
(3) with not adding compared with the Behavior of Hardened Cement Paste of toughener, the compression strength for adding the Behavior of Hardened Cement Paste of toughener is increased slightly, And flexural strength then significantly rises.From the point of view of compression strength/flexural strength this index, to add the crisp of the Behavior of Hardened Cement Paste of toughener Property significantly reduces.Magnesium carbonate whisker toughener significantly reduces the brittleness of hardened oilwell cement, improves hardened oilwell cement mechanics Performance.
Embodiment
Each embodiment of preparation and performance test below by way of magnesium carbonate whisker toughener further illustrates the present invention.
Embodiment 1
Prepare as follows for reducing the brittle magnesium carbonate whisker toughener relevant parameter of oil/gas well Behavior of Hardened Cement Paste：
Solution is prepared：0.05mol/LNa2SiO3Aqueous solution 100mL.
Whisker processing：10g magnesium carbonate whiskers are added in 100mL deionized waters, and ultrasonic wave disperses 10min.
Precipitate capsulation condition：80 DEG C of waters bath with thermostatic control, are passed through CO2To pH of suspension=8.
Digestion time：2h.
Coat drying：120 DEG C, 24h.
Coupling agent：Concentration is 0.5 mass %.
Soaking time：20min.
Spray drying：100 DEG C, 30min.
After magnesium carbonate whisker toughener prepares, it (is weight below to add in cement and prepare well cementation toughness reinforcing cement mortar again Part)：Weigh 100 parts of oil-well cement, 2 parts of sodium carboxymethylcellulose, 0.5 part of lignosulfonates, 5 parts of SILICA FUME, alleged dry powder It is uniformly mixed；60 parts of water is weighed, 1~10 part of 0.1 part of tributyl phosphate and toughener is soluble in water.By the water containing toughener Solution is pre-mixed in a reservoir with uniform mixed dry powder, and blender is rotated for (4000 ± 200 revs/min) with low speed, and 15 The powder mixture weighed is added in second, covers the lid of blender, continues stirring 35 under (12000 ± 500 revs/min) at a high speed Second, up to toughness reinforcing cement mortar of cementing the well.
The engineering property of well cementation toughness reinforcing cement mortar is tested according to API specification.The test condition of thickening time：90℃× 50MPa (heating-up time 50min).Behavior of Hardened Cement Paste curing condition：30 DEG C/60 DEG C/90 DEG C × normal pressure × 1d/3d/7d.
The cement mortar is shown in Tables 1 and 2 with cement properties situation.
Well cementation toughness reinforcing cement mortar engineering property prepared by 1 embodiment 1 of table
Well cementation toughness reinforcing cement strength performance prepared by 2 embodiment 1 of table
Embodiment 2
Prepare as follows for reducing the brittle magnesium carbonate whisker toughener relevant parameter of oil/gas well Behavior of Hardened Cement Paste：
Solution is prepared：0.10mol/LNa2SiO3Aqueous solution 100mL.
Whisker processing：20g magnesium carbonate whiskers are added in 100mL deionized waters, and ultrasonic wave disperses 20min.
Precipitate capsulation condition：80 DEG C of waters bath with thermostatic control, are passed through CO2To pH of suspension=8.5.
Digestion time：2.5h.
Coat drying：120 DEG C, 24h.
Coupling agent：Concentration is 1.0 mass %.
Soaking time：30min.
Spray drying：150 DEG C, 30min.
Prepare well cementation toughness reinforcing cement mortar (being parts by weight below)：Weigh 100 parts of oil-well cement, sodium carboxymethylcellulose 2 Part, 0.5 part of lignosulfonates, 5 parts of SILICA FUME, alleged dry powder blend is uniform；60 parts of water is weighed, by 0.1 part of tributyl phosphate It is soluble in water with 1~10 part of toughener.Aqueous solution containing toughener and uniform mixed dry powder are pre-mixed in a reservoir, Blender added the powder mixture weighed with (4000 ± 200 revs/min) rotations of low speed in 15 seconds, covered blender Lid, continues stirring 35 seconds, up to toughness reinforcing cement mortar of cementing the well under (12000 ± 500 revs/min) at a high speed.
The engineering property of well cementation toughness reinforcing cement mortar is tested according to API specification.The test condition of thickening time：90℃× 50MPa (heating-up time 50min).Behavior of Hardened Cement Paste curing condition：30℃/90℃×21MPa×28d.
The cement mortar is shown in Table 3 and table 4 with cement properties situation.
Well cementation toughness reinforcing cement mortar engineering property prepared by 3 embodiment 2 of table
Well cementation toughness reinforcing cement strength performance prepared by 4 embodiment 2 of table
Embodiment 3
Prepare as follows for reducing the brittle magnesium carbonate whisker toughener relevant parameter of oil/gas well Behavior of Hardened Cement Paste：
Solution is prepared：0.15mol/LNa2SiO3Aqueous solution 100mL.
Whisker processing：30g magnesium carbonate whiskers are added in 100mL deionized waters, and ultrasonic wave disperses 30min.
Precipitate capsulation condition：80 DEG C of waters bath with thermostatic control, are passed through CO2To pH of suspension=9.
Digestion time：3h.
Coat drying：120 DEG C, 24h.
Coupling agent：Concentration is 1.5 mass %.
Soaking time：40min.
Spray drying：200 DEG C, 30min.
Prepare well cementation toughness reinforcing cement mortar (being parts by weight below)：Weigh 100 parts of oil-well cement, sodium carboxymethylcellulose 2 Part, 0.5 part of lignosulfonates, 5 parts of SILICA FUME, alleged dry powder blend is uniform；60 parts of water is weighed, by 0.1 part of tributyl phosphate It is soluble in water with 1~10 part of toughener.Aqueous solution containing toughener and uniform mixed dry powder are pre-mixed in a reservoir, Blender added the powder mixture weighed with (4000 ± 200 revs/min) rotations of low speed in 15 seconds, covered blender Lid, continues stirring 35 seconds, up to toughness reinforcing cement mortar of cementing the well under (12000 ± 500 revs/min) at a high speed.
The engineering property of well cementation toughness reinforcing cement mortar is tested according to API specification.The test condition of thickening time：90℃× 50MPa (heating-up time 50min).Behavior of Hardened Cement Paste curing condition：30 DEG C/60 DEG C/90 DEG C × normal pressure × 1d/3d/7d.
The cement mortar is shown in Table 5 and table 6 with cement properties situation.
Well cementation toughness reinforcing cement mortar engineering property prepared by 5 embodiment 3 of table
Well cementation toughness reinforcing cement strength performance prepared by 6 embodiment 3 of table

Claims (1)

1. one kind is used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste, prepared by following steps：
(1) precipitation method SiO is passed through2Coat magnesium carbonate whisker：
Prepare the Na of 0.05~0.15mol/L2SiO3Aqueous solution 100mL, by 10~30g magnesium carbonate whiskers be added to 100mL go from In sub- water, disperse 10~30min using ultrasonic wave, the solution containing magnesium carbonate whisker is moved in 80 DEG C of water bath with thermostatic control, stirred Mix lower dropwise addition Na2SiO3Solution, while constantly it is passed through CO2, when the pH value of suspension reaches 8~9, stop logical CO2, ageing 2~ 3h, then washing and filtering is carried out to suspension, the dry 24h under the conditions of 120 DEG C, screening obtains the SiO that length is 40~80 μm2Bag Cover magnesium carbonate whisker particle；
(2) using silane coupling agent to SiO2Cladding magnesium carbonate whisker particle is modified：
Silane coupling agent is made into the dilution that concentration is 0.5~1.5 mass % with absolute ethyl alcohol, SiO2It is brilliant to coat magnesium carbonate After palpus particle immersion wherein 20~40min, cleaned repeatedly with clear water and remove excess surface coupling agent；
(3) it is spray-dried：
Coupling agent modified whisker particle is placed in spray drying device, drying temperature is 100~200 DEG C, after handling 30min Take out, up to being used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste.
CN201510925384.2A 2015-12-11 2015-12-11 One kind is used to reduce the brittle magnesium carbonate whisker toughener of oil/gas well Behavior of Hardened Cement Paste Active CN105368411B (en)

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CN112299736B (en) * 2019-07-30 2022-07-12 中国石油化工股份有限公司 Cementing composition, composite cementing material and cementing fluid
CN112226218B (en) * 2020-11-06 2022-07-01 西南石油大学 Composite toughening channeling-preventing agent suitable for oil well cement and preparation method thereof

Citations (4)

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JPH01320219A (en) * 1988-06-23 1989-12-26 Nippon Chem Ind Co Ltd Magnesium hydroxide coated with silica and its production
CN1556154A (en) * 2004-01-08 2004-12-22 上海交通大学 Method of inorganic whisker surface treatment
CN1569746A (en) * 2004-04-29 2005-01-26 上海交通大学 Method for preparing inorganic crystal whisker with SiO2-coated surface
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Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH01320219A (en) * 1988-06-23 1989-12-26 Nippon Chem Ind Co Ltd Magnesium hydroxide coated with silica and its production
CN1556154A (en) * 2004-01-08 2004-12-22 上海交通大学 Method of inorganic whisker surface treatment
CN1569746A (en) * 2004-04-29 2005-01-26 上海交通大学 Method for preparing inorganic crystal whisker with SiO2-coated surface
CN102137813A (en) * 2008-09-01 2011-07-27 赢创德固赛有限责任公司 Process for preparing precipitated silicas, precipitated silicas and their use

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