CA2788620C - Use of csh suspensions in well cementing - Google Patents
Use of csh suspensions in well cementing Download PDFInfo
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- CA2788620C CA2788620C CA2788620A CA2788620A CA2788620C CA 2788620 C CA2788620 C CA 2788620C CA 2788620 A CA2788620 A CA 2788620A CA 2788620 A CA2788620 A CA 2788620A CA 2788620 C CA2788620 C CA 2788620C
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- comb polymer
- water
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- cement slurry
- setting
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- 239000000725 suspension Substances 0.000 title claims description 8
- 239000004568 cement Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000378 calcium silicate Substances 0.000 claims abstract description 14
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 14
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002480 mineral oil Substances 0.000 claims abstract description 7
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 7
- 230000003068 static effect Effects 0.000 claims abstract description 7
- 239000003345 natural gas Substances 0.000 claims abstract description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000002343 natural gas well Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011398 Portland cement Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000004058 oil shale Substances 0.000 claims description 3
- -1 silicate compound Chemical class 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 229940043430 calcium compound Drugs 0.000 claims description 2
- 150000001674 calcium compounds Chemical class 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 238000005227 gel permeation chromatography Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000008239 natural water Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 23
- 239000003129 oil well Substances 0.000 claims 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000008030 superplasticizer Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 235000011148 calcium chloride Nutrition 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The use of a setting accelerator composition for inorganic binders which comprises at least one water-soluble comb polymer suitable as a superplasticizer for hydraulic binders and calcium silicate hydrate particles in the development, exploitation and completion of underground mineral oil and natural gas deposits and in deep wells is proposed. The use according to the invention not only accelerates the setting and hardening of the cement slurries but also shortens the time in which the static gel strength of the hardening cement slurries increases from 100 lb/100 ft2 (4.88 kg/m2) to 500 lb/100 ft2 (24.4 kg/m2).
Description
Use of CSH suspensions in well cementing The present invention relates to the use of CSH suspensions in the development, exploitation and completion of underground mineral oil and natural gas deposits and in deep wells.
Underground mineral oil, natural gas and water deposits are often under high pressure.
Drilling in such formations requires that the pressure of the circulating well fluid be sufficiently high to counteract effectively the pressure of the underground formations and thus prevent the uncontrolled emergence of the formation fluids into the well.
As a rule, wells are lined section by section with steel pipes. The annular gap between the well casings and the underground formations is then filled with cement.
This can be effected by forcing a cement slurry directly into the annular gap or through the well casing into the well in order then to flow backwards into this annular gap as a result of the pressure applied. The hardened cement firstly prevents formation fluids from emerging in an uncontrolled manner into the well and secondly prevents formation fluids from penetrating unhindered into other formations.
The temperature conditions of the deposits vary considerably. The temperatures in surface-near areas of permafrost regions, such as, for example, Alaska, Canada and Siberia, and in offshore wells at high latitudes may be below freezing point and may be up to 400 C in the case of geothermal wells. For this reason, the setting behavior of the cement slurries used must always be adapted to the prevailing conditions.
While retardants are generally required at elevated temperatures, setting accelerators often have to be used at low temperatures. Moreover, the use of superplasticizers and/or fluid loss additives known per se in the prior art in the cement slurries used can lead to a prolongation of the setting times, which likewise necessitates the use of accelerators.
According to Erik B. Nelson, Well Cementing, Schlumberger Educational Services, Sugar Land, Texas, 1990, chapter 3-3, calcium chloride is without a doubt the most frequently used, most effective and most economical setting accelerator for Portland cements. The CaCl2 is as a rule used in concentrations of 2-4% bwoc (% by weight, based on the cement fraction). Unfortunately, the results are unforeseeable at concentrations above 6% bwoc, and premature setting reactions may occur. In addition, there is a risk of corrosion of the casing string by the chloride ions.
The object of the present invention was therefore substantially to avoid the
Underground mineral oil, natural gas and water deposits are often under high pressure.
Drilling in such formations requires that the pressure of the circulating well fluid be sufficiently high to counteract effectively the pressure of the underground formations and thus prevent the uncontrolled emergence of the formation fluids into the well.
As a rule, wells are lined section by section with steel pipes. The annular gap between the well casings and the underground formations is then filled with cement.
This can be effected by forcing a cement slurry directly into the annular gap or through the well casing into the well in order then to flow backwards into this annular gap as a result of the pressure applied. The hardened cement firstly prevents formation fluids from emerging in an uncontrolled manner into the well and secondly prevents formation fluids from penetrating unhindered into other formations.
The temperature conditions of the deposits vary considerably. The temperatures in surface-near areas of permafrost regions, such as, for example, Alaska, Canada and Siberia, and in offshore wells at high latitudes may be below freezing point and may be up to 400 C in the case of geothermal wells. For this reason, the setting behavior of the cement slurries used must always be adapted to the prevailing conditions.
While retardants are generally required at elevated temperatures, setting accelerators often have to be used at low temperatures. Moreover, the use of superplasticizers and/or fluid loss additives known per se in the prior art in the cement slurries used can lead to a prolongation of the setting times, which likewise necessitates the use of accelerators.
According to Erik B. Nelson, Well Cementing, Schlumberger Educational Services, Sugar Land, Texas, 1990, chapter 3-3, calcium chloride is without a doubt the most frequently used, most effective and most economical setting accelerator for Portland cements. The CaCl2 is as a rule used in concentrations of 2-4% bwoc (% by weight, based on the cement fraction). Unfortunately, the results are unforeseeable at concentrations above 6% bwoc, and premature setting reactions may occur. In addition, there is a risk of corrosion of the casing string by the chloride ions.
The object of the present invention was therefore substantially to avoid the
2 disadvantages associated with the prior art. In particular, there was a need for alternative accelerators which do not have the above disadvantages.
This object was achieved by the features of claim 1. The dependent claims relate to preferred embodiments.
WO 2010/026155 Al describes curing accelerator compositions which, in addition to a water-soluble comb polymer suitable as a superplasticizer for hydraulic binders, also comprise calcium silicate hydrate particles of suitable size (see for example claims 40 to 52 of the WO specification).
It has now surprisingly been found that such compositions can also be used as setting accelerator compositions for inorganic binders in the development, exploitation and completion of underground mineral oil and natural gas deposits and in deep wells.
The present invention accordingly relates to the use of a setting accelerator composition for inorganic binders which comprises at least one water-soluble comb polymer suitable as a superplasticizer for hydraulic binders and calcium silicate hydrate particles in the development, exploitation and completion of underground mineral oil and natural gas deposits and in deep wells.
The setting accelerator composition is used here either as a suspension, preferably as an aqueous suspension, or in powder form.
The comb polymer is preferably a copolymer which has side chains comprising polyether functions as well as acid functions, which are present on a main chain. It is obtainable, for example, by free radical copolymerization of acid monomers and polyether macromonomers, the copolymer as a whole comprising at least 45 mol%, preferably at least 80 mol%, of structural units derived from the acid monomers and/or the polyether macromonomers.
The comb polymer preferably comprises structural units derived from (meth)acrylic acid, maleic acid, polyalkylene glycol vinyl ethers, polyalkylene glycol allyl ethers and/or polyalkylene glycol (meth)acrylates. For a detailed discussion of suitable structural units, reference is made to claims 47 to 49 of WO 2010/026155 Al.
Suitable comb polymers expediently have average molecular weights (Mw) of from 5000 to 200 000 g/mol, preferably from 10 000 to 80 000 g/mol and in particular from 20 000 to 70 000 g/mol, measured by means of gel permeation chromatography.
In addition to said comb polymer, polycondensates, in particular of the type disclosed in claims 28 to 33 and 50 of WO 2010/026155 Al, may also be present.
This object was achieved by the features of claim 1. The dependent claims relate to preferred embodiments.
WO 2010/026155 Al describes curing accelerator compositions which, in addition to a water-soluble comb polymer suitable as a superplasticizer for hydraulic binders, also comprise calcium silicate hydrate particles of suitable size (see for example claims 40 to 52 of the WO specification).
It has now surprisingly been found that such compositions can also be used as setting accelerator compositions for inorganic binders in the development, exploitation and completion of underground mineral oil and natural gas deposits and in deep wells.
The present invention accordingly relates to the use of a setting accelerator composition for inorganic binders which comprises at least one water-soluble comb polymer suitable as a superplasticizer for hydraulic binders and calcium silicate hydrate particles in the development, exploitation and completion of underground mineral oil and natural gas deposits and in deep wells.
The setting accelerator composition is used here either as a suspension, preferably as an aqueous suspension, or in powder form.
The comb polymer is preferably a copolymer which has side chains comprising polyether functions as well as acid functions, which are present on a main chain. It is obtainable, for example, by free radical copolymerization of acid monomers and polyether macromonomers, the copolymer as a whole comprising at least 45 mol%, preferably at least 80 mol%, of structural units derived from the acid monomers and/or the polyether macromonomers.
The comb polymer preferably comprises structural units derived from (meth)acrylic acid, maleic acid, polyalkylene glycol vinyl ethers, polyalkylene glycol allyl ethers and/or polyalkylene glycol (meth)acrylates. For a detailed discussion of suitable structural units, reference is made to claims 47 to 49 of WO 2010/026155 Al.
Suitable comb polymers expediently have average molecular weights (Mw) of from 5000 to 200 000 g/mol, preferably from 10 000 to 80 000 g/mol and in particular from 20 000 to 70 000 g/mol, measured by means of gel permeation chromatography.
In addition to said comb polymer, polycondensates, in particular of the type disclosed in claims 28 to 33 and 50 of WO 2010/026155 Al, may also be present.
3 In the calcium silicate hydrate used, the molar ratio of calcium to silicon is preferably from 0.6 to 2.0, in particular from 1.1 to 1.8. The molar ratio of calcium to water in the calcium silicate hydrate is preferably from 0.6 to 6, particularly preferably from 0.6 to 2.0 and in particular from 0.8 to 2Ø
The calcium silicate hydrate particles used are expediently obtainable by reacting a water-soluble calcium compound with a water-soluble silicate compound, the reaction preferably taking place in the presence of an aqueous solution of the water-soluble comb polymer suitable as a superplasticizer for hydraulic binders. Regarding further details of a suitable preparation process, reference is made to claims 1 to 38 of WO 2010/026155 Al.
Suitable calcium silicate hydrate particles are expediently smaller than 5 pm, preferably smaller than 1 pm, more preferably smaller than 500 nm, particularly preferably smaller than 200 nm and in particular smaller than 100 nm.
Preferably, Portland cements, calcium aluminate cements, gypsum, anhydrite, blast furnace slag, slag sands, fly ashes, silica dust, metakaolin, natural and synthetic pozzolanas and/or calcined oil shale, preferably Portland cements, are suitable as inorganic binders whose setting is accelerated according to the invention.
These binders are expediently used in the form of a cement slurry, the water/cement value preferably being in the range from 0.2 to 1.0, in particular in the range from 0.3 to 0.6.
One field of use which is considered in particular according to the invention is well cementing of mineral oil and natural gas wells, in particular in permafrost regions and in the offshore sector.
Here, the use according to the invention accelerates the setting of the cement slurry. At the same time, the hardening rate of the cement slurry is advantageously increased.
Moreover, the time in which the static gel strength of the hardening cement slurry increases from 100 lb/100 ft2 (4.88 kg/m2) to 500 lb/100 ft2 (24.4 kg/m2) is advantageously shortened. This is advantageous particularly in well cementing since the hardening cement slurry tends to crack in the middle range of gel strength owing to ascending gas bubbles. This range is passed through quickly according to the invention.
The setting accelerator composition is used according to the invention advantageously together with other additives customary in well cementing, in particular superplasticizers, water retention agents and/or rheology-modifying additives.
The calcium silicate hydrate particles used are expediently obtainable by reacting a water-soluble calcium compound with a water-soluble silicate compound, the reaction preferably taking place in the presence of an aqueous solution of the water-soluble comb polymer suitable as a superplasticizer for hydraulic binders. Regarding further details of a suitable preparation process, reference is made to claims 1 to 38 of WO 2010/026155 Al.
Suitable calcium silicate hydrate particles are expediently smaller than 5 pm, preferably smaller than 1 pm, more preferably smaller than 500 nm, particularly preferably smaller than 200 nm and in particular smaller than 100 nm.
Preferably, Portland cements, calcium aluminate cements, gypsum, anhydrite, blast furnace slag, slag sands, fly ashes, silica dust, metakaolin, natural and synthetic pozzolanas and/or calcined oil shale, preferably Portland cements, are suitable as inorganic binders whose setting is accelerated according to the invention.
These binders are expediently used in the form of a cement slurry, the water/cement value preferably being in the range from 0.2 to 1.0, in particular in the range from 0.3 to 0.6.
One field of use which is considered in particular according to the invention is well cementing of mineral oil and natural gas wells, in particular in permafrost regions and in the offshore sector.
Here, the use according to the invention accelerates the setting of the cement slurry. At the same time, the hardening rate of the cement slurry is advantageously increased.
Moreover, the time in which the static gel strength of the hardening cement slurry increases from 100 lb/100 ft2 (4.88 kg/m2) to 500 lb/100 ft2 (24.4 kg/m2) is advantageously shortened. This is advantageous particularly in well cementing since the hardening cement slurry tends to crack in the middle range of gel strength owing to ascending gas bubbles. This range is passed through quickly according to the invention.
The setting accelerator composition is used according to the invention advantageously together with other additives customary in well cementing, in particular superplasticizers, water retention agents and/or rheology-modifying additives.
4 The present invention will now be explained in more detail an the basis of the following working example with reference to fig. 1. Here:
Fig. 1 shows the increase in the compressive strengths of different cement slurries as a function of time.
Use example 1 The preparation of the cement slurries was effected according to API
specification 10, section 5 and appendix A. For this purpose:
700 g of cement (Lafarge, class H) 266g of tap water 3.5 g of Liquiment K3F (superplasticizer, product of BASF Construction Polymers GmbH) 3.5 g of Polytrol FL 34 (fluid loss additive, product of BASF Construction Polymers GmbH) 1.0 g of tributyl phosphate (antifoam) were homogeneously mixed. Either no additives (blank value), 0.80% bwoc of CaCl2 or different amounts of X-Seed 100 (product of BASF Construction Polymers GmbH;
aqueous calcium silicate hydrate suspension, particle size < 100 nm, solids content about 21% by weight, active proportion of calcium silicate hydrate about 7% by weight, comb polymers used: MVA2500 and EPPR312, both according to the present invention, likewise commercial products of BASF) were added to the samples.
The X-Seed 100 was added in an amount of 0.07% bwoc, 0.15% bwoc, 0.30% bwoc and 1.50% bwoc, based in each case on the active proportion of calcium silicate hydrate.
The samples were measured in a static gel strength analyzer (Chandler Engineering) at a temperature of 23 C and a pressure of 1000 psi (about 69 bar). The time in which the static gel strength of the samples increased from 100 lb/100 ft2 (4.88 kg/m2) to 500 lb/100 ft2 (24.4 kg/m2) is stated in table 1 Table 1 Sample Time [min]
Blank value 76.5 0.80% bwoc of CaCl2 44.0 0.07% bwoc of X-Seed 100 52.5 0.15% bwoc of X-Seed 100 38.0 0.30% bwoc of X-Seed 100 13.5 1.50% bwoc of X-Seed 100 15.5 .. 5 In addition, the variation of the compressive strength with time was measured.
The results are shown in graphical form in fig. 1.
It is evident that the calcium silicate hydrate suspension accelerates the increase in the compressive strength to a greater extent at lower dose than CaCl2, at the same time the time in which the static gel strength of the samples passes through the critical range being substantially shortened.
Fig. 1 shows the increase in the compressive strengths of different cement slurries as a function of time.
Use example 1 The preparation of the cement slurries was effected according to API
specification 10, section 5 and appendix A. For this purpose:
700 g of cement (Lafarge, class H) 266g of tap water 3.5 g of Liquiment K3F (superplasticizer, product of BASF Construction Polymers GmbH) 3.5 g of Polytrol FL 34 (fluid loss additive, product of BASF Construction Polymers GmbH) 1.0 g of tributyl phosphate (antifoam) were homogeneously mixed. Either no additives (blank value), 0.80% bwoc of CaCl2 or different amounts of X-Seed 100 (product of BASF Construction Polymers GmbH;
aqueous calcium silicate hydrate suspension, particle size < 100 nm, solids content about 21% by weight, active proportion of calcium silicate hydrate about 7% by weight, comb polymers used: MVA2500 and EPPR312, both according to the present invention, likewise commercial products of BASF) were added to the samples.
The X-Seed 100 was added in an amount of 0.07% bwoc, 0.15% bwoc, 0.30% bwoc and 1.50% bwoc, based in each case on the active proportion of calcium silicate hydrate.
The samples were measured in a static gel strength analyzer (Chandler Engineering) at a temperature of 23 C and a pressure of 1000 psi (about 69 bar). The time in which the static gel strength of the samples increased from 100 lb/100 ft2 (4.88 kg/m2) to 500 lb/100 ft2 (24.4 kg/m2) is stated in table 1 Table 1 Sample Time [min]
Blank value 76.5 0.80% bwoc of CaCl2 44.0 0.07% bwoc of X-Seed 100 52.5 0.15% bwoc of X-Seed 100 38.0 0.30% bwoc of X-Seed 100 13.5 1.50% bwoc of X-Seed 100 15.5 .. 5 In addition, the variation of the compressive strength with time was measured.
The results are shown in graphical form in fig. 1.
It is evident that the calcium silicate hydrate suspension accelerates the increase in the compressive strength to a greater extent at lower dose than CaCl2, at the same time the time in which the static gel strength of the samples passes through the critical range being substantially shortened.
Claims (23)
1. A method for accelerating the setting of a cement slurry comprising adding a sufficient amount of an accelerator composition to a cement slurry;
wherein the cement slurry comprises water and an inorganic binder;
wherein the accelerator composition comprises a water-soluble comb polymer;
and particles consisting of calcium silicate hydrate, wherein said particles are smaller than 5 pm;
wherein the comb polymer has a main chain;
wherein the comb polymer has side chains comprising polyether functions and acid functions;
wherein the side chains are present on the main chain; and wherein the inorganic binder comprises Portland cement.
wherein the cement slurry comprises water and an inorganic binder;
wherein the accelerator composition comprises a water-soluble comb polymer;
and particles consisting of calcium silicate hydrate, wherein said particles are smaller than 5 pm;
wherein the comb polymer has a main chain;
wherein the comb polymer has side chains comprising polyether functions and acid functions;
wherein the side chains are present on the main chain; and wherein the inorganic binder comprises Portland cement.
2. The method of claim 1, wherein the time in which the static gel strength of the hardening cement slurry increases from 4.88 kg/m2to 24.4 kg/m2 is shortened compared to the time in which the static gel strength of an identical hardening cement slurry that does not comprise the accelerator composition increases from 4.88 kg/m2 to 24.4 kg/m2.
3. The method of claim 1, wherein the setting accelerator composition is a suspension.
4. The method of claim 3, wherein the suspension is an aqueous suspension.
5. The method of claim 1, wherein the comb polymer is a copolymer which is obtained by free radical copolymerization of acid monomers and polyether macromonomers, the copolymer as a whole comprising at least 45 mol % of the acid monomer or the polyether macromonomer structural units.
6. The method of claim 1, wherein the comb polymer comprises at least one member selected from the group consisting of (meth)acrylic acid, maleic acid, a polyalkylene glycol vinyl ether, a polyalkylene glycol allyl ether and polyalkylene glycol (meth)acylate structural units.
7. The method of claim 1, wherein the comb polymer has an average molecular weight (Mw) of from 5,000 to 200,000 g/mol as measured by gel permeation chromatography.
8. The method of claim 1, wherein the calcium silicate hydrate has a molar ratio of calcium to silicon of from 0.6 to 2Ø
9. The method of claim 1, wherein the molar ratio of calcium to water in the calcium silicate hydrate is from 0.6 to 6.
10. The method of claim 1, wherein said particles are obtained by reacting a water-soluble calcium compound with a water-soluble silicate compound, wherein the reaction is effected in the presence of an aqueous solution of the water-soluble comb polymer.
11. The method of claim 1, wherein the inorganic binder further comprises at least one member selected from the group consisting of a calcium aluminate cement, anhydrite, blast furnace slag, slag sand, fly ash, silica dust, metakaolin, natural pozzolanas, synthetic pozzolanas and calcined oil shale.
12. The method of claim 1, wherein the inorganic binder further comprises calcined oil shale.
13. The method of claim 1, wherein said particles are smaller than 1 µm.
14. The method of claim 1, wherein the accelerating of the setting of the cement slurry occurs in an underground oil or natural gas well.
15. The method of claim 14, wherein the underground oil or natural gas well is offshore.
16. The method of claim 14, wherein the underground oil or natural gas well is in permafrost region.
17. The method of claim 14, wherein the underground oil or natural gas well is in a permafrost region or is offshore.
18. The method of claim 1, wherein said particles are smaller than 500 nm.
19. The method of claim 1, wherein said particles are smaller than 200 nm.
20. The method of claim 1, wherein said particles are smaller than 100 nm.
21. The method of claim 1, wherein the setting accelerator composition is a powder.
22. The method of claim 1, wherein the comb polymer comprises at least one member selected from the group consisting of a polyalkylene glycol vinyl ether and polyalkylene glycol (meth)acrylate structural units.
23. The method of claim 1, wherein the accelerating of the setting of the cement slurry occurs in an underground mineral oil, natural gas, or water deposit, wherein the deposit is under high pressure and varying temperature conditions.
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PCT/EP2011/051138 WO2011131378A1 (en) | 2010-04-21 | 2011-01-27 | Use of csh suspensions in cementing wells |
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CN (1) | CN102782080B (en) |
BR (1) | BR112012026716A2 (en) |
CA (1) | CA2788620C (en) |
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US8561701B2 (en) * | 2010-12-21 | 2013-10-22 | Halliburton Energy Services, Inc. | Methods for cementing in a subterranean formation using a cement composition containing calcium silicate hydrate seeds |
EP2759337A1 (en) | 2013-01-25 | 2014-07-30 | Basf Se | Additive for hydraulically setting masses |
EP2826827B1 (en) * | 2013-07-18 | 2019-06-12 | Basf Se | CMP composition comprising abrasive particles containing ceria |
PT2878585T (en) | 2013-11-27 | 2017-08-28 | Fundacíon Tecnalia Res & Innovation | Method for the manufacturing of cementitious c-s-h seeds |
US10793471B2 (en) | 2016-03-22 | 2020-10-06 | Sika Technology Ag | Composition based on calcium oxide |
DE102016207858A1 (en) | 2016-05-06 | 2017-11-09 | Baustoffwerke Löbnitz GmbH & Co. KG | insulation |
CN106747130B (en) * | 2016-11-09 | 2019-08-02 | 嘉华特种水泥股份有限公司 | A kind of high temperature resistant oil well sealing agent |
DE102017205822A1 (en) | 2017-04-05 | 2018-10-11 | Baustoffwerke Löbnitz GmbH & Co. KG | Method and device for producing porous mineral building material |
CN107162469B (en) * | 2017-05-26 | 2019-10-25 | 中建商品混凝土有限公司 | A kind of ultra-small grain size micellar solution early strength agent and preparation method thereof |
DE102018212322A1 (en) | 2018-07-24 | 2020-01-30 | Baustoffwerke Löbnitz GmbH & Co. KG | Process for the production of porous mineral building material with improved strength |
RU2710862C1 (en) * | 2019-07-31 | 2020-01-14 | Публичное акционерное общество «Татнефть» имени В.Д. Шашина | Composition for isolating water influx into well |
CN110746551B (en) * | 2019-10-09 | 2022-03-29 | 中国石油天然气股份有限公司 | Copolymer containing double-polyoxyethylene-ether branched chain structure and preparation and application thereof |
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SU1006713A1 (en) * | 1981-05-28 | 1983-03-23 | Московский Ордена Трудового Красного Знамени Институт Нефтехимической И Газовой Промышленности Им.И.М.Губкина | Disperse reinforced plugging mix for well cementing and method for preparing the same |
FR2708592B1 (en) * | 1993-07-29 | 1995-09-29 | Lafarge Coppee | Accelerating and hardening agent for silicic hydraulic binders. |
KR20090012372A (en) * | 2001-03-05 | 2009-02-03 | 제임스 하디 인터내셔널 파이낸스 비.브이. | Low density calcium silicate hydrate strength accelerant additive for cementitious products |
US20030230407A1 (en) * | 2002-06-13 | 2003-12-18 | Vijn Jan Pieter | Cementing subterranean zones using cement compositions containing biodegradable dispersants |
FR2841549B1 (en) * | 2002-06-28 | 2004-08-13 | Rhodia Chimie Sa | PROCESS FOR ACCELERATING THE TAKING OF A COMPOSITION OF HYDRAULIC MINERAL BINDERS ADJUVENTED AS AN ADDITIVE COMPRISING HYDROPHILIC FUNCTIONS, AS WELL AS THE COMPOSITION WHICH CAN BE OBTAINED BY THIS PROCESS AND ITS USE |
CA2490928C (en) * | 2003-12-12 | 2012-06-12 | Brine-Add Fluids Ltd. | Fluid loss additives and methods |
AU2006259585B2 (en) * | 2005-06-14 | 2011-07-14 | United States Gypsum Company | Modifiers for gypsum slurries and method of using them |
US7422061B2 (en) * | 2005-11-07 | 2008-09-09 | Calfrac Well Services Ltd. | Fluid loss additives and methods |
US8096359B2 (en) * | 2006-11-17 | 2012-01-17 | Baker Hughes Incorporated | Method of cementing using polymeric retarder |
AU2009289267B2 (en) | 2008-09-02 | 2014-05-22 | Construction Research & Technology Gmbh | Plasticizer-containing hardening accelerator composition |
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DK2561034T3 (en) | 2019-08-12 |
WO2011131378A1 (en) | 2011-10-27 |
BR112012026716A2 (en) | 2016-07-12 |
RU2012149412A (en) | 2014-05-27 |
EP2561034A1 (en) | 2013-02-27 |
CA2788620A1 (en) | 2011-10-27 |
EP2561034B1 (en) | 2019-05-22 |
CN102782080A (en) | 2012-11-14 |
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