WO2015152860A1 - Compositions and methods for well completions - Google Patents

Compositions and methods for well completions Download PDF

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Publication number
WO2015152860A1
WO2015152860A1 PCT/US2014/032310 US2014032310W WO2015152860A1 WO 2015152860 A1 WO2015152860 A1 WO 2015152860A1 US 2014032310 W US2014032310 W US 2014032310W WO 2015152860 A1 WO2015152860 A1 WO 2015152860A1
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WIPO (PCT)
Prior art keywords
silicate
cement
composition
combinations
hydraulic cement
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PCT/US2014/032310
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French (fr)
Inventor
Anthony Loiseau
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Schlumberger Canada Limited
Services Petroliers Schlumberger
Schlumberger Holdings Limited
Schlumberger Technology B.V.
Prad Research And Development Limited
Schlumberger Technology Corporation
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Priority to PCT/US2014/032310 priority Critical patent/WO2015152860A1/en
Publication of WO2015152860A1 publication Critical patent/WO2015152860A1/en

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    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00Sealing or packing boreholes or wells
    • E21B33/10Sealing or packing boreholes or wells in the borehole
    • E21B33/13Methods or devices for cementing, for plugging holes, crevices, or the like

Definitions

  • compositions and methods for treating subterranean formations in particular, compositions and methods for cementing and completing wells in which the set cement may be exposed to carbon dioxide or sulfates.
  • the tubular body may comprise drillpipe, casing, liner, coiled tubing or combinations thereof.
  • the purpose of the tubular body is to act as a conduit through which desirable fluids from the well may travel and be collected.
  • the tubular body is normally secured in the well by a cement sheath.
  • the cement sheath provides mechanical support and hydraulic isolation between the zones or layers that the well penetrates. The latter function is important because it prevents hydraulic communication between zones that may result in contamination. For example, the cement sheath blocks fluids from oil or gas zones from entering the water table and polluting drinking water.
  • the cement sheath achieves hydraulic isolation because of its low permeability.
  • intimate bonding between the cement sheath and both the tubular body and borehole is necessary to prevent leaks.
  • the cement sheath can deteriorate and become permeable.
  • the bonding between the cement sheath and the tubular body or borehole may become compromised. Principal causes of deterioration and debonding include physical stresses associated with tectonic movements, temperature changes and chemical deterioration of the cement.
  • cement-sheath deterioration There have been several proposals to deal with the problems of cement-sheath deterioration.
  • One approach is to design the cement sheath to mechanically survive physical stresses that may be encountered during its lifetime.
  • Another approach is to employ additives that improve the physical properties of the set cement.
  • Amorphous metal fibers may be added to cements to improve the strength and impact resistance.
  • Addition of flexible materials may confer a degree of flexibility to the cement sheath.
  • Cement compositions may also be formulated to be less sensitive to temperature fluctuations during the setting process.
  • self-healing cement systems have been developed that are tailored to the mixing, pumping and curing conditions associated with cementing subterranean wells.
  • superabsorbent polymers may be added and may be encapsulated. If the permeability of the cement matrix rises, or the bonding between the cement sheath and the tubular body or borehole wall is disrupted, the superabsorbent polymer becomes exposed to formation fluids. Most formation fluids contain some water, and the polymer swells upon water contact. The swelling fills voids in the cement sheath, restoring the low cement-matrix permeability.
  • the polymer will swell and restore isolation. Rubber particles that swell when exposed to liquid hydrocarbons may also be incorporated in cements. Like the superabsorbent polymers, the swelling of the rubber particles restores and maintains zonal isolation.
  • Carbon sequestration is a geo-engineering technique for the long-term storage of carbon dioxide or other forms of carbon, for various purposes such as the mitigation of "global warming".
  • Carbon dioxide may be captured as a pure byproduct in processes related to petroleum refining or from the flue gases from power plants that employ fossil fuels. The gas is then usually injected into subsurface saline aquifers or depleted oil and gas reservoirs.
  • One of the challenges is to trap the carbon dioxide and prevent leakage back to the surface; maintaining a competent and impermeable cement sheath is a critical requirement.
  • the present disclosure describes improvements by providing cement systems that are resistant to carbon dioxide and sulfate waters encountered in a subterranean well.
  • compositions comprising water, a hydraulic cement and a silicate.
  • the silicate is encapsulated by a coating that isolates the silicate from the water and cement.
  • the encapsulated silicate is in the form of particles.
  • embodiments relate to methods for maintaining zonal isolation in a subterranean well having a borehole wall, at least one tubular body and a cement sheath occupying an annular space between the tubular body and the borehole wall.
  • a well cementing composition is prepared that comprises water, a hydraulic cement and a silicate.
  • the silicate is encapsulated by a coating that isolates the silicate from the water and cement.
  • the encapsulated silicate is in the form of particles.
  • the composition is placed in the annular space, then allowed to set and establish zonal isolation. Should zonal isolation become compromised, the coating is allowed to deteriorate, thereby releasing the silicate.
  • the silicate is allowed to react with calcium hydroxide in the set composition, thereby forming calcium silicate hydrate and reestablishing zonal isolation.
  • a concentration range listed or described as being useful, suitable, or the like is intended that any and every concentration within the range, including the end points, is to be considered as having been stated.
  • a range of from 1 to 10 is to be read as indicating each and every possible number along the continuum between about 1 and about 10.
  • Crystalline calcium hydroxide Ca(OH) 2 reacts with carbonic acid to form calcium carbonate, CaC0 3 .
  • the C-S-H gel also reacts to produce amorphous silica gel.
  • Sulfate attack is also a common form of cement deterioration. This attack occurs when cement is in contact with water containing S0 4 .
  • the attack is due to two principal reactions: the reaction of sodium sulfate (Na 2 S0 4 ) or magnesium sulfate (MgS0 4 ) with calcium hydroxide Ca(OH) 2 to form gypsum (Eqs. 5 and 6) and the reaction of the formed gypsum with calcium aluminate hydrates to form ettringite (Eq. 7).
  • Expansion due to ettringite formation causes tensile stresses to develop in the cement. If these stresses become greater than the cement tensile strength, the cement can crack. This failure by expansion is often observed in the civil engineering applications.
  • compositions and methods by which the calcium hydroxide content in set cement may be reduced before attack by C0 2 or S0 4 , but after the cement has set.
  • aqueous sodium silicate Na 2 Si0 3
  • Ca(OH) 2 is available for attack; moreover, formation of C-S-H is a beneficial result as C-S-H gel is a binding material natural to concrete.
  • the silicate may be encapsulated.
  • the capsules may be added during the preparation of the cement slurry, promoting even dispersion throughout the slurry.
  • An advantage of having the reaction occur after the curing of the cement is that the reactive material will be used only for the purpose of calcium hydroxide consumption.
  • C-S-H gel comprises roughly 65 wt% of fully hydrated Portland cement.
  • concentration of Ca(OH) 2 usually varies between 15 wt% and 20 wt%.
  • the silicate concentration may also be between 2.0 moles and 2.7 moles of set cement to achieve full consumption Ca(OH) 2 .
  • Other hydraulic cement blends of the disclosure represent a wider range of Ca(OH)2 concentrations.
  • the silicate concentration may be between 0.5 and 3.0 moles per kg of hydraulic cement, or between 2.0 and 2.7 moles per kg of hydraulic cement.
  • compositions comprising water, a hydraulic cement and a silicate.
  • the silicate is encapsulated by a coating that isolates the silicate from the water and cement.
  • the encapsulated silicate is in the form of particles.
  • embodiments relate to methods for maintaining zonal isolation in a subterranean well having a borehole wall, at least one tubular body and a cement sheath occupying an annular space between the tubular body and the borehole wall.
  • a well cementing composition is prepared that comprises water, a hydraulic cement and a silicate.
  • the silicate is encapsulated by a coating that isolates the silicate from the water and cement.
  • the encapsulated silicate is in the form of particles.
  • the composition is placed in the annular space, then allowed to set and establish zonal isolation. Should zonal isolation become compromised, the coating is allowed to deteriorate, thereby releasing the silicate.
  • the silicate is allowed to react with calcium hydroxide in the set composition, thereby forming calcium silicate hydrate and reestablishing zonal isolation.
  • Zonal isolation may be compromised by fracturing of the cement sheath, exposure to carbon dioxide, or exposure to sulfates or combinations thereof. Coating deterioration may result from mechanical stress, exposure to heat, dissolution, swelling or degradation or combinations thereof.
  • the hydraulic cement may comprise portland cement, lime-silica blends, lime-fly ash blends, lime-blast furnace slag blends or zeolites or combinations thereof.
  • the silicate may comprise one or more alkali silicates, one or more alkaline-earth silicates or methyl silicate or combinations thereof.
  • the coating may comprise an epoxy resin, a phenolic resin, a furan resin, a cellulosic polymer, polyvinylidene chloride, poly(methyl methacrylate), polylactic acid, polyglycolic acid, polyvinylalcohol, urea-formaldehyde polymers, silicones, gelatins, lipids, styrene acrylic resins, or waxes or combinations thereof.
  • the encapsulated particles may have diameters between 1 micron and 1000 microns.
  • compositions may further comprise accelerators, retarders, extenders, weighting agents, dispersants, fluid-loss control agents, lost- circulation control agents, antifoam agents, gas-generating agents or fibers or combinations thereof.
  • the viscosity of the composition during placement in the well may be lower than 1000 cP at a shear rate of 100 s -1 .

Abstract

Cement compositions comprise water, a hydraulic cement and an encapsulated silicate. The silicate may be released from the capsules by exposure to mechanical stress, heat, dissolution, swelling or coating degradation. Upon release, the silicate reacts with calcium hydroxide in the cement matrix to form calcium silicate hydrate. The consumption of calcium hydroxide renders the set cement more resistant to deterioration upon exposure to carbon dioxide, sulfates or both.

Description

COMPOSITIONS AND METHODS FOR WELL COMPLETIONS BACKGROUND
[0001] The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
[0002] This disclosure relates to compositions and methods for treating subterranean formations, in particular, compositions and methods for cementing and completing wells in which the set cement may be exposed to carbon dioxide or sulfates.
[0003] During the construction of subterranean wells, it is common, during and after drilling, to place a tubular body in the wellbore. The tubular body may comprise drillpipe, casing, liner, coiled tubing or combinations thereof. The purpose of the tubular body is to act as a conduit through which desirable fluids from the well may travel and be collected. The tubular body is normally secured in the well by a cement sheath. The cement sheath provides mechanical support and hydraulic isolation between the zones or layers that the well penetrates. The latter function is important because it prevents hydraulic communication between zones that may result in contamination. For example, the cement sheath blocks fluids from oil or gas zones from entering the water table and polluting drinking water. In addition, to optimize a well's production efficiency, it may be desirable to isolate, for example, a gas-producing zone from an oil-producing zone.
[0004] The cement sheath achieves hydraulic isolation because of its low permeability. In addition, intimate bonding between the cement sheath and both the tubular body and borehole is necessary to prevent leaks. However, over time the cement sheath can deteriorate and become permeable. Alternatively, the bonding between the cement sheath and the tubular body or borehole may become compromised. Principal causes of deterioration and debonding include physical stresses associated with tectonic movements, temperature changes and chemical deterioration of the cement.
[0005] There have been several proposals to deal with the problems of cement-sheath deterioration. One approach is to design the cement sheath to mechanically survive physical stresses that may be encountered during its lifetime. Another approach is to employ additives that improve the physical properties of the set cement. Amorphous metal fibers may be added to cements to improve the strength and impact resistance. Addition of flexible materials (rubber or polymers) may confer a degree of flexibility to the cement sheath. Cement compositions may also be formulated to be less sensitive to temperature fluctuations during the setting process.
[0006] A number of proposals have been made concerning "self-healing" concretes in the construction industry. The concept involves the release of chemicals inside the set-concrete matrix. The release is triggered by matrix disruption arising from mechanical or chemical stresses. The chemicals are designed to restore and maintain the concrete -matrix integrity. This concept is described in the following publication: Dry, CM: "Three designs for the internal release of sealants, adhesives and waterproofing chemicals into concrete to reduce permeability." Cement and Concrete Research 30 (2000) 1969-1977. None of these concepts are immediately applicable to well-cementing operations because of the need for the cement slurry to be pumpable during placement, and because of the temperature and pressure conditions associated with subterranean wells.
[0007] More recently, self-healing cement systems have been developed that are tailored to the mixing, pumping and curing conditions associated with cementing subterranean wells. For example, superabsorbent polymers may be added and may be encapsulated. If the permeability of the cement matrix rises, or the bonding between the cement sheath and the tubular body or borehole wall is disrupted, the superabsorbent polymer becomes exposed to formation fluids. Most formation fluids contain some water, and the polymer swells upon water contact. The swelling fills voids in the cement sheath, restoring the low cement-matrix permeability. Likewise, should the cement/tubular body or cement/borehole wall bonds become disrupted, the polymer will swell and restore isolation. Rubber particles that swell when exposed to liquid hydrocarbons may also be incorporated in cements. Like the superabsorbent polymers, the swelling of the rubber particles restores and maintains zonal isolation.
[0008] Detailed information concerning the performance of self-healing cements in the oilfield may be found in the following publications: Le Roy-Delage S et al.: "Self-Healing Cement System— A Step Forward in Reducing Long-Term Environmental Impact," paper SPE 128226 (2010); Bouras H et al.: "Responsive Cementing Material Prevents Annular Leaks in Gas Wells," paper SPE 116757 (2008); Roth J et al.: "Innovative Hydraulic Isolation Material Preserves Well Integrity," paper SPE 112715 (2008); Cavanagh P et al: "Self-Healing Cement— Novel Technology to Achieve Leak-Free Wells," paper SPE 105781 (2007).
[0009] The aforementioned technologies and publications are mainly concerned with traditional hydrocarbon producing wells. However, the well-cementing industry also has to contend with wells into which carbon dioxide is injected, in which carbon dioxide is stored or from which carbon dioxide is recovered. Carbon dioxide injection is a well-known enhanced oil recovery (EOR) technique. In addition, there are some oil and gas wells whose reservoirs naturally contain carbon dioxide. Subterreanean waters containing sulfates may also be deleterious to cement sheath integrity.
[0010] A relatively new category of wells involving carbon dioxide is associated with carbon-sequestration projects. Carbon sequestration is a geo-engineering technique for the long-term storage of carbon dioxide or other forms of carbon, for various purposes such as the mitigation of "global warming". Carbon dioxide may be captured as a pure byproduct in processes related to petroleum refining or from the flue gases from power plants that employ fossil fuels. The gas is then usually injected into subsurface saline aquifers or depleted oil and gas reservoirs. One of the challenges is to trap the carbon dioxide and prevent leakage back to the surface; maintaining a competent and impermeable cement sheath is a critical requirement.
SUMMARY
[0011] The present disclosure describes improvements by providing cement systems that are resistant to carbon dioxide and sulfate waters encountered in a subterranean well.
[0012] In an aspect, embodiments relate to compositions comprising water, a hydraulic cement and a silicate. The silicate is encapsulated by a coating that isolates the silicate from the water and cement. The encapsulated silicate is in the form of particles.
[0013] In a further aspect, embodiments relate to methods for maintaining zonal isolation in a subterranean well having a borehole wall, at least one tubular body and a cement sheath occupying an annular space between the tubular body and the borehole wall. A well cementing composition is prepared that comprises water, a hydraulic cement and a silicate. The silicate is encapsulated by a coating that isolates the silicate from the water and cement. The encapsulated silicate is in the form of particles. The composition is placed in the annular space, then allowed to set and establish zonal isolation. Should zonal isolation become compromised, the coating is allowed to deteriorate, thereby releasing the silicate. The silicate is allowed to react with calcium hydroxide in the set composition, thereby forming calcium silicate hydrate and reestablishing zonal isolation.
DETAILED DESCRIPTION
[0014] At the outset, it should be noted that in the development of any such actual embodiment, numerous implementation— specific decisions must be made to achieve the developer's specific goals, such as compliance with system related and business related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time consuming but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. In addition, the composition used/disclosed herein can also comprise some components other than those cited. In the summary and this detailed description, each numerical value should be read once as modified by the term "about" (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the summary and this detailed description, it should be understood that a concentration range listed or described as being useful, suitable, or the like, is intended that any and every concentration within the range, including the end points, is to be considered as having been stated. For example, "a range of from 1 to 10" is to be read as indicating each and every possible number along the continuum between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific, it is to be understood that Applicants appreciate and understand that any and all data points within the range are to be considered to have been specified, and that inventors possessed knowledge of the entire range and all points within the range.
[0015] In an environment rich in carbon dioxide, the cement sheath protecting the casing could be subject to carbonation. Carbonation is the attack of the calcium hydroxide in set hydraulic cements. Reaction of hydrated Portland cement with C02 can be summarized as a reaction with calcium hydroxide to produce calcium carbonate, and the decalcification of the C-S-H gel to form calcium carbonate and an amorphous silica gel. The first step is the dissolution of C02 forming carbonic acid, H2C03, in the presence of water. If the C02 is in gaseous or supercritical state then solvation occurs within the cement, which is followed by a hydration step. Only a small proportion of the dissolved C02 will form carbonic acid and the capacity of water to dissolve C02 increases with pressure and decreases with temperature. The following describes the dissolution of C02 and the formation of carbonic acid.
C02 (g)— C02 (aq) (1)
C02 (aq) + H20 (aq)— H2C03 (aq) (2)
[0016] Crystalline calcium hydroxide Ca(OH)2 reacts with carbonic acid to form calcium carbonate, CaC03. The C-S-H gel also reacts to produce amorphous silica gel. Ca(OH)2 (s) + H2C03 (aq)→ CaC03 (s) + H20 (aq) (3)
C-S-H + H+ + HC03 (aq)→ CaC03 (s) + Si02 (am) (4)
[0017] Sulfate attack is also a common form of cement deterioration. This attack occurs when cement is in contact with water containing S04. The attack is due to two principal reactions: the reaction of sodium sulfate (Na2S04) or magnesium sulfate (MgS04) with calcium hydroxide Ca(OH)2 to form gypsum (Eqs. 5 and 6) and the reaction of the formed gypsum with calcium aluminate hydrates to form ettringite (Eq. 7). Expansion due to ettringite formation causes tensile stresses to develop in the cement. If these stresses become greater than the cement tensile strength, the cement can crack. This failure by expansion is often observed in the civil engineering applications.
Na2S04 + Ca(OH)2 + 2 H20 = CaS04.»2 H20 + 2 NaOH
MgS04 + Ca(OH)2 + 2 H20 = CaS04.»2 H20 + Mg(OH)2
3CaOAl203'12H20 + 3(CaS04.»2H20) + 13H20 =
3CaOAl203'3CaS(V31H20
[0018] One of the most common ways of protecting cement against sulfate attack is to reduce the alumina content by limiting the C3A in Portland cement. The addition of fly ash or blast furnace slag is the most common practice. The additives induce the consumption of calcium hydroxide to form additional C-S-H gel, therefore the reduction of Ca(OH)2 content increases the cement's resistance to carbon dioxide and sulfates.
[0019] This disclosure proposes compositions and methods by which the calcium hydroxide content in set cement may be reduced before attack by C02 or S04, but after the cement has set. For example, aqueous sodium silicate (Na2Si03) may react with calcium hydroxide to produce calcium silicate hydrate (C-S-H) (Eq. 8). Once this reaction is completed, less Ca(OH)2 is available for attack; moreover, formation of C-S-H is a beneficial result as C-S-H gel is a binding material natural to concrete.
Na20 · Si02 + Ca(OH)2→ x(CaO · Si02 H20 + Na20 (8)
[0020] The silicate may be encapsulated. The capsules may be added during the preparation of the cement slurry, promoting even dispersion throughout the slurry. An advantage of having the reaction occur after the curing of the cement is that the reactive material will be used only for the purpose of calcium hydroxide consumption.
[0021] For example, C-S-H gel comprises roughly 65 wt% of fully hydrated Portland cement. By contrast the concentration of Ca(OH)2 usually varies between 15 wt% and 20 wt%. Thus, there may be between 2.0 moles and 2.7 moles of Ca(OH)2 per kg of set portland cement. From Eq. 8, it follows that the silicate concentration may also be between 2.0 moles and 2.7 moles of set cement to achieve full consumption Ca(OH)2. Other hydraulic cement blends of the disclosure represent a wider range of Ca(OH)2 concentrations. Thus, the silicate concentration may be between 0.5 and 3.0 moles per kg of hydraulic cement, or between 2.0 and 2.7 moles per kg of hydraulic cement.
[0022] After placement and setting of the cement, several triggers may induce release of the silicate from the capsules, including mechanical stress, exposure to heat, dissolution, swelling or degradation or combinations thereof. Degradation may occur in the form of chemical processes such as hydrolysis.
[0023] In an aspect, embodiments relate to compositions comprising water, a hydraulic cement and a silicate. The silicate is encapsulated by a coating that isolates the silicate from the water and cement. The encapsulated silicate is in the form of particles.
[0024] In a further aspect, embodiments relate to methods for maintaining zonal isolation in a subterranean well having a borehole wall, at least one tubular body and a cement sheath occupying an annular space between the tubular body and the borehole wall. A well cementing composition is prepared that comprises water, a hydraulic cement and a silicate. The silicate is encapsulated by a coating that isolates the silicate from the water and cement. The encapsulated silicate is in the form of particles. The composition is placed in the annular space, then allowed to set and establish zonal isolation. Should zonal isolation become compromised, the coating is allowed to deteriorate, thereby releasing the silicate. The silicate is allowed to react with calcium hydroxide in the set composition, thereby forming calcium silicate hydrate and reestablishing zonal isolation.
[0025] Zonal isolation may be compromised by fracturing of the cement sheath, exposure to carbon dioxide, or exposure to sulfates or combinations thereof. Coating deterioration may result from mechanical stress, exposure to heat, dissolution, swelling or degradation or combinations thereof.
[0026] For both aspects, the hydraulic cement may comprise portland cement, lime-silica blends, lime-fly ash blends, lime-blast furnace slag blends or zeolites or combinations thereof. The silicate may comprise one or more alkali silicates, one or more alkaline-earth silicates or methyl silicate or combinations thereof.
[0027] For both aspects, the coating may comprise an epoxy resin, a phenolic resin, a furan resin, a cellulosic polymer, polyvinylidene chloride, poly(methyl methacrylate), polylactic acid, polyglycolic acid, polyvinylalcohol, urea-formaldehyde polymers, silicones, gelatins, lipids, styrene acrylic resins, or waxes or combinations thereof. The encapsulated particles may have diameters between 1 micron and 1000 microns.
[0028] For both aspects, the compositions may further comprise accelerators, retarders, extenders, weighting agents, dispersants, fluid-loss control agents, lost- circulation control agents, antifoam agents, gas-generating agents or fibers or combinations thereof.
[0029] For both aspects, the viscosity of the composition during placement in the well may be lower than 1000 cP at a shear rate of 100 s-1.

Claims

A well cementing composition, comprising:
(i) water;
(ii) a hydraulic cement; and
(iii) a silicate, the silicate being encapsulated by a coating that isolates the silicate from the water and the hydraulic cement, thereby forming particles.
The composition of claim 1, wherein the hydraulic cement comprises portland cement, lime-silica blends, lime-fly ash blends, lime -blast furnace slag blends or zeolites or combinations thereof.
The composition of claim 1 or 2, wherein the coating comprises an epoxy resin, a phenolic resin, a furan resin, a cellulosic polymer, polyvinylidene chloride, poly(methyl methacrylate), polylactic acid, polyglycolic acid, polyvinylalcohol, urea-formaldehyde polymers, silicones, gelatins, lipids, styrene acrylic resins, or waxes or combinations thereof.
The composition of any one of claims 1-3, wherein the silicate comprises one of more alkali silicates, one or more alkaline-earth silicates or methyl silicate or combinations thereof.
The composition of any one of claims 1-4, wherein the composition further comprises accelerators, retarders, extenders, weighting agents, dispersants, fluid- loss control agents, lost-circulation control agents, antifoam agents, gas-generating agents or fibers or combinations thereof.
The composition of any one of claims 1-5, wherein the particles have diameters between 1 micron and 1000 microns.
The composition of any one of claims 1-6, wherein the silicate is present at a concentration between 0.5 and 3.0 moles per kg of hydraulic cement.
A method for maintaining zonal isolation in a subterranean well having a borehole wall, at least one tubular body and a cement sheath occupying an annular space between the tubular body and the borehole wall, comprising:
(i) preparing a well cementing composition comprising water, a hydraulic cement and a silicate, the silicate being encapsulated by a coating that isolates the silicate from the water and the hydraulic cement, thereby forming particles;
(ii) placing the composition in the annular space;
(iii) allowing the composition to set and establish zonal isolation;
(iv) allowing the coating to deteriorate, thereby releasing the silicate; and
(v) allowing the silicate to react with calcium hydroxide in the set composition, thereby forming calcium silicate hydrate.
9. The method of claim 8, wherein the coating deterioration results from mechanical stress, exposure to heat, dissolution, swelling or degradation or combinations thereof.
10. The method of claim 8 or 9, wherein the hydraulic cement comprises portland cement, lime-silica blends, lime-fly ash blends, lime -blast furnace slag blends or zeolites or combinations thereof.
11. The method of any one of claims 8-10, wherein the coating comprises an epoxy resin, a phenolic resin, a furan resin, a cellulosic polymer, polyvinylidene chloride, poly(methyl methacrylate), polylactic acid, polyglycolic acid, polyvinylalcohol, urea-formaldehyde polymers, silicones, gelatins, lipids, styrene acrylic resins, or waxes or combinations thereof.
12. The method of any one of claims 8-11, wherein the silicate comprises one or more alkali silicates, one or more alkaline-earth silicates or methyl silicate or combinations thereof.
13. The method of any one of claims 8-12, wherein the composition further comprises accelerators, retarders, extenders, weighting agents, dispersants, fluid-loss control agents, lost-circulation control agents, antifoam agents, gas-generating agents or fibers or combinations thereof.
14. The method of any one of claims 8-13, wherein the particles have diameters between 1 micron and 1000 microns.
15. The method of any one of claims 8-14, wherein the silicate is present at a concentration between 0.5 and 3.0 moles per kg of hydraulic cement.
PCT/US2014/032310 2014-03-31 2014-03-31 Compositions and methods for well completions WO2015152860A1 (en)

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CN113811518A (en) * 2019-04-02 2021-12-17 含氧低碳投资有限责任公司 Method relating to cement using carbon dioxide as reactant

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