WO2007135442A2 - Composition de ciment - Google Patents

Composition de ciment Download PDF

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Publication number
WO2007135442A2
WO2007135442A2 PCT/GB2007/001933 GB2007001933W WO2007135442A2 WO 2007135442 A2 WO2007135442 A2 WO 2007135442A2 GB 2007001933 W GB2007001933 W GB 2007001933W WO 2007135442 A2 WO2007135442 A2 WO 2007135442A2
Authority
WO
WIPO (PCT)
Prior art keywords
cement
aplite
acid
composition
settable
Prior art date
Application number
PCT/GB2007/001933
Other languages
English (en)
Other versions
WO2007135442A3 (fr
Inventor
Rune GODØY
Hallvar Eide
Arild Saasen
Original Assignee
Statoilhydro Asa
Cockbain, Julian
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Statoilhydro Asa, Cockbain, Julian filed Critical Statoilhydro Asa
Publication of WO2007135442A2 publication Critical patent/WO2007135442A2/fr
Publication of WO2007135442A3 publication Critical patent/WO2007135442A3/fr

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Classifications

    • 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
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/041—Aluminium silicates other than clay
    • 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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • 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
    • 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

Definitions

  • This invention relates to improvements in and relating to cement and concrete, and in particular to cements and concretes which in use may be exposed to an acid environment, e.g. to combustion fumes (for example in tunnels and chimneys), to acid fluids leaching from a material adjacent to or contained by the cement or concrete, or to carbon dioxide being injected underground (for example to enhance hydrocarbon recovery), and to methods of well construction and permanent plugging and abandonment of wells, especially methods of construction and permanent plugging and abandonment of geothermal wells and wells for hydrocarbon extraction.
  • an acid environment e.g. to combustion fumes (for example in tunnels and chimneys)
  • acid fluids leaching from a material adjacent to or contained by the cement or concrete for example to enhance hydrocarbon recovery
  • carbon dioxide being injected underground
  • Cements and concrete are usually set by exposing the cement or concrete mixture to a base (i.e. to a pH above 7). Exposure to an acid environment, before or after setting, can lead to failure to set properly or to cement or concrete corrosion. Thus for example exposure of set Portland cements to carbon dioxide is known to lead to cement corrosion and cement or concrete porosification. The more porous the set cement (or concrete) is, the higher will be the corrosion rate and loss of zonal isolation.
  • cements and concretes are exposed to acid environments, e.g. to oxide gases such as carbon, sulphur and nitrogen oxides or acidic fluids leaching from material adjacent to or contained by the cement or concrete.
  • oxide gases such as carbon, sulphur and nitrogen oxides or acidic fluids leaching from material adjacent to or contained by the cement or concrete.
  • inorganic cements based on aplite and concretes made therewith i.e. cement and aggregate admixtures
  • cement and aggregate admixtures can be set by the use of acids rather than bases and thus offer the prospect of acid resistant cements and concretes.
  • the invention thus provides a settable cement or concrete composition
  • a settable cement or concrete composition comprising: an acid-settable aplite-based cement; at least one of (a) an aqueous acidic solution and (b) an acid in water-soluble form; and optionally an aggregate.
  • the invention provides a method of producing a set cement or concrete comprising exposing an acid-settable aplite-based cement or an admixture thereof with an aggregate to an acidic aqueous solution whereby to set said cement or admixture.
  • the invention provides an element, e.g. a container or building element, comprising an acid-set aplite-based cement or concrete.
  • the invention provides a method of cement coating of a surface comprising applying to said surface a settable cement composition comprising an aplite-based cement and an aqueous acidic solution.
  • the invention provides a method of generating a set cement in a subterranean bore hole, e.g. a water or hydrocarbon well, which method comprises introducing an aqueous, acid-settable aplite-based cement composition into said bore hole and if necessary subsequently introducing an acid in dissolved or water-soluble form.
  • a subterranean bore hole e.g. a water or hydrocarbon well
  • the invention provides an optionally sealed, fluid extraction or introduction well comprising a bore-hole having at at least one depth therein an annular, borehole well-lining comprising a set-cement produced using a pulverulent aplite and optionally carbon fibre containing acid-settable cement composition, e.g. a composition as described herein.
  • the cement compositions used according to the invention may contain aplite as the sole cement base or alternatively they may additionally contain at least one further cement base, preferably an inorganic cement such as Portland cement.
  • the aplite will constitute at least 82% wt. of the total cement content, preferably at least 84% wt., more preferably at least 85% wt., especially at least 90% wt., e.g. at least 95% wt.
  • Cement compositions containing aplite at at least 82% wt. relative to total cement composition are also novel and form a further aspect of the present invention as does their use in the various ways described herein.
  • one preferred use of the invention is in methods of well construction and permanent plugging and abandonment of wells, especially methods of construction and permanent plugging and abandonment of geothermal wells and wells for hydrocarbon extraction.
  • a cylindrical metal tube, the casing or liner is placed in the borehole and the space between the outer wall of the tube and the inner wall of the borehole is filled with cement.
  • fluid e.g. water, gas or oil
  • cement is also used for permanent plugging and abandonment of wells. Down hole cementing is described for example in "Well Cementing" edited by E.B. Nelson, Schlumberger Educational Services, Sugar Land, Texas, USA, 1990.
  • Carbon fibre may be added to the cement or concrete of the invention so as to affect several important properties thereof.
  • the most essential of these properties are those related to the set cement, but also in the fluid state, carbon fibres in the cement may increase the ability of the cement to reduce fluid losses. Fluid loss is often a problem during well cementing operations, since the cement often has a higher density than the drilling fluid it displaces. The carbon fibres might in some cases bridge the small fractures causing the losses, and thus lessen the losses during the pumping operation.
  • the carbon fibres will effect properties such as compressive strength, tensile strength and bond to casing/ formation. Compressive strength is important, but even more important is the increased tensile strength the carbon fibres will give the set cement.
  • Temperature- and pressure-cycling in a well is especially critical, for the set cement, since it causes the casing/tube to expand/contract. This movement of the casing is known to cause the set cement to fail, causing poor zonal isolation along the wellbore. By using carbon fibres together with aplite in a well cement, the most critical mechanical properties can be controlled for optimum zonal isolation.
  • Suitable carbon fibres for use in the invention include those from Devoid AMT AS, N-6030 Langevag, Norway.
  • the carbon fibres are between 0.1 cm and 10.0 cm in length, more preferably between 0.3 cm and 2.5 cm especially preferably between 0.5 cm and 1.0 cm.
  • Preferred fibres have a diameter of between 1 ⁇ m and 15 ⁇ m, preferably between 3 ⁇ m and 10 ⁇ m, more especially between 6 ⁇ m and 8 ⁇ m, particularly 7 ⁇ m.
  • the amount of fibre added per m 3 of cement mix is preferably 0.1 kg to 10 kg, more preferably 0.3 kg to 7 kg, especially preferably 0.5 kg/m 3 to 5 kg/m 3 .
  • well or bore hole means a well for extraction of fluids from below the earth's surface or for the subsurface injection of fluids.
  • wells will be for water or hydrocarbon (e.g. gas or oil) extraction or for injection of water, carbon dioxide or hydrocarbon gas, especially for introduction of carbon dioxide.
  • hydrocarbon e.g. gas or oil
  • compositions are capable of setting (e.g. setting down-hole following its application) either with or without intervention. Intervention in this regard might typically involve addition of an acid, an acid generating catalyst, or a pH modifier following placement of the cement composition. Where the intervention required involves addition of a further material, e.g. an acid or a pH modifier, the compositions are referred to herein as “non-self-settable”.
  • Aplite is a granitoid mineral found for example in Montpelier, Virginia, USA, Owens Valley, California, USA and in Finnvolldalen in Norway as well as in Japan, Russia and Italiany, Italy. Aplite is currently used almost exclusively as a flux in single-fired ceramic tile production. Aplite may be obtained commercially, e.g. from Maffei Natural Resources, Italy and the US Silica Company, West Virginia, USA. Typically aplite contains silicon, magnesium, iron, sodium, aluminium, potassium, titanium and calcium with the major components (expressed as oxide content) being silicon and aluminium, these generally being present at 60- 85% wt. and 10 to 25% wt. respectively.
  • the aplite used according to the present invention is preferably a high silicon content aplite, e.g. with a silicon content (expressed as oxide content) of at least 68% wt., more preferably at least 70% wt., especially at least 75% wt.
  • a silicon content expressed as oxide content
  • the silicon content is expressed as an oxide content as it is standard geological practice to express elemental contents in this fashion.
  • the US Silica Company provides a typical chemical analysis for its aplite (from Montpelier) Of SiO 2 62.0%, Fe 2 O 3 0.18%, Al 2 O 3 21.7%, TiO 2 0.30%, CaO 5.6%, MgO 0.034%, Na 2 O 5.5%, K 2 O 2.9%, P 2 O 5 0.22% and LOI (loss on ignition) 0.1%.
  • the pulverulent aplite used according to the invention preferably has a particle size of less than 250 ⁇ m, more preferably less than 200 ⁇ m, e.g. 1 to 180 ⁇ m, more typically 10 to 150 ⁇ m, e.g. 50 to 100 ⁇ m, especially less than 75 ⁇ m- Particle size in this regard may be measured by screening or using particle size measuring apparatus. Where it is stated that the particle size is less than a certain value, then normally at least 50% volume will be that size or smaller, preferably at least 80% volume. Alternatively particle size may be taken to be mode particle size as measured by a particle size analyser, e.g. a Coulter particle size analyser. Coarse aplite may be transformed into finer grained aplite by conventional rock pulverizing techniques, optionally followed by screening to separate out oversized and/or undersized grains.
  • aplite is a well understood geological term, it should be emphasized herein that other granitoid rocks having the same or similar acid-settable effect, may be used according to the invention in place of materials formally recognised as aplites and that such usage is considered to be according to the invention, although less preferred than the use of materials recognised as aplites.
  • pulverulent silicates e.g. silica, in particular silica flour
  • the weight ratio of non-aplite silicate to aplite will be in the range of 0:100 to 90:10, more particularly 2:98 to 70:30, especially 10:90 to 30:70.
  • compositions herein described comprise an amount of pulverulent material (e.g. pulverulent aplite) having a particle size of less than 15 ⁇ m, preferably less than 10 ⁇ m.
  • pulverulent material e.g. pulverulent aplite
  • the production of such fine material is achieved by grinding coarser particles, preferably by grinding coarse aplite.
  • a further advantage of the cements of the present invention is the very low porosity and/or very low permeability of the resulting set cement compositions. Reduced permeability will reduce the invasion of any fluid or gas and will thus reduce the corrosion of the cement and the transfer of gas or fluid across the cement plug or wall.
  • the water permeability of set Portland cement with slurry density of 1.90 SG is around 0.0010 mD (millidarcies), and increases as density is reduced. If reduced to 1.44 SG the water permeability increases to approximately 0.1380 mD.
  • API Spec.10, section 11.4 describes how these permeability tests are performed and will be familiar to one of skill in the art.
  • aplite-containing cements of the present invention have reduced permeability in comparison with non-aplite containing equivalents.
  • aplite in a Portland cement reduces the permeability over a Portland cement composition of equivalent density. This decreased permeability thereby reduces the invasion of any fluid or gas which will cause cement corrosion and/ or loss of zonal isolation.
  • Aplite content in the cement compositions of the invention is defined as a percentage by dry weight relative to the total cement composition, i.e. excluding other additives such as colorants, antimicrobials, organic polymers, fibres, (e.g. carbon fibres or inorganic fibres such as glass or "rock wool” fibres), etc.
  • additives such as colorants, antimicrobials, organic polymers, fibres, (e.g. carbon fibres or inorganic fibres such as glass or "rock wool” fibres), etc.
  • Such other additives with the exception of additives significantly contributing to the structural (e.g. load-bearing) properties of the set cement, such as silica, will generally contribute no more than 10% wt. dsb to the total cement composition, typically less than 5% wt.
  • the cement composition may, as discussed above, comprise a further cement base, i.e.
  • cement bases such as Portland cement
  • cement bases are well known and require no further description here. Cements are discussed for example in Lea, "The Chemistry of Cement and Concrete", 3rd Edition, Edward Arnold, Old Woking, UK, 1970, and Taylor, “Cement Chemistry”, Academic Press, London, UK, 1990.
  • blast furnace slag may be used as part of the n ⁇ n-aplite cement base.
  • BFS blast furnace slag
  • the cement compositions of the invention may also be used for other cementing applications where acid resistant cement is desired, e.g. for plugging or filling crevices in rock or for the lining of other subterranean volumes such as storage volumes, pipes or tunnels. Such applications are also deemed to form part of the present invention. They may also be used for tunnel or chimney lining or construction or for the manufacture of containers, e.g. waste (in particular radioactive waste) containers, or building elements, e.g. bricks, blocks, tiles, slabs, conduits, channels, etc.
  • containers e.g. waste (in particular radioactive waste) containers
  • building elements e.g. bricks, blocks, tiles, slabs, conduits, channels, etc.
  • cement and concrete compositions of the invention may be applied by procedures and equipment conventional in the art for settable cement and concrete compositions.
  • an aggregate e.g. sand, pebbles or rocks
  • aplite as the aggregate is especially preferred.
  • the acid used in setting the cements and concretes of the invention may be any strong or weak acid, e.g. a mineral acid such as hydrochloric acid or an organic acid such as a carboxylic acid, e.g. citric, malic, acetic, etc. acids.
  • a mineral acid such as hydrochloric acid
  • an organic acid such as a carboxylic acid, e.g. citric, malic, acetic, etc. acids.
  • the cement (or concrete) is formulated as a solid mix using a solid or encapsulated water-soluble acid, e.g. an acid encapsulated in a soluble polymer, for example a biopolymer such as gelatin.
  • a solid or encapsulated water-soluble acid e.g. an acid encapsulated in a soluble polymer, for example a biopolymer such as gelatin.
  • an acid may be applied in fluid form, e.g. as a pure liquid acid or an aqueous solution.
  • the acid may even be applied in gaseous form, e.g. by bubbling it through the cement or concrete composition.
  • the acid will be used at a concentration or in an amount such that the pH of the aqueous phase of the cement or concrete composition is in the range 2 to 6.9, preferably 3 to 6, more preferably 4 to 5.
  • a neutral pH may be used to set high aplite-content cements and concretes and such use is also deemed to fall within the scope of the invention.
  • One particular advantage of the high aplite content elements of the invention is that by selection of the aplite particle size and the aplite content, the temperature reached within the cement during setting may be regulated, e.g. to keep it below 60°C in temperature sensitive environments or end-uses.
  • Example 1 The products and processes of the invention will now be illustrated further with reference to the following non-limiting Examples.
  • Example 1 The products and processes of the invention will now be illustrated further with reference to the following non-limiting Examples.
  • a dry cement composition is prepared by mixing 23.5 parts by weight Class G
  • the mixture is cured under ambient conditions for 2 to 3 hours and then at 40°C for 8 hours.
  • a cement composition was prepared according to Example 1 by adding fresh water to Class G aplite of particle size 10-75 ⁇ m (achieved by crushing and sieving). pH was adjusted to 4-5 using hydrochloric acid and the composition was allowed to set for 24 hours at 15O 0 C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne une composition de ciment ou de béton durcissable comprenant un ciment à base d'aplite durcissable à l'acide, (a) une solution acide aqueuse et/ou (b) un acide sous forme hydrosoluble, et éventuellement un agrégat.
PCT/GB2007/001933 2006-05-24 2007-05-24 Composition de ciment WO2007135442A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0610338A GB2438398A (en) 2006-05-24 2006-05-24 Settable cement or concrete composition
GB0610338.6 2006-05-24

Publications (2)

Publication Number Publication Date
WO2007135442A2 true WO2007135442A2 (fr) 2007-11-29
WO2007135442A3 WO2007135442A3 (fr) 2008-01-31

Family

ID=36687679

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2007/001933 WO2007135442A2 (fr) 2006-05-24 2007-05-24 Composition de ciment

Country Status (2)

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GB (1) GB2438398A (fr)
WO (1) WO2007135442A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110159233A (zh) * 2019-06-10 2019-08-23 中国石油大学(华东) 一种通过人工致密盖层提高天然气水合物藏采收率的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987000828A1 (fr) * 1985-08-08 1987-02-12 Aktieselskabet Aalborg Portland-Cement-Fabrik Article façonne et son procede de fabrication
US6248697B1 (en) * 1997-02-12 2001-06-19 Kb Technologies, Ltd. Composition and method for a dual-function soil-grouting excavating or boring fluid
GB2425531A (en) * 2005-04-26 2006-11-01 Statoil Asa Oil well cement containing aplite
WO2006115415A1 (fr) * 2005-04-26 2006-11-02 Hallvar Eide Element de construction et son procede de fabrication
WO2006118467A1 (fr) * 2005-04-26 2006-11-09 Hallvar Eide Composition cimentaire et beton obtenu a partir d’une telle composition
GB2431639A (en) * 2005-10-14 2007-05-02 Statoil Asa Aplite cement with carbon fibres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987000828A1 (fr) * 1985-08-08 1987-02-12 Aktieselskabet Aalborg Portland-Cement-Fabrik Article façonne et son procede de fabrication
US6248697B1 (en) * 1997-02-12 2001-06-19 Kb Technologies, Ltd. Composition and method for a dual-function soil-grouting excavating or boring fluid
GB2425531A (en) * 2005-04-26 2006-11-01 Statoil Asa Oil well cement containing aplite
WO2006115415A1 (fr) * 2005-04-26 2006-11-02 Hallvar Eide Element de construction et son procede de fabrication
WO2006118467A1 (fr) * 2005-04-26 2006-11-09 Hallvar Eide Composition cimentaire et beton obtenu a partir d’une telle composition
GB2431639A (en) * 2005-10-14 2007-05-02 Statoil Asa Aplite cement with carbon fibres

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110159233A (zh) * 2019-06-10 2019-08-23 中国石油大学(华东) 一种通过人工致密盖层提高天然气水合物藏采收率的方法

Also Published As

Publication number Publication date
WO2007135442A3 (fr) 2008-01-31
GB0610338D0 (en) 2006-07-05
GB2438398A (en) 2007-11-28

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