CN106866086B - A kind of low-density oil-well cement - Google Patents
A kind of low-density oil-well cement Download PDFInfo
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- CN106866086B CN106866086B CN201710165226.0A CN201710165226A CN106866086B CN 106866086 B CN106866086 B CN 106866086B CN 201710165226 A CN201710165226 A CN 201710165226A CN 106866086 B CN106866086 B CN 106866086B
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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
- C04B28/06—Aluminous cements
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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
- 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
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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
- 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
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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
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of low-density oil-well cements, belong to oil gas well cementing operation technical field.The oil-well cement includes following raw material by weight percentage: clinker 82~90%, gypsum 1~8%, hollow glass micropearl 5~10%, dispersing agent 0~0.3%, retarder 0.5~0.8%；The clinker is one of sulphoaluminate cement clinker, high belite sulphoaluminate cement clinker.The specific surface area of the sulphoaluminate cement clinker is 470~520cm2/g；Anhydrous calcium sulphoaluminate C in sulphoaluminate cement clinker mineral4A3
Description
Technical field
The present invention relates to a kind of low-density oil-well cements, belong to oil gas well cementing operation technical field.
Background technique
In drilling operation course, in case of shallow gas blowout, it will bring more serious as a result, especially drilling well at sea
It will cause the bowl-type at earth's surface in operation, when blowout is serious to collapse, ship and platform loss etc..Shallow-layer loose lithology, pressure-bearing energy
Power is low, causes pressure window narrow, presses steady control difficult, shallow stratum temperature is low, and cement slurry hydration rate is slow, Behavior of Hardened Cement Paste early strength
It is low, the risk of has channeling is exacerbated, surface layer annular space volume is big, replacement efficiency is low, the cement slurry of packing top shallow gas is by drilling fluid
Injury is serious, it is difficult to guarantee the good cementing of Behavior of Hardened Cement Paste.Therefore for shallow stratum, shallow gas is the main of surface casing cementing
Difficult point realizes effective sealing of shallow gas to guarantee its cementing quality, sets to the selection of mortar architecture, optimization cement slurry column
Meter is vital.
Light weight cement in the prior art, such as Publication No. " CN101463248 ", entitled " deep-sea low-temperature low-density
The oil-well cement of the patent of invention of degree oil-well cement ", the patent disclosure is increased by cement material, lightening material, dispersing agent and cement
Strong agent composition is characterized in that the cement material in the component is low temperature hard substrate cement fastly, and in product preparation, mixture enters to mitigate
The cement intensifier of material, dispersing agent sum solves the problems, such as cementing operation under the conditions of deep sea low temperature, in 5 DEG C, normal pressure, 8 hours
Under the conditions of, cement strength can achieve 3.5MPa or more, and cement slurry density is controlled in 1.50 ± 0.02g/cm3In range, water
Mud fluidity >=220mm meets the requirement of deep sea drilling well cementation.
The low temperature environment that the application environment of the cement is 5 DEG C, if existed in the use environment of application of the invention
Two problems, first, hydrolysis product of cement is not explicitly pointed out due to the low temperature mentioned in above-mentioned patent hard substrate cement fastly,
So under the conditions of 30 DEG C, 12h intensity > 12MPa, the index of intensity > 24MPa can not necessarily reach for 24 hours；Second, the water
Retarder is not added in mud system, while in order to realize low-temperature high-early strength, joined the cement intensifier of carbonate, meeting
The setting time for shortening cement is discontented with special surface casing cementing environment to early strong demand height, the requirement of setting time length.
For another example Publication No. " CN101805596A ", the patent of invention of entitled " non-floating bead low-density oil-well cement " should
The oil-well cement of patent disclosure is by 100 parts of oil-well cements, 12~20 parts of nanometer wollastonites, 120~180 parts of flyash, 3~6 parts
Early strength agent and 4~8 parts of cement dispersants compositions, wherein oil-well cement is by ratio of weight and the number of copies by 100 parts of cement slurries, 3~5 parts of stones
Cream and 1~3 part of copper tailing are made.
The oil-well cement that the patent uses is formed by oil-well cement clinker grinding, which becomes silicic acid three
Calcium, dicalcium silicate, tricalcium aluminate, four kinds of solid solution such as tetra calcium aluminoferrite, cement slurry density are 1.60 ± 0.02g/cm3, are resisted
20 DEG C of Compressive Strength, be for 24 hours 4.2MPa, and 40 DEG C, compression strength is 5.2MPa for 24 hours, and compression strength is not high enough, is not able to satisfy special list
The requirement of layer well cementation.
To sum up, the early strength of light weight cement in the prior art is not high enough, and the thickening time is short, and it is special not to be able to satisfy
Under the conditions of cementing operation.
Summary of the invention
Present invention seek to address that light weight cement in the prior art is early strong not high enough, thickening time short technical problem,
A kind of new low-density oil-well cement is provided, had not only been able to satisfy early strong demand, but also there is the longer thickening time, it is special to can satisfy
It is steady that surface casing cementing environment to the particular/special requirement of intensity and thickening, before realizing entire well cementation, in well cementation and after well cementation is all satisfied pressure
It is required that.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of low-density oil-well cement, it is characterised in that: including following raw material by weight percentage: clinker 82
~90%, gypsum 1~8%, hollow glass micropearl 5~10%, dispersing agent 0~0.3%, retarder 0.5~0.8%；
The clinker is one of sulphoaluminate cement clinker, high belite sulphoaluminate cement clinker；
The specific surface area of the sulphoaluminate cement clinker is 470~520cm2/g；In sulphoaluminate cement clinker mineral
Anhydrous calcium sulphoaluminate C4A3 Content is 50~75%.
It is well known to those skilled in the art, because thickening time and early strength are two indexs runed counter to, conventional low-density
Cement cannot meet simultaneously the requirement of the two indices, therefore not be suitable for needing early strong, the brill that the longer thickening time requires
Well operations.Above-mentioned technical proposal of the present invention, by selecting specific clinker: sulphoaluminate cement clinker, high belite sulphur
One of aluminate cement clinker, so that light weight cement has early strong characteristic；And by the gypsum of addition 1~8%, it can
Guarantee while having the thickening time of 180min~240min adjustable, and early strong high characteristic.Specifically, gypsum is that have to delay
Solidifying and promotion C4A3 The double action of aquation.
1. gypsum deferred action inhibits aquation to carry out: C in sulfoaluminate clinker4A3 For main phase, existing for gypsum
In the case of, C4A3 It reacting to form entringite with gypsum, under the action of gypsum, the entringite speed of formation is greatly speeded up,
These crystal are covered on unhydrated C quickly4A3 And the surface β-C2S, make unhydrated particle and gypsum, the catalytic chance of water
Greatly reduce, weaken its hydration rate, the effect of gypsum is based on slow setting at this time.
2. gypsum is to the facilitation of aquation: facilitation of the gypsum to aquation.Gypsum is to C4A3 Aquation, which has, to be promoted to make
With and C4A3 , β-C2S and 2CaSO42H2Mutual promoting action between O can be improved the early strength of cement slurry.Work as stone
When cream volume is big, it is remaining that there are also part gypsum other than being used to form cover film, the SO in liquid phase3 2-Concentration is larger, and aquation is anti-
It can should still carry out.At this time, the hydrated product of generation is mainly internal hydrated product, and the volume expansion of this product shells cover film
It falls, exposes new surface, and open the advantageous channel (i.e. crackle) for carrying out hydration reaction, in this way, gypsum promotes aquation to make
With occupying an leading position again, initial configuration is quickly formed.
The volume of selection for amount of gypsum, gypsum has vital effect for early strength and thickening time,
The invention selects gypsum addition 1~8%, is the early strength for 24 hours due to cement slurry requirement 12h, in its aquation of the volume
The generating rate and diffusion rate of product match very well, as the growth β-C2S aquation of age carries out, silica gel are generated, into one
Step filling space, structure is finer and close, and stable long-term strength increases, and accelerates mineral aquation, can promote the formation of entringite,
Increase morning Qiang Qiangdu.If gypsum addition is excessive, C in cement4A3 Hydration rate is too fast, forms crystalline texture.Crystalline texture
Net is prematurely formed, though it is advantageous to early strength, the smooth diffusion of the hydrated product subsequently generated is limited, in a limited space
Hydrated product bulk deposition and the very big expansion potential energy of generation, hurt structural damage, gain in strength is slow；In addition gypsum addition increases,
The deferred action of gypsum can weaken hydration rate as leading role, lead to the reduction of early strong intensity.
In order to which the present invention is better achieved, further, the lightening material be hollow glass micropearl, density 0.3~
0.6g/cm3, breakage rate < 10% under 40MPa intensity.
Further, the oil-well cement in configuration the ratio of mud that uses for 0.40~0.5.
The gypsum is anhydrite, and the specific surface area of gypsum is 450~500cm2/g。
The dispersing agent is one of polyaromatic sulfonate and formaldehyde condensation product FND, UNF, CFR-H.
The retarder is one of boric acid, borax, citric acid or two kinds.
Beneficial effects of the present invention:
(1) compared with light weight cement in the prior art, the present invention is matched by specific clinker with gypsum
Than and the materials such as a small amount of retarder being added, while guaranteeing light weight cement high early strength, so that cement also has
The thickening time of 180min~240min adjustable characteristic, to meet the special use environment of shallow stratum, to effectively protect
Its cementing quality is demonstrate,proved, realizes effective sealing of shallow gas.By test, cement slurry density of the invention can reach 1.5 ±
0.02 g/cm3, and the cement carries out compression test, 12h compression strength >=14MPa, for 24 hours resistance to compression under 30 DEG C, condition of normal pressure
Intensity >=25MPa.
(2) in the present invention, lightening material is hollow glass micropearl, 0.3~0.6g/cm of density3, damaged under 40MPa intensity
Rate < 10% can reduce the ratio of mud (preferably 0.40~0.50) using the hollow glass micropearl in the indication range, to improve
The stability of slurry, conversely, the settlement stability of cement slurry can be made using the ratio of mud 0.7 of Publication No. CN101463248
Property is bad.
(3) in the present invention, gypsum is anhydrite, and the specific surface area of gypsum is 450~500cm2/ g, the kind of gypsum with mix
Amount has very important influence to cement early strength, and China's anhydrite mineral resources are very rich, and raw material are easy to get, and can be improved
The utilization rate of China's anhydrite.Anhydrite is higher to the activity of sulphate aluminium cement, for accelerating the formation of entringite, improves early
The effect of phase intensity is better than other type gypsum.The specific surface area for increasing anhydrite can significantly improve the aquation rate of anhydrite, but
It is the increase with specific surface area, water requirement can also increase, and the ratio of mud is 0.4-0.5, gypsum specific surface area in the present invention
It will lead to very much cement slurry retrogradation greatly, in addition specific surface area increase can also consume more energy consumption of mill, therefore gypsum of the present invention ratio
Surface area is controlled in 450~500cm2/ g is preferable.
(4) in the present invention, the dispersing agent is polyaromatic sulfonate and formaldehyde condensation product FND, UNF, CFR-
One of H.The dispersing agent outstanding as oil-well cement, it is necessary to have good absorption dispersion performance to ensure cement
Slurry provides good rheological property, this depends on the structure and physical and chemical performance of dispersing agent, and above-mentioned dispersing agent passes through induction effect
Answer, the modes such as conjugation and three-dimensional effect exert one's influence to the absorption of polar end, dispersibility, by taking FDN as an example, FDN points
The conjugation of sulfonic group and naphthalene nucleus in son strengthens sulfonic electronic action power and improves absorption, dispersibility, by
In FDN etc. dispersion, wetting the effects of, promote the initial stage aquation of cement, can be improved early strength；Such dispersing agent is in sulphur
In use, consumptive use of water normal consistence can be substantially reduced in aluminate cement slurry, meanwhile, the reduction of water consumption is also beneficial to cement
Gelinite agglomerates the formation of network, this is the main reason for FDN etc. accelerates cement setting, improves early strength.When FDN volume
After reaching saturation point, the ionic adsorption that FDN dissociates electrification increases its ζ-potential on cement micelle surface, the stabilization of system
Time is just longer, while this layer of negative ion suck film and the moisture film as caused by hydrogen bond association, often hinders cement
Contact between particle and water, thus can rise and delay coagulation, the thickening time for increasing mortar architecture of the present invention has
Facilitation.
(5) in the present invention, retarder is one of boric acid, borax, citric acid or two kinds, and borax, boric acid etc. are inorganic
After acid or salt are added in aluminium sulfate water, it is wrapped in cement granules aquation layer surface due to forming line borate, keeps cement outstanding
Floating body tends towards stability, and cement particle is prevented to agglomerate, therefore can delay the condensation of cement.Citric acid belongs to organic acid, works as lemon
After lemon acid is added in sulphate aluminium cement, the generation of calcium citrate decreases Ca in solution2+Concentration, this allows for cement
Aquation induction period extends, and reaches slow setting purpose.It is based on inorganic that borax, boric acid, two kinds therein of citric acid, which are used in mixed way,
Acid is compounded with organic acid, is able to extend the thickening time of cement slurry, is expanded the Applicable temperature range of retarder, have retarder
Dispersibility, suspension etc..
Specific embodiment
The present invention is described in further detail below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of low-density oil-well cement, by following raw material by mass percentage: sulphoaluminate cement clinker 87.15%,
Anhydrite 6%, hollow glass micropearl 6%, dispersing agent C FR-H 0.1%, citric acid 0.75%, the ratio of mud 0.50.
In the present embodiment, gypsum specific surface area 462cm2/ g, the index 0.5g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 520cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 57%.
Embodiment 2
A kind of low-density oil-well cement, by following raw material by mass percentage: sulphoaluminate cement clinker 85%, firmly
Gypsum 4.2%, hollow glass micropearl 10%, dispersing agent FDN 0.3%, borax 0.5%, the ratio of mud 0.40.
In the present embodiment, gypsum specific surface area 450cm2/ g, the index 0.3g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 470cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 60%.
Embodiment 3
A kind of low-density oil-well cement, by following raw material by mass percentage: sulphoaluminate cement clinker 84.6%,
Anhydrite 10%, hollow glass micropearl 5%, dispersing agent FDN 0.1%, citric acid 0.3%, the ratio of mud 0.46.
In the present embodiment, gypsum specific surface area 473cm2/ g, the index 0.5g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 500cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 55%.
Embodiment 4
A kind of low-density oil-well cement, by following raw material by mass percentage: sulphoaluminate cement clinker 87.2%,
Anhydrite 4%, hollow glass micropearl 8%, boric acid 0.5%, 0.3% ratio of mud of citric acid are 0.42.
In the present embodiment, gypsum specific surface area 458cm2/ g, the index 0.5g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 490cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 52%.
Embodiment 5
A kind of low-density oil-well cement, by following raw material by mass percentage: sulphoaluminate cement clinker 90%, firmly
Gypsum 1%, hollow glass micropearl 8%, dispersing agent UNF 0.2%, boric acid 0.8%, the ratio of mud 0.46.
In the present embodiment, gypsum specific surface area 462cm2/ g, the index 0.5g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 500cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 52%.
Embodiment 6
A kind of low-density oil-well cement, by following raw material by mass percentage: sulphoaluminate cement clinker 82%, firmly
Gypsum 7%, hollow glass micropearl 10%, dispersing agent FDN0.15%, borax 0.65%, citric acid 0.20%, the ratio of mud 0.40.
In the present embodiment, gypsum specific surface area 500cm2/ g, the index 0.6g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 470cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 75%.
Embodiment 7
A kind of low-density oil-well cement, by following raw material by mass percentage: high belite sulphate aluminium cement is ripe
Material 86%, anhydrite 5.2%, hollow glass micropearl 8%, dispersing agent UNF 0.15%, 0.65% ratio of mud of borax are 0.45.
In the present embodiment, gypsum specific surface area 480cm2/ g, the index 0.3g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 492cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 50%.
Embodiment 8
A kind of low-density oil-well cement, by following raw material by mass percentage: high belite sulphate aluminium cement is ripe
Material 85.3%, anhydrite 8%, hollow glass micropearl 6%, dispersing agent FDN0.2%, borax 0.5%；The ratio of mud 0.48.
In the present embodiment, gypsum specific surface area 490cm2/ g, the index 0.4g/cm of glass microballoon3, sulphate aluminium cement is ripe
Expect specific surface area 510cm2/ g, anhydrous calcium sulphoaluminate C4A3 Content 63%.
The cement of embodiment 1 ~ 8 is detected, as a result as follows:
As can be seen from the above table, low-density oil-well cement of the invention can meet early strength height, thickening time simultaneously
It is long, it can satisfy the requirement of Special use environment.
The above is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, it is all according to
According to technical spirit any simple modification to the above embodiments of the invention, equivalent variations, protection of the invention is each fallen within
Within the scope of.
Claims (3)
1. a kind of low-density oil-well cement, it is characterised in that: including following raw material by weight percentage: clinker 82~
90%, gypsum 1~8%, hollow glass micropearl 5~10%, dispersing agent 0~0.3%, retarder 0.5~0.8%；
The clinker is one of sulphoaluminate cement clinker, high belite sulphoaluminate cement clinker；
The specific surface area of the sulphoaluminate cement clinker is 470~520cm2/g；Anhydrous sulphur in sulphoaluminate cement clinker mineral
Calcium aluminate C4A3`S content is 50~75%；Hollow glass micropearl, 0.3~0.6g/cm of density3, breakage rate < under 40MPa intensity
10%；The oil-well cement in configuration the ratio of mud that uses for 0.40~0.50；The gypsum is anhydrite, the ratio table of gypsum
Area is 450~500cm2/g。
2. a kind of low-density oil-well cement as described in claim 1, it is characterised in that: the dispersing agent is polyaromatic sulfonic acid
One of salt formaldehyde condensation products FND, UNF, CFR-H.
3. a kind of low-density oil-well cement as described in claim 1, it is characterised in that: the retarder is boric acid, borax, lemon
One of lemon acid or two kinds.
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| CN109516745A (en) * | 2017-09-18 | 2019-03-26 | 中国石油天然气集团公司 | Cement paste for well cementation and preparation method thereof |
| CN108675752B (en) * | 2018-06-19 | 2021-03-23 | 葛洲坝石门特种水泥有限公司 | High-strength high-temperature-resistant anti-erosion oil well cement and preparation method thereof |
| EP3750857A1 (en) * | 2019-06-14 | 2020-12-16 | Sika Technology Ag | Method for the kinetic regulation of cementitious binders |
| CN110357460B (en) * | 2019-07-11 | 2021-11-23 | 葛洲坝石门特种水泥有限公司 | Oil well cement suitable for salt-gypsum layer well cementation operation and preparation method thereof |
| CN111825399A (en) * | 2019-09-12 | 2020-10-27 | 尧柏特种水泥技术研发有限公司 | Low-thixotropy low-density high-strength cement paste |
| CN116262654A (en) * | 2021-12-15 | 2023-06-16 | 中国石油天然气集团有限公司 | In-situ toughness well cementation cement, well cementation cement paste and preparation method thereof |
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| CN1148577A (en) * | 1995-10-24 | 1997-04-30 | 淄博市张店特种水泥工业集团公司 | Oil-well cement |
| CN101054513A (en) * | 2007-05-21 | 2007-10-17 | 中国石油大学(华东) | Deep water low temperature cementing cement system |
| CN101463248A (en) * | 2007-12-21 | 2009-06-24 | 四川嘉华企业（集团）股份有限公司 | Low temperature low density oil well cement for deep sea |
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