WO2008145975A1 - Additifs de ciment à base de polysaccharide - Google Patents

Additifs de ciment à base de polysaccharide Download PDF

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Publication number
WO2008145975A1
WO2008145975A1 PCT/GB2008/001774 GB2008001774W WO2008145975A1 WO 2008145975 A1 WO2008145975 A1 WO 2008145975A1 GB 2008001774 W GB2008001774 W GB 2008001774W WO 2008145975 A1 WO2008145975 A1 WO 2008145975A1
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WO
WIPO (PCT)
Prior art keywords
polysaccharide
composition
cement
combinations
gum
Prior art date
Application number
PCT/GB2008/001774
Other languages
English (en)
Inventor
Bairreddy Raghava Reddy
Anindya Ghosh
Russell M. Fitzgerald
Original Assignee
Halliburton Energy Services, Inc
Curtis, Philip, Anthony
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
Priority claimed from US11/755,270 external-priority patent/US8569214B2/en
Priority claimed from US11/755,271 external-priority patent/US8586508B2/en
Application filed by Halliburton Energy Services, Inc, Curtis, Philip, Anthony filed Critical Halliburton Energy Services, Inc
Publication of WO2008145975A1 publication Critical patent/WO2008145975A1/fr

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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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/168—Polysaccharide derivatives, e.g. starch sulfate
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • 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
    • C09K8/40—Spacer compositions, e.g. compositions used to separate well-drilling from cementing masses
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • 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
    • 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
    • C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents

Definitions

  • This disclosure relates to servicing a wellbore. More specifically, it relates to servicing a wellbore with compositions comprising a polysaccharide based cement additive and methods of making same.
  • Natural resources such as gas, oil, and water residing in a subterranean formation or zone are usually recovered by drilling a wellbore down to the subterranean formation while circulating a drilling fluid in the wellbore. After terminating the circulation of the drilling fluid, a string of pipe, e.g., casing, is run in the wellbore. The drilling fluid is then usually circulated downward through the interior of the pipe and upward through the annulus, which is located between the exterior of the pipe and the walls of the wellbore.
  • a string of pipe e.g., casing
  • Wellbore servicing fluids e.g., cement slurries, fracturing fluids, drilling fluids
  • cement compositions can be modified using additives such as dispersants, fluid loss control agents, viscosifiers, premature gelation inhibitors, transition time modifiers and the like.
  • additives such as dispersants and fluid loss control agents are often formulated from materials that are deemed environmentally unacceptable for use in locations subject to stringent environmental regulations. Their status as unacceptable environmental materials stems from their inability to undergo complete biodegradation in the environment which may result in undesirable effects if the materials are released into the environment or if they accumulate in animal and plant tissues for long periods. Thus, it would be desirable to develop biodegradable additives that function as dispersants, fluid loss agents, viscosifiers, gelation inhibitors, transition time modifiers and the like.
  • a composition comprising a carboxylated, sulfonated polysaccharide and a wellbore servicing fluid.
  • a wellbore servicing composition comprising a hydraulic cement and a carboxylated, sulfonated polysaccharide.
  • a wellbore servicing composition comprising a polysaccharide having carboxylate and sulfonate groups.
  • a method of servicing a wellbore comprising introducing to the wellbore a wellbore servicing fluid comprising an additive composition comprising a polysaccharide having carboxylate and sulfonate groups.
  • a method of servicing a wellbore comprising preparing at the well site an additive composition comprising a polysaccharide having carboxylate and sulfonate groups, introducing the additive composition into a wellbore servicing fluid, and placing the wellbore servicing fluid into a subterranean formation.
  • a wellbore servicing fluid comprising contacting a polysaccharide composition with an oxidizing agent to form an oxidized polysaccharide, and contacting the oxidized polysaccharide with a sulfonating agent to form a carboxylated sulfonated polysaccharide, and contacting the carboxylated sulfonated polysaccharide with a wellbore servicing fluid.
  • Figure 1 is the chemical structure of cellulose.
  • Figure 2 is the FTIR spectra of the starch samples from Example 1.
  • Figures 3 and 4 are thickening time plots of the cement samples from Example 1.
  • Figure 5 is a thickening time plot of a cement sample from Example 1.
  • the additive compositions comprise polysaccharides such as for example starch or cellulose.
  • the polysaccharides may be modified as disclosed herein to produce additive compositions having different functions.
  • a single additive composition may be prepared so as to have at least two functional groups.
  • the additive - A - compositions disclosed herein may be prepared just prior to use in physical proximity to their end-use location. Alternatively, such compositions may be prepared and stored for use at some later time and/or at a location not proximate to their end-use location.
  • the additive compositions disclosed herein are included in wellbore servicing fluids to modify the properties of said fluids.
  • wellbore servicing fluids include, but are not limited to, cement slurries, non-cementitious sealants, drilling fluids or muds, spacer fluids, fracturing fluids or completion fluids, all of which are well known in the art.
  • the additive composition comprises a polysaccharide.
  • Polysaccharides are relatively complex carbohydrates composed of monosaccharides joined together via glycosidic linkages as shown in Figure 1 for a polysaccharide, cellulose.
  • suitable polysaccharides include, but are not limited to, natural or derivatized polysaccharides that are soluble, dispersible, or swellable in an aqueous liquid (for example starches), gums (for example galactomannan gums such as guar gum), celluloses and derivatives thereof, and combinations thereof.
  • the polysaccharide comprises starch.
  • Starch consists of two types of molecules, amylose which normally comprises 20-30% of the starch and amylopectin which normally comprises 70-80% of the starch. Both consist of polymers of ⁇ -D-glucose units. In amylose the glucose monomers are linked (l—*4), whereas in amylopectin about one glucose residue in about every twenty is also linked (1 — >6) forming branch-points.
  • amylose to amylopectin and consequently (1— >6) branch-points both depend on the source of the starch, for example amylomaizes contain over 50% amylose whereas 'waxy' maize may have almost none (0 to ⁇ 10%).
  • the solubility in water at room temperature increases with higher amylopectin content and may be more suitable when concentrated solutions are needed, hi an embodiment, a starch suitable for use in accordance with the present disclosure may be obtained from renewable glucose sources such as potatoes, corn, maize, tapioca, cereal grains, or combinations thereof.
  • the polysaccharide comprises a galactomannan gum.
  • Galactomannans are polysaccharides consisting of a mannose backbone with galactose side groups. Specifically, a (l-4)-linked beta-D-mannopyranose backbone with branchpoints from their 6-positions linked to alpha-D-galactose, i.e. 1-6-linked alpha-D-galactopyranose.
  • Examples of galatctomann gums include without limitation guar gum, locust bean gum, gum ghatti, gum karaya, tamarind gum, tragacanth gum, or combinations thereof.
  • the polysaccharide comprises cellulose. Cellulose is a straight chain polymer of beta-glucose monomelic units.
  • the cellulose is modified or derivatized, for example hydroxyethylated, alternatively the cellulose is unmodified.
  • a polysaccharide suitable for use in this disclosure has a molecular weight ranging from about 500 Daltons to about 1,000,000 Daltons, alternatively from about 700 to about 500,000, alternatively from about 1000 to about 200,000.
  • the polysaccharide may be present in the additive composition solution in an amount of from about 3 to about 50%, alternatively from about 5 to about 40%, alternatively from about 10 to about 35% by weight of the additive composition.
  • the additive composition comprises a polysaccharide composition that has been modified to introduce anionic functionalities wherein the anionic functionalities comprise carboxylate and sulfonate groups.
  • a method for preparation of the additive composition comprises contacting a polysaccharide composition with an oxidizing agent to form a partially carboxylated, oxidized polysaccharide composition and contacting the partially carboxylated, oxidized polysaccharide composition with a sulfonating agent to fom ⁇ a carboxylated, sulfonated polysaccharide composition.
  • the carboxylated, sulfonated polysaccharide composition may then be used as an additive composition to modify the properties of a wellbore servicing fluid or may be further processed, as will be described in more detail later herein.
  • a method for the preparation of an additive composition comprises contacting a polysaccharide composition with an oxidizing agent.
  • Contacting of the polysaccharide composition with an oxidizing agent may result in the cleavage of glycosidic linkages or hydroxylated carbon-carbon bonds (for example, C 2 -C 3 bonds) or isolated alcohol groups (for example, C 6 -OH bonds) within the polysaccharide and result in the formation of reactive carbonyl-containing groups including carboxylic acid groups, ketones, aldehydes, anhydrides, and ester groups.
  • An oxidizing agent suitable for use in this disclosure may comprise any material capable of oxidizing a polysaccharide of the type disclosed herein to generate carbonyl-containing groups.
  • the oxidizing agent may further be characterized by the ability to react with a polysaccharide and produce by-products that cannot further oxidize the polysaccharide compositions.
  • Use of such oxidizing agents may result in an increased product stability over a long time period, for example during storage of the polysaccharide compositions. This is in contrast to oxidizing agents, for example, periodate and chlorite salts, which upon initial oxidation of polysaccharides, form by-products (e.g., iodate and hypochlorite salts) which may detrimentally further oxidize the polysaccharide composition during storage.
  • Suitable oxidizing agents may comprise hydrogen peroxide or contain a peroxy bond (-O-O-) and release hydrogen peroxide upon reaction with water.
  • the oxidizing agent comprises hydrogen peroxide.
  • the oxidizing agent comprises a salt having X waters of crystallization wherein X is equal to or greater than 1 and wherein at least one of the waters of crystallization has been replaced with hydrogen peroxide.
  • Such salts may be represented by the general formula wherein Y is a salt, n is equal to or greater than zero and m is equal to or greater than 1.
  • the oxidizing agent comprises sodium percarbonate, Na 2 CCVLS H 2 O 2 .
  • the extent of oxidation of the polysaccharide may be adjusted by varying the reaction conditions (e.g. oxidizing agent, reaction time, reaction temperature).
  • the extent of oxidation refers to the number of cleaved bonds such as the number of glycosidic linkages, hydroxylated carbon-carbon bonds (for example, C 2 -C 3 bonds) or isolated alcohol group bonds (for example, C 6 -OH bond); the percent of monosaccharide rings oxidized; the number of alcohol groups oxidized per ring; and also to the nature of the functional groups generated.
  • the percent of monosaccharide rings oxidized per polysaccharide chain in the polysaccharide composition may range from about 1 % to about 30%, alternatively from about 5% to about 25%, alternatively from about 10% to about 20%.
  • the average number of hydroxyl groups oxidized per oxidized monosaccharide may range from about 1 to about 3, alternatively from about 1.5 to about 2.0.
  • the polysaccharide composition may be oxidized to generate aldehyde, ketone and carboxylate groups. The ratio of these groups will vary depending on the reaction conditions and may be adjusted by one of ordinary skill in the art to meet the needs of the user. [0026]
  • the oxidized polysaccharide may be contacted with a sulfonating agent.
  • the sulfonating agent may be any material capable of reacting with the oxidized polysaccharide to generate sulfonate groups.
  • Sulfonating agents are known to one of ordinary skill in the art and include for example and without limitation sodium sulfite.
  • aldehyde and ketone groups of the oxidized polysaccharide may react with the sulfonating agent to generate sulfonate groups chemically bonded to the modified polysaccharide as pendant groups.
  • the number of carboxylate groups present in the additive composition may be increased by contacting the oxidizing agent with the polysaccharide composition under conditions that allow for the maximum conversion of aldehyde functionalities to carboxylates.
  • the number of carboxylate groups present in the additive composition may be decreased by contacting the oxidizing agent with the polysaccharide composition under conditions that allow for the minimum conversion of aldehyde functionalities to carboxylates.
  • the reaction conditions may be adjusted so as to allow for the maximum number of sulfonate groups to be present in the final formulation of the additive composition.
  • the additive composition comprises both carboxylate and sulfonate functionalities.
  • the additive composition comprising a polysaccharide having a number of carboxylate groups and a number of sulfonate groups in water may be used in a wellbore servicing fluid without further processing.
  • the additive composition may be further processed such as for example by drying to have the solvent (e.g., water) removed and form a solid which may be stored and used at some later time in a wellbore servicing fluid.
  • the additive composition may be suspended (for example, in a non-aqueous solvent) or remain suspended or dissolved in a solvent (e.g., water) for storage and use at some later time in a wellbore servicing fluid.
  • the additive composition refers to the carboxylated, sulfonated polysaccharide composition whether used as is following preparation or processed (e.g., solvent removal) and used at some later time.
  • the additive composition may be included in the wellbore servicing fluid (e.g., cement) wherein it may perform any number of functions.
  • the additive composition prepared as described comprises a carboxylated, sulfonated polysaccharide having x number of carboxylate functionalities and y number of sulfonate functionalities wherein x and y are greater than 1.
  • the ratio of carboxylate functionalities to sulfonate functionalities, x/y may determine the utility of the composition for a particular application.
  • the x/y ratio may range from about 0.1 to about 4 as determined by infrared spectroscopy by dividing the ratio of peak heights at 1596.8 cm "1 to 624.8 cm "1 .
  • increasing the number of carboxylate functionalities may result in an increase in the retarding capabilities of the composition.
  • increasing the number of sulfonate functionalities may result in a composition more suitable for use as a fluid loss agent or a dispersant.
  • the exact ratio of carboxylate to sulfonate in the additive composition necessary to produce a desired effect may be adjusted as disclosed herein by one of ordinary skill in the art to meet the needs of the user.
  • the additive composition functions as a dispersant.
  • Dispersants are used to reduce the apparent viscosities of the cement compositions in which they are utilized. The reduction of the viscosity of a cement composition allows the cement composition to be pumped with less fi ⁇ ction pressure and utilizing less pump horsepower. In addition, the lower viscosity often allows the cement composition to be pumped in turbulent flow. Turbulent flow characteristics are desirable when pumping cement compositions in wells to more efficiently remove drilling fluid from surfaces in the well bore as the drilling fluid is displaced by the cement composition being pumped. The inclusion of dispersants in cement compositions is also desirable in that the presence of the dispersants facilitates the mixing of the cement compositions and reduces the water required for the cement compositions. Cement compositions having reduced water content are characterized by improved compressive strength development.
  • the additive composition functions as a fluid loss control agent.
  • Fluid loss control agents are used in well cement compositions to reduce fluid loss from the cement compositions to permeable formations or zones into or through which the cement compositions are pumped, hi primary cementing, the loss of fluid, i.e., water, to permeable subterranean formations or zones can result in premature gelation of the cement composition whereby bridging of the annular space between the permeable formation or zone and the pipe string being cemented prevents the cement composition from being placed over the entire length of the annulus.
  • the additive composition functions as a gelation inhibitor and/or a transition time modifier.
  • Gelation inhibitors and/or transition time modifiers may be included in cement compositions to prevent the premature gelation of said compositions or unwanted gas or water migration through the cement slurry.
  • Gas migration is caused by the behavior of the cement slurry during a transition phase in which the cement slurry changes from a true hydraulic fluid to a highly viscous mass showing some solid characteristics. When first placed in the annulus, the cement slurry acts as a true liquid and thus transmits hydrostatic pressure.
  • the gel strength of the cement slurry increases to a value sufficient to resist the pressure exerted by the gas in the formation against the slurry.
  • the cement slurry then sets into a solid mass.
  • the flow channels formed in the cement during such gas or water migration remain in the cement once it has set. Those flow channels can permit further migration of gas or water through the cement even long after the cement is set.
  • the addition of a gelation inhibitor and/or transition time modifier may allow the cement residing in the annulus to effectively maintain isolation of the adjacent subterranean formation.
  • the additive compositions of this disclosure may be present in a wellbore servicing fluid in an amount of from about 0.1 to about 4%, alternatively of from about 0.2 to about 3%, alternatively of from about 0.3 to about 2% by weight of water, for example in water-based drilling fluids or by weight of cement in the case of cement slurries.
  • the additive compositions disclosed herein can be included in any wellbore servicing fluid (WSF) which may in turn be used for any purpose.
  • WSF wellbore servicing fluid
  • the WSFs are used to service a wellbore that penetrates a subterranean formation.
  • subterranean formation encompasses both areas below exposed earth and areas below earth covered by water such as ocean or fresh water.
  • Servicing a wellbore includes, without limitation, positioning the WSF in the wellbore to isolate the subterranean formation from a portion of the wellbore; to support a conduit in the wellbore; to plug a void or crack in the conduit; to plug a void or crack in a cement sheath disposed in an annulus of the wellbore; to plug a perforation; to plug an opening between the cement sheath and the conduit; to prevent the loss of aqueous or nonaqueous drilling fluids into loss circulation zones such as a void, vugular zone, or fracture; to plug a well for abandonment purposes; a temporary plug to divert treatment fluids; as a chemical packer to be used as a fluid in front of cement slurry in cementing operations; and to seal an annulus between the wellbore and an expandable pipe or pipe string.
  • the WSF may viscosity in a loss-circulation zone and thereby restore circulation.
  • the viscosified mixture can set into a flexible, resilient and tough material, which may prevent further fluid losses when circulation is resumed.
  • the WSF may withstand substantial amounts of pressure, e.g., the hydrostatic pressure of a drilling fluid or cement slurry, without being dislodged or extruded.
  • the WSF may provide a relatively viscous mass inside the loss-circulation zone.
  • the WSF can also form a non-flowing, intact mass inside the loss-circulation zone. This mass plugs the zone and inhibits loss of subsequently pumped drilling fluid, which allows for further drilling.
  • the WSF may be employed in well completion operations such as primary and secondary cementing operations. Said fluids may be placed into an annulus of the wellbore and allowed to set such that it isolates the subterranean formation from a different portion of the wellbore. The WSF thus form a barrier that prevents fluids in that subterranean formation from migrating into other subterranean formations. Within the annulus, the fluid also serves to support a conduit, e.g., casing, in the wellbore.
  • a conduit e.g., casing
  • the wellbore in which the WSFs are positioned belongs to a multilateral wellbore configuration. It is to be understood that a multilateral wellbore configuration includes at least two principal wellbores connected by one or more ancillary wellbores.
  • the WSF may be strategically positioned in the wellbore to plug a void or crack in the conduit, to plug a void or crack in the hardened sealant (e.g., cement sheath) residing in the annulus, to plug a relatively small opening known as a microannulus between the hardened sealant and the conduit, and so forth, thus acting as a sealant composition.
  • Various procedures that may be followed to use a WSF in a wellbore are described in U.S. Patent Nos. 5,346,012 and 5,588,488, which are incorporated by reference herein in their entirety.
  • Additive compositions such as those disclosed herein may be introduced to cementitious materials which may comprise a hydraulic cement that sets and hardens by reaction with water.
  • hydraulic cements include but are not limited to Portland cements (e.g., classes A, B, C, G, and H Portland cements), pozzolana cements, gypsum cements, phosphate cements, high alumina content cements, silica cements, high alkalinity cements, shale cements, acid/base cements, magnesia cements, fly ash cement, zeolite cement systems, cement kiln dust cement systems, slag cements, micro-fine cement, metakaolin, and combinations thereof.
  • Portland cements e.g., classes A, B, C, G, and H Portland cements
  • pozzolana cements e.g., gypsum cements
  • phosphate cements phosphate cements
  • high alumina content cements silica cements
  • the cement comprises a Sorel cement composition, which typically comprises magnesium oxide and a chloride or phosphate salt which together form for example magnesium oxychloride.
  • Sorel cement composition typically comprises magnesium oxide and a chloride or phosphate salt which together form for example magnesium oxychloride.
  • magnesium oxychloride cements are disclosed in U.S. Patent Nos. 6,664,215 and 7,044,222, each of which is incorporated herein by reference in its entirety.
  • the cementitious material may further comprise water.
  • the cementitous material includes a sufficient amount of water to form a pumpable slurry.
  • the water may be fresh water or salt water, e.g., an unsaturated aqueous salt solution or a saturated aqueous salt solution such as brine or seawater.
  • the cement slurry may be a lightweight cement slurry containing density-reducing additives such as for example foam (e.g., foamed cement) and/or hollow beads/microspheres.
  • an additive composition prepared as disclosed herein may be introduced to a cementitious material and decrease the transition time of said material such that the cement exhibits right angle set.
  • Right angle set refers to cement compositions that exhibit a relatively constant viscosity for a period of time after they are initially prepared and while they are being placed in their intended locations in the wellbore, i.e., during the period when the slurry is in motion.
  • the cement compositions quickly set such that the viscosity increases from about 35 Bc to equal to or higher than 70 Bc in a short period of time (i.e. less than about 1 hour).
  • This sudden jump in viscosity may be very desirable in preventing unwanted events such as gas or water migration into the slurry because it indicates the quick formation of an impermeable mass from a gelled state after placement.
  • Such cement compositions are called "Right Angle Set Cement Compositions" in reference to the near right angle increase shown in a plot of viscosity v. time.
  • an additive composition of the type disclosed herein is prepared at the site of use and/or just prior to use such that the composition is not stored for a duration of time equal to or less than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 24, or 48 hours from production.
  • an additive composition may be prepared by transporting a polysaccharide, an oxidizing agent and a sulfonating agent to a wellsite.
  • the polysaccharide e.g. starch
  • an oxidizing agent e.g. sodium percarbonate
  • the mixture may be allowed to react under conditions that allow for the fo ⁇ nation of carboxylate groups.
  • the mixture may then be contacted with a sulfonating agent (e.g. sodium sulfite) and reacted to allow for the formation of sulfonate groups.
  • a sulfonating agent e.g. sodium sulfite
  • the exact reaction conditions for formation of either carboxylate or sulfonate groups may be varied by one of ordinary skill in the art to adjust the relative ratio of carboxylates and sulfonates produced as has been described previously herein.
  • the resultant mixture may be added to a wellbore servicing fluid (e.g. cementitious slurry) which may then be placed in the wellbore.
  • the additive composition when prepared as described herein and the materials used to prepare the additive composition may be classified as substances that Pose Little Or NO Risk (PLONOR) to the environment or as "Readily Biodegradable” with a biodegradability of greater than 20% in 68 days when the biodegradability tests are performed according to Organization for Economic Cooperation and Development (OECD) test protocols for OECD 302 and/or OECD 306 procedures and whose environmental effects (e.g., toxicity) are considered to be well known.
  • the additive compositions are biodegradable and as such may undergo degradation over time if accidentally released into the environment or intentionally discharged into the environment for disposal.
  • Additive compositions were prepared according to the following procedures: 30 g starch (Cargill Dry MD 01960) was dissolved in 100 mL of water using a blender and to this solution was added 5.8 g sodium percarbonate (Na 2 CO 3 * 1.5H 2 O 2 ) and stirred to mix the solution. To this solution 60 mg of FeSO 4 ⁇ 7H 2 O was added and mixed. The solution turned red-brown due to the formation of Fe 3+ salt. The solution was stirred at room temperature for either 1 or 2 hours. The solution turned optically clear during stirring. To this solution was added 5g sodium sulfite and the solution was then heated at 75 °C for 1 hour.
  • the concentration of the active polymer content was estimated to be 32%.
  • the sample that was stirred at room temperature for 1 hour is referred to as the “1 hr sample” while the sample stirred at room temperature for 2 hours is referred to as the "2 hr sample”.
  • the ratio of carboxylate groups to sulfonate groups for the 1 hr and 2 hr samples were determined by Fourier transform infrared spectroscopy (FTIR).
  • FTIR spectra of the 1 hr and 2 hr samples along with a control sample comprising an unmodified starch composition are shown in Figure 2.
  • the results demonstrate that the extent of carboxylation and sulfonation and the ratio of carboxylate to sulfonate groups in a polysaccharide composition can be determined by measuring changes in the FTIR spectra of the composition.
  • the carboxylate group has a characteristic absorption band at a frequency of 1596.8 cm " while the sulfonate group has a characteristic absorption band at a frequency of 624.8 cm '] .
  • the presence of these absorption bands and their relative intensities can be used to determine the ratio of carboxylate to sulfonate groups in the composition.
  • the respective band heights in the FTIR spectra ( Figure 2) were measured and those values are presented in Table 1.
  • the thickening time refers to the time required for the composition to achieve 70 Bearden units of Consistency (Bc). At about 70 Bc, the slurry undergoes a conversion from a pumpable fluid state to a non-pumpable paste.
  • the thickening time of the slurries were measured in accordance with API 1OB. Thickening time charts for the lhr and 2 hi" sample at 0.1 % by weight of cement (bwoc), Slurry #2 and Slurry #3, are shown in Figures 3 and 4.
  • the results demonstrate the ability of the additive compositions of this disclosure to minimize gel formation under dynamic conditions.
  • the additive compositions of this disclosure have a very short duration between a slurry viscosity of 40 Bc to 70 Bc and 70 Bc to 100 Bc thus; the slurries are expected to exhibit Right Angle Set Behavior.
  • Figure 5 is the thickening time chart of the 2 hr Sample, Slurry #4, at an amount of 0.05 % bwoc.
  • compositions of sulfite adducts of oxidized starch were prepared according to the procedures described in U.S. Published Application No. 2005-0274291 Al, hereinafter '291, using sodium periodate as the oxidizer. A portion of these solutions were exposed to air and another portion was left in partially-filled, closed bottles. The air exposed solution discolored quickly within a week and lost their ability to act as cement slurry dispersants. The solution kept in a partially-filled bottle discolored slowly over a period of about a month and lost their effectiveness to disperse cement slurries.
  • the carboxylated, sulfonated polysaccharide products of present disclosure did not lose their color even after 3 months of storage in a partially-filled, closed bottle thus demonstrating longer shelf life.
  • the results suggest that the compositions described in '291 may be breaking down because of the presence of active by-products of the oxidizing agent used (for example, iodate salt) and/or the reaction product is of a different chemical nature that is air sensitive thus limiting its use.
  • reaction product described in '291 sulfite ion forms a charge-transfer type of adduct with an aldehyde group, whereas in the present disclosures it forms a full-fledged covalent sulfonate group by the addition of sulfite group to a carbonyl group of ketone or an aldehyde group.
  • Examples 1-6 demonstrate that the additive compositions of this disclosure can be included in wellbore servicing fluids to control parameters such as thickening time, rheology and gelation.
  • the additive compositions of this disclosure are prepared using a simple method involving contacting polysaccharides, an oxidizing agent and a sulfite salt to produce carboxylated, sulfonated polysaccharide compositions which can be produced on site for immediate use or stored for later use.

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

Abstract

L'invention concerne une composition comprenant un polysaccharide carboxylé, sulfoné et un fluide d'entretien de puits; un procédé d'entretien d'un puits comprenant l'introduction dans le puits d'un fluide d'entretien de puits comprenant une composition d'additif comportant un polysaccharide ayant des groupes carboxylate et sulfonate.
PCT/GB2008/001774 2007-05-30 2008-05-23 Additifs de ciment à base de polysaccharide WO2008145975A1 (fr)

Applications Claiming Priority (4)

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US11/755,270 2007-05-30
US11/755,270 US8569214B2 (en) 2007-05-30 2007-05-30 Methods of using polysaccharide based cement additives
US11/755,271 US8586508B2 (en) 2007-05-30 2007-05-30 Polysaccharide based cement additives
US11/755,271 2007-05-30

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110203486A1 (en) * 2010-02-25 2011-08-25 Luc Nicoleau Hardening Accelerator Composition Containing Dispersants
CN103534222A (zh) * 2011-05-17 2014-01-22 建筑研究和技术有限公司 制备水泥基材料的添加剂的方法，添加剂和包含添加剂的混合物
US9102568B2 (en) 2009-09-02 2015-08-11 Construction Research & Technology Gmbh Sprayable hydraulic binder composition and method of use
US9388077B2 (en) 2012-08-13 2016-07-12 Construction Research & Technology Gmbh Hardening accelerator composition
US9650298B2 (en) 2012-08-13 2017-05-16 Construction Research & Technology Gmbh Hardening accelerator composition for cementitious compositions
US9926233B2 (en) 2014-12-18 2018-03-27 Basf Se Construction chemical composition for tile mortar

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Publication number Priority date Publication date Assignee Title
EP0879826A1 (fr) * 1996-11-27 1998-11-25 Kao Corporation Derives polysaccharidiques et compositions hydrauliques
DE10021476A1 (de) * 2000-04-04 2001-10-11 Sueddeutsche Kalkstickstoff Wasserlösliche Pfropfpolymere, Verfahren zu ihrer Herstelleung und deren Verwendung
US20040103824A1 (en) * 2001-03-22 2004-06-03 Lars Einfeldt Use of water-soluble polysaccharide derivatives as dispersing agents for mineral binder suspensions
US20040206502A1 (en) * 2003-04-15 2004-10-21 Reddy B Raghava Biodegradable dispersants for cement compositions and methods of cementing in subterranean formations

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0879826A1 (fr) * 1996-11-27 1998-11-25 Kao Corporation Derives polysaccharidiques et compositions hydrauliques
DE10021476A1 (de) * 2000-04-04 2001-10-11 Sueddeutsche Kalkstickstoff Wasserlösliche Pfropfpolymere, Verfahren zu ihrer Herstelleung und deren Verwendung
US20040103824A1 (en) * 2001-03-22 2004-06-03 Lars Einfeldt Use of water-soluble polysaccharide derivatives as dispersing agents for mineral binder suspensions
US20040206502A1 (en) * 2003-04-15 2004-10-21 Reddy B Raghava Biodegradable dispersants for cement compositions and methods of cementing in subterranean formations

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9102568B2 (en) 2009-09-02 2015-08-11 Construction Research & Technology Gmbh Sprayable hydraulic binder composition and method of use
US20110203486A1 (en) * 2010-02-25 2011-08-25 Luc Nicoleau Hardening Accelerator Composition Containing Dispersants
US9567262B2 (en) 2010-02-25 2017-02-14 Construction Research & Technology Gmbh Hardening accelerator composition containing dispersants
CN103534222A (zh) * 2011-05-17 2014-01-22 建筑研究和技术有限公司 制备水泥基材料的添加剂的方法，添加剂和包含添加剂的混合物
EP2709964A1 (fr) * 2011-05-17 2014-03-26 Construction Research & Technology GmbH Procédé pour la préparation d'additifs pour des matériaux à base de ciment, additif et mélange comprenant l'additif
JP2014519466A (ja) * 2011-05-17 2014-08-14 コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー セメント質材料用添加剤の製造方法、添加剤、および添加剤を含む混合物
EP2709964A4 (fr) * 2011-05-17 2014-10-29 Constr Res & Tech Gmbh Procédé pour la préparation d'additifs pour des matériaux à base de ciment, additif et mélange comprenant l'additif
US9388077B2 (en) 2012-08-13 2016-07-12 Construction Research & Technology Gmbh Hardening accelerator composition
US9650298B2 (en) 2012-08-13 2017-05-16 Construction Research & Technology Gmbh Hardening accelerator composition for cementitious compositions
US9926233B2 (en) 2014-12-18 2018-03-27 Basf Se Construction chemical composition for tile mortar

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