WO2024192251A1 - Additifs de ciment multifonctionnels et procédés pour leur utilisation - Google Patents

Additifs de ciment multifonctionnels et procédés pour leur utilisation Download PDF

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Publication number
WO2024192251A1
WO2024192251A1 PCT/US2024/019954 US2024019954W WO2024192251A1 WO 2024192251 A1 WO2024192251 A1 WO 2024192251A1 US 2024019954 W US2024019954 W US 2024019954W WO 2024192251 A1 WO2024192251 A1 WO 2024192251A1
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Prior art keywords
acid
additive
cement
composition
sugar
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English (en)
Inventor
LoongYi TAN
Jun Su An
Jason HELANDER
Ara Jeknavorian
Amit Desai
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Solugen Inc
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Solugen Inc
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Priority to MX2025010836A priority Critical patent/MX2025010836A/es
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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
    • 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
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • 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
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • 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
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
    • 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
    • C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete

Definitions

  • the present disclosure relates generally to compositions and methods for use with materials that form a hardened mass when hydrated. More particularly, the present disclosure relates to cement additives and methods of using same.
  • cement additives are included in cement compositions in order to influence one or more user and/or application-desired properties.
  • Cement additives are generally described as chemicals and/or materials added to a cement slurry to modify the characteristics of the slurry and/or the set cement.
  • Cement additives may be broadly divided into six different categories that include: (i) water reducers, (ii) set retarders, (iii) accelerants, (iv) superplasticizers, (v) corrosion inhibitors, and (vi) air entrainers.
  • cement additives that are single or dual functionality products.
  • lignosulfonates are chemicals that are conventionally employed as both a set retarder and plasticizer.
  • Another widely used chemical additive comprising gluconate, glucoheptonate, or both also exhibits dual functionality.
  • a challenge to the use of these materials is that multiple additional compounds are needed to provide cementitious compositions having tailored, application-desired properties. Accordingly, an ongoing need exists for novel additives for use in cement and/or concrete that exhibit higher levels of functionality.
  • Figure 1 is an aspect of a process flow diagram for a chemoenzymatic process of the type disclosed herein.
  • a multifunctional cement additive comprising (i) a sugar derivative comprising glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, gluconic acid oxidation products disaccharides, oxidized disaccharides, uronic acid, aldaric acid, galactonic acid, galactaric acid, glutamic acid glucodialdose, 2- ketoglucose, salts thereof, lactones thereof, or a combination thereof and (ii) a solvent.
  • composition comprising (a) a cementitious material (b) a multifunctional additive comprising a sugar oxidation product and (c) a solvent wherein the multifunctional additive comprising a sugar oxidation product is a mixture of two compounds selected from the group consisting essentially of dextrose, glucose, fructose, sucrose, glucaric acid, glucodialdose, gluconic acid, erythorbic acid, galactaric acid, galacturonic acid, galactonic acid and 2-ketoglucose.
  • compositions for use as cement additives are multifunctional cement additives having at least three functionalities selected from the group consisting of water reducers, set retarders, accelerants, superplasticizers, corrosion inhibitors, strength enhancers, grinding aids, quality improvers, viscosity modifiers, shrinkage reducers and air entrainers.
  • these materials are referred to as “cement additives with higher functionality” or CAHF.
  • the CAHF comprises a sugar derivative and a solvent.
  • cementitious materials include, but are not limited to, cement, concrete, shotcrete, mortar, grout, asphalt, and the like.
  • cements and cementitious compositions although other compositions comprising materials that set and harden upon hydration are also contemplated.
  • the CAHF comprises at least one oxidized sugar or, additionally or alternatively, a mixture comprising sugars and at least one oxidized sugar. Additionally or alternatively, in some aspects, the CAHF comprises a sugar, an oxidized sugar, a partially-oxidized sugar, derivatives thereof, or a combination thereof. [0014] In one or more aspects, the CAHF comprises a sugar oxidation product.
  • the sugar oxidation product may comprise an aldaric acid, uronic acid, glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, gluconic acid oxidation products, disaccharides, oxidized disaccharides, n-keto-acids, C2-C6 diacids, galactonic acid, galactaric acid, glutamic acid, glucodialdose, 2-ketoglucose, glucodiamine, glycolaldehyde, glyoxal, salts thereof, lactones thereof and a combination thereof.
  • a sugar oxidation product suitable for use in the CAHF comprises less than about 5 wt.% maltose, maltotriose, fructose, higher molecular weight polysaccharides, oxidation products thereof or a combination thereof based on the total weight of the sugar oxidation product.
  • the CAHF comprises aldonic acid, uronic acid, aldaric acid, or a combination thereof.
  • the CAHF is a mixture of aldaric acid, and uronic acids.
  • the CAHF comprises a glucose oxidation product, a gluconic acid oxidation product, a gluconate, or a combination thereof. In one or more aspects, the CAHF comprises glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, gluconic acid oxidation products or a combination thereof. In one or more aspects, the CAHF comprises disaccharides, oxidized disaccharides, uronic acid, aldaric acid or a combination thereof. In one or more aspects, the CAHF comprises gluconic acid, glucaric acid, glucuronic acid, n-keto-acids, C2 to Ce diacids or a combination thereof.
  • the CAHF comprises galactonic acid, galactaric acid, an oxidation product comprising predominantly (e.g., greater than about 50 weight percent) galactonic acid and/or galactaric acid with minor component species of n-keto-acids, C2 to CB diacids or a combination thereof.
  • the CAHF comprises glutamic acid.
  • the CAHF comprises glucodialdose, 2- ketoglucose or a combination thereof.
  • the CAHF comprises a buffered glucose oxidation product, a buffered gluconic acid oxidation product, an oxidized glucuronolactone, a uronic acid oxidation product or a combination thereof.
  • the buffered glucose oxidation product, the buffered gluconic acid oxidation product, or combinations thereof are buffered to a suitable pH.
  • the CAHF may comprise a mixture of sugars and sugar oxidation products.
  • the CAHF may comprise dextrose, glucose, fructose, sucrose, glucaric acid and, glucodialdose, gluconic acid, erythorbic acid, galactaric acid, galacturonic acid, galactonic acid, 2-ketoglucose, salts thereof, lactones thereof, or a combination thereof.
  • Any sugar oxidation product for use in the CAHF may comprise a counter-cation such as a Group 1 alkali metal, a Group 2 alkaline earth metal or a combination thereof.
  • the counter-cation may comprise silicates, borates, aluminum, calcium, magnesium, ammonium, sodium, potassium, cesium, strontium or a combination thereof.
  • the CAHF comprises dextrose, glucose, fructose, sucrose, glucaric acid, glucodialdose, gluconic acid erythorbic acid, galactaric acid, galacturonic acid, galactonic acid, 2-ketoglucose, salts thereof, lactones thereof, or a combination thereof.
  • the CAHF comprises a crude mixture of sugars and sugar oxidation products.
  • the crude mixture may be a reaction product that contains at least 40 weight percent, alternatively at least 50 wt.%, alternatively at least 60 wt.% or alternatively from about 40 wt.% to about 60 wt.% of sugars and sugar oxidation products combined based on the total weight of the CAHF.
  • the crude mixture may be derived from a cellulose feedstock, for example, a waste cellulose feedstock.
  • waste cellulose feedstocks include recycled cardboard, paperboard, fiberboard, paper, and cotton textiles.
  • the cellulose feedstock comprises cardboard waste.
  • the CAHF comprises a mixture of two compounds selected from the group consisting essentially of dextrose, glucose, fructose, sucrose, glucaric acid an, glucodialdose, gluconic acid, erythorbic acid, galactaric acid, galacturonic acid, galactonic acid and 2-ketoglucose, where the ratio of the two compounds is from about 10:90 to about 90: 10, alternatively from about 20:80 to about 80:20 or alternatively about 50:50.
  • the CAHF comprises a cellulose-derived reaction product which is present in an amount of from about 20 wt.% to about 80 wt.%, additionally or alternatively, from about 25 wt.% to about 75 wt.% or, additionally or alternatively, from about 50 wt.% to about 75 wt.% based on the total weight of the CAHF.
  • the CAHF further comprises a solvent.
  • solvent suitable for use in the CAHF include methanol, ethanol, water, acetonitrile, and combinations thereof.
  • the solvent is water.
  • Nonlimiting example of water suitable for use in the CAHF may be salt water, fresh water, brackish water, ground water, non-potable water (i.e., water that is not of drinking water quality), raw water (i.e., water that has not yet passed through a water treatment facility) and recycled water / reclaimed water.
  • a solvent suitable for use is compatible with the components of the CAHF and able to solubilize the components at room temperature. In one or more aspects, the solvent constitutes the remainder of the CAHF once all other components are accounted for.
  • a method of the present disclosure comprises contacting a CAHF, a cementitious material and an aqueous fluid to form a homogenous slurry.
  • Contacting of the components (CAHF, cementitious material, aqueous fluid) may be carried out by the mixing components using mixing equipment (e.g., a jet mixer, recirculating mixer, a batch mixer, a blender, a mixing head of a solid feeding system) to form a pumpable slurry (e.g., a homogeneous fluid).
  • mixing equipment e.g., a jet mixer, recirculating mixer, a batch mixer, a blender, a mixing head of a solid feeding system
  • a pumpable slurry e.g., a homogeneous fluid
  • the cementitious material comprises a hydraulic cement.
  • Hydraulic cements generally comprise calcium oxide, silicon dioxide, aluminum oxide, ferric oxide, and sulfur oxide, and harden by reaction with water.
  • hydraulic cements suitable for use in the present disclosure include 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 such as Sorel cements, fly ash cement, zeolite cement systems, kiln dust cement systems, slag cements, micro-fine cement, metakaolin, and combinations thereof.
  • the cement is a Portland cement, which is a mixture of calcium oxide, silicon dioxide, aluminum oxide, ferric oxide, and sulfur oxide.
  • the cement is present in the slurry in an amount of from about 10 wt.% to about 90 wt.%, alternatively from about 20 wt.% to about 80 wt.% or alternatively from about 25 wt.% to about 80 wt.% based on the total weight of the cement slurry.
  • the CAHF is present in the slurry in a range of from about 0.01 % to about 5% by weight of cementitious material (BWOC), additionally or alternatively, from about 0.1 % to about 5%, additionally or alternatively, from about 0.1 % to about 1 % or, additionally or alternatively, from about 2% to about 10%.
  • BWOC cementitious material
  • the cementitious composition includes a sufficient amount of an aqueous fluid to form a pumpable cement slurry.
  • the aqueous fluid 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 aqueous fluid is present within the cement slurry in an amount of from about 20 % to about 180 % BWOC, alternatively from about 28 % to about 60 % BWOC, or alternatively from about 36 % to about 66 % BWOC.
  • the cementitious composition comprises one or more additives, in addition to the CAHF.to meet some user and/or process objective.
  • the one or more additives can include a viscosifier, a rate of penetration enhancer, spotting fluid, a sweeping agent, a deflocculant, a degreaser, a pH buffer, a wetting agent, a lubricant, a shale inhibitor, a friction reducer, a strength-stabilizing agent, an emulsifier, an expansion agent, a salt, a fluid loss agent, a vitrified shale, a thixotropic agent, a dispersing agent, a weight reducing additive (e.g., hollow glass or ceramic beads), a heavyweight additive, a surfactant, a scale inhibitor, a clay stabilizer, a silicate-control agent, a biocide, a biostatic agent, a storage stabilizer, a filtration control additive, a suspending agent,
  • the cement slurry is formed at the jobsite or the site of intended use (e.g., at the well site where the completion operation is being performed).
  • This site may include construction sites, mixing sites, or at an oil gas wellbore.
  • the cementitious slurry is formed off-site and then later used at the site of intended use or jobsite (e.g., a well site).
  • the CAHF may be dry blended with the cement at a location remote from the jobsite, transported to the well site, formed into a pumpable slurry and placed.
  • the cementitious slurry with the CAHF is placed in a construction location, or down a wellbore at the well site.
  • the CAHF can be added as an aqueous solution (e.g., concentrate) to the mixed water that is later contacted with the cementitious material.
  • the CAHF is formulated as an aqueous emulsions/dispersion that may be injected into the slurry during the cementing operation.
  • the CAHF when added to a cement slurry results in an increase in the compressive strength of the set cement when compared to a set cement lacking a CAHF.
  • the compressive strength of the set cement comprising a CAHF is increased by from about 5% to about 100%, alternatively from about 10% to about 50% or, alternatively from about 5% to about 30%.
  • the set cement comprising a CAHF of the type disclosed herein has a compressive strength of from about 500 psi to about 8000 psi, alternatively from about 5000 psi about 8000 psi, alternatively from about 500 psi to about 3000 psi or alternatively from about 2000 psi to about 6000 psi as determined in accordance with ASTM C39.
  • a cement slurry comprising a CAHF of the type disclosed herein has an increase in slump of from about 0.5 inches (in.) to about 9 in. alternatively from about 1 in. to about 5 in., alternatively from about 0.5 in. to about 3 in., or alternatively from about 3 in. to about 7 in.
  • Slump is a measure of the consistency of a concrete mix, or its ability to flow, and is often used to evaluate how much water has been used in the mix.
  • a cement slurry comprising a CAHF of the type disclosed herein has a slump of from about 5.6 in. to about 9 in., alternatively from about 7 in. to about 9 in., alternatively from about 6 in. to about 8 in., or alternatively from about 5.6 in. to about 7.2 in. as determined in accordance with ASTM C31 .
  • CAHFs of the type disclosed herein may have at least three functionalities selected from the group consisting of water reducers, set retarders, accelerants, superplasticizers, corrosion inhibitors, strength enhancers, grinding aids, quality improvers, viscosity modifiers, shrinkage reducers and air entrainers.
  • a CAHF of the type disclosed herein increases the thickening time of the cement by from about 5% to about 400%, alternatively from about 100 % to about 400%, alternatively from about 5% to about 50% or alternatively from about 40% to about 200% when compared to an otherwise similar cementitious composition lacking a CAHF.
  • a CAHF of the type disclosed herein has a thickening time of from about 2 hours (hrs) to about 34 hrs, alternatively from about 2 hrs to about 8 hrs, alternatively from about 4 hrs to about 30 hrs or alternatively from about 6 hrs to about 34 hrs.
  • thickening time refers to the time required for the cementitious composition to achieve 70 Bearden units of Consistency (Be) after preparation of the cementitious composition. At about 70 Be, the cementitious composition undergoes a conversion from a pumpable fluid state to a non-pumpable gel. A measurement of Be can be considered a thickening time test which is performed on a moving fluid. Thickening time can be measured in accordance with API RP 10B-2 clause 9 and ASTM C403.
  • a CAHF of the type disclosed herein reduces the setting time of the cementitious composition by from about 20% to about 90%, alternatively from about 40% to about 80%, alternatively from about 60% to about 90% or alternatively from about 20% to about 50% when compared to an otherwise similar cementitious composition lacking a CAHF as determined in accordance with a suitable standard reference such as API RP 10B-2 clause 9, ASTM C 150 , AASHTO T 131 or ASTM C 191.
  • a CAHF of the type disclosed herein functions as a corrosion inhibitor of the cement by reducing the conductivity of the cement by from about 10% to about 10000%, alternatively from about 400% to about 800%, alternatively from about 600% to about 10000% or alternatively from about 10% to about 500% when compared to an otherwise similar cementitious composition lacking a CAHF.
  • a CAHF of the type disclosed herein has a conductivity of from about 0.1 uS/c 2 t0 about 25 pS/'cm 2 , alternatively from about 0.1 pS/cm 2 to about 1 pS/c 2 , alternatively from about 2 pS/cm 2 to about 25 pS/cm 2 or alternatively from about 1 pS/cm 2 to about 20 pS/cm 2 as determined in accordance with ASTM G180 Polarization Resistance Test.
  • the CAHF functions as a waterreducer.
  • a water reducer refers to a material that reduces the water to cement ratio of a cementitious composition without adversely affecting the rheological properties of the slurry. Water reducers can decrease the concrete porosity, increase the concrete strength, increase the workability of the cement slurry, reduce the water permeability of the set cement, and reduce the diffusivity of aggressive agents in the concrete thereby improving the durability of concrete and providing a better surface finish.
  • the CAHF functions as a superplasticizer in the absence of other conventional superplasticizers.
  • a superplasticizer also known as a high range water reducer, refers to a material that (i) enables the production of cement with a reduction in water content of 30% or more and (ii) retards curing of the cement.
  • Superplasticizers are used where a well-dispersed particle suspension is desired to improve the slurry rheology. Their addition to cementitious compositions allows the reduction of the water to cement ratio without negatively affecting the workability of the mixture, and enables the production of self-consolidating cementitious and high- performance cementitious compositions.
  • a cementitious composition comprising a CAHF has a water: cement ratio that is reduced by from about 5% to about 40%, alternatively by from about 10% to about 30% or alternatively by from about 10% to about 20% when compared to the watercement ratio used for an otherwise identical cementitious composition lacking a CAHF.
  • the CAHF is included in the cement with conventional superplasticizers such as phosphonic acid-terminated polyethers and naphthalenesulfonate/formaldehyde polymer or conventional water reducers such as lignosulfates and hydroxycarboxylic acids.
  • the CAHF functions as a set retarder in the absence of other conventional set retarders.
  • a set retarder refers to a material used to increase the thickening time of cement slurries to enable proper placement. The need for cement retardation increases with depth due to the greater time required to complete the cementing operation and the effect of increased temperature on the cement-setting process.
  • a cementitious composition comprising a CAHF has a set time that is increased by from about 20% to about 200%, additionally or alternatively, by from about 40% to about 150% or, additionally or alternatively, by from about 50% to about 100% when compared to the set time observed for an otherwise identical cementitious composition lacking a CAHF.
  • the CAHF is included in the cement with conventional set retarders such as lignosulfonates, welan gum, xanthan gum, cellulose, polyanionic cellulose, organic acids, alkali metal salts of organic acids, carboxy hexoses and the corresponding lactones, polyvalent metal salts (e.g., polyvalent metal halides), and the like.
  • conventional set retarders such as lignosulfonates, welan gum, xanthan gum, cellulose, polyanionic cellulose, organic acids, alkali metal salts of organic acids, carboxy hexoses and the corresponding lactones, polyvalent metal salts (e.g., polyvalent metal halides), and the like.
  • the CAHF functions as an accelerant in the absence of other conventional accelerants.
  • an accelerant refers to a material used to reduce the time required for the set cement to develop compressive strength sufficient to enable operations to continue. Accelerators are generally used in near-surface applications in which the temperature is relatively low.
  • a cementitious composition comprising a CAHF reduces the amount of time required for the set cement to develop compressive strength by from about 10% to about 100%, additionally or alternatively, by from about 20% to about 80% or, additionally or alternatively, by from about 25% to about 50% when compared to the set time observed for an otherwise identical cementitious composition lacking a CAHF.
  • the CAHF is included in the cement with one or more conventional accelerants such as calcium nitrite, calcium nitrate, calcium chloride, calcium formate, or tricalcium silicate.
  • the CAHF functions as a corrosion inhibitor in the absence of other conventional corrosion inhibitors.
  • a corrosion inhibitor refers to a material used to protect metal-containing components (e.g., iron-containing, steel-containing) in an operation from degradation by caustic materials.
  • the CAHF comprises a diacid, it may provide corrosion resistance to metal surfaces by binding to metal surfaces, and passivating and forming a corrosion resistant film.
  • the CAHF may be effective to solubilize metal cations and/or to keep metal cations in solution, providing a higher concentration of metals in solution.
  • the CAHF may solubilize metals such iron, copper, manganese, and molybdenum and increase the solubility of these metals in solution by equal to or greater than about 10%, additionally or alternatively, equal to or greater than about 25%, additionally or alternatively, equal to or greater than about 50% or, additionally or alternatively, from about 10% to about 100% when compared to the solubility of the metal in the absence of a CAHF.
  • CAHF of the type disclosed herein as a corrosion inhibitor
  • the CAHF is included in the cement with conventional corrosion inhibitors such as nitrites and nitrates.
  • the CAHF functions as an air entrainer in the absence of other conventional air entrainers.
  • an air entrainer refers to a material that facilitates the intentional creation of air bubbles in the cementitious slurry. The air bubbles are created during mixing of the easy flowing, not hardened cementitious material, and most of them survive to be part of the hardened cementitious material.
  • air entrainment may be effective to increase the durability of the hardened cementitious material, especially in climates subject to freeze-thaw cycles, and to increase workability of the concrete while in a plastic (flowing) state.
  • the CAHF is combined with conventional air entrainers such as natural wood resins, animal fats, wetting agents, and water-soluble soaps of certain acids [0047]
  • the CAHF functioning as a water reducer, reduces the water needed to form a pumpable cementitious slurry having one or more user and/or application desired properties.
  • the cementitious composition having a lower water to cement ratio may exhibit a decreased permeability when compared to a cementitious composition prepared in the absence of a CAHF.
  • the permeability of the cementitious composition may be decreased by from about 5% to about 50%, additionally or alternatively, from about 10% to about 40% or, additionally or alternatively, from about 25% to about 40% when compared to the permeability of an otherwise identical cementitious composition lacking a CAHF.
  • the cementitious composition exhibiting reduced permeability may display beneficial attributes such as improved freeze-thaw resistance and a reduced degree of chemical attack by species such as sulfates and chlorides.
  • Low permeability cementitious compositions can also help reduce the potential for reinforcing steel to corrode when exposed to chlorides by limiting the permeation of those chlorides into the cementitious composition.
  • a cementitious composition comprising the CAHF may be generated using a lower ratio of water to cement without altering workability (slump).
  • the amount of cement utilized is reduced without altering the compressive strength when compared to a concrete prepared in the absence of a CAHF.
  • the lower cement content may result in a cementitious composition having a decreased carbon (CO2) footprint.
  • the CAHF may reduce the carbon footprint of the cementitious composition by from about 1 % to about 10% or alternatively from about 1 % to about 5% when compared to the carbon footprint of a cementitious composition lacking a CAHF.
  • the CAHF reduces shrinkage and increases the temperature-insensitive settling of concrete.
  • a sugar source e.g., a cellulose-derived reaction product
  • tank 10 which is conveyed to an Enzyme Oxidation Reactor (EOR) 20.
  • the EOR 20 contains one or more enzymes capable of oxidizing the sugar source.
  • the EOR may comprise an oxidizing enzyme (e.g., alcohol oxidase, a copper radical oxidase).
  • the EOR 20 may be operated under any conditions suitable for the formation of an oxidized sugar source, hereinafter termed a first intermediate.
  • the first intermediate from EOR 20 may then be conveyed to a Metal Oxidation Reactor (MOR) 30.
  • MOR Metal Oxidation Reactor
  • the MOR 30 comprises a metal catalyst, alternatively a transition metal catalyst, alternatively a noble metal catalyst, or alternatively a metal oxidation catalyst.
  • the metal catalyst is a metal oxidation catalyst or a supported metal catalyst.
  • the support comprises carbon, silica, alumina, titania (TiO2), zirconia (ZrO2), a zeolite, or any combination thereof, which contains less than about 1.0 weight percent (wt.%), additionally or alternatively, less than about 0.1 wt.% or, additionally or alternatively, less than about 0.01 wt.% SiO2 binders based on the total weight of the support.
  • the metal comprises one or more noble metals, for example, a Group 8 metal (e.g., Re, Os, Ir, Pt, Ru, Rh, Pd, Ag), a 3d transition metal, an early transition metal, or combinations thereof.
  • the metal oxidation catalyst comprises gold, Au.
  • the intermediate may be contacted with a metal oxidation catalyst in the MOR 30 under conditions suitable for oxidation of the first intermediate to form a second intermediate that is further oxidized .
  • the first intermediate, the second intermediate or a combination thereof may be used without additional processing as the CAHF.
  • at least a portion of the sugar source in Figure 1 is from waste streams, such as recycled cardboard. Additionally or alternatively, the sugar source in Figure 1 may be cellulosic sugars.
  • a CAHF of the type disclosed herein is a readily biodegradable product obtained from a chemoenzymatic process. This is in sharp contrast to conventional cement additives such as lignosulfonates, which commonly go through a process where sulfuric or nitric acid is introduced, producing environmentally detrimental sulfate or nitrate-based waste.
  • CAHF nitrites, nitrates, and sulfate products that are manufactured, for example, for inclusion in a cementitious composition, leading to a lower carbon footprint, as well as ancillary benefits such as lower nitrate/nitrite wastewater discharge.
  • addition of a CAHF to a cementitious material result in a delayed setting of the cementitious material. Delayed setting of the cementitious can advantageously enable increased bleed water, which is beneficial for freshly poured concrete flatwork exposed to hot dry windy environment.
  • a CAHF may be used as a set retarder in gypsum plaster formulations.
  • CAHF can replace traditional retarders (e.g., tartaric acid).
  • the CAHF is present in the gypsum plaster formulation in an amount ranging from about 0.01 wt.% to about 10 wt.% by weight of gypsum, alternatively from about 0.01 wt.% to about 5 wt.%, alternatively from about 0.1 wt.% to about 5 wt.%, alternatively from about 0.1 wt.% to about 1 wt.% or alternatively from about 2 wt.% to about 10 wt.%.
  • a CAHF of the type disclosed herein is very flexible in terms of its compatibility and can also be combined with existing corrosion inhibitors, set retarders, water reducers, air entrainers, accelerators and superplasticizers, as desired to further enhance their performance. Additional benefits of the use of a CAHF with a cementitious material include enabled re-use of returned concrete; enablement of normal later age strength development under hot weather conditions; eliminating the discharge of truck wash water which could then be used as concrete batch water For example, using a CAHF as set retarders and water reducers may allow for the use of cementitious material that is a mixture used concrete and fresh concrete. Without wishing to be limited by theory, in hot weather conditions, concrete sets fast and becomes brittle. CAHFs of the type disclosed herein may delay this process and facilitate the development of compressive strength.
  • a first aspect which is a multifunctional cement additive comprising (i) a sugar derivative comprising glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, gluconic acid oxidation products disaccharides, oxidized disaccharides, uronic acid, aldaric acid, galactonic acid, galactaric acid, glutamic acid glucodialdose, 2- ketoglucose, salts thereof, lactones thereof, or a combination thereof and (ii) a solvent.
  • a second aspect which is the additive of the first aspect wherein the sugar derivative is sourced from a cellulose feedstock.
  • a third aspect which is the additive of any of the first through second aspects wherein the sugar derivative comprises a crude mixture of sugars and sugar oxidation products.
  • a fourth aspect which is the additive of the third aspect wherein the crude mixture is a reaction product that contains at least 40 wt.% sugars and sugar oxidation products based on the total weight of the additive.
  • a fifth aspect which is the additive of any of the first through fourth aspects wherein the sugar derivative comprises a mixture of glucaric acid and gluconic acid.
  • a sixth aspect which is the additive of fifth aspect wherein the amount of glucaric acid and gluconic acid ranges from about 20 wt.% to about 80 wt.% based on the total weight of the additive.
  • a seventh aspect which is the additive of any of the first through sixth aspects wherein the sugar derivative is a mixture of two compounds selected from the group consisting essentially of dextrose, glucose, fructose, sucrose, glucaric acid, glucodialdose, gluconic acid, erythorbic acid, galactaric acid, galacturonic acid, galactonic acid and 2-ketoglucose.
  • An eighth aspect which is the additive of any of the seventh aspect where a ratio of the two compounds is from about 10:90 to about 90: 10.
  • a ninth aspect which is the additive of any of the first through ninth aspects wherein the solvent comprises methanol, ethanol, water, acetonitrile, or a combination thereof.
  • a tenth aspect which is a composition comprising (a) a cementitious material (b) a multifunctional additive comprising a sugar oxidation product and (c) a solvent wherein the multifunctional additive comprising a sugar oxidation product is a mixture of two compounds selected from the group consisting essentially of dextrose, glucose, fructose, sucrose, glucaric acid, glucodialdose, gluconic acid, erythorbic acid, galactaric acid, galacturonic acid, galactonic acid and 2-ketoglucose.
  • An eleventh aspect which is the composition of the tenth aspect wherein the multifunctional additive comprising a sugar oxidation product comprises a mixture of glucaric acid and gluconic acid.
  • a twelfth aspect which is the composition of any of the tenth through eleventh aspects wherein the amount of glucaric acid and gluconic acid ranges from about 0.1 % to about 5% based on the total weight of cementitious material.
  • a thirteenth aspect which is the composition of any of the tenth through twelfth aspects wherein the cementitious material comprises cement, concrete, shotcrete, mortar, grout, asphalt, or a combination thereof.
  • a fourteenth aspect which is the composition of any of the tenth through thirteenth aspects wherein the cementitious material comprises 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, limestone cements or a combination thereof.
  • the cementitious material comprises 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, limestone cements or
  • a fifteenth aspect which is the composition of any of the tenth through fourteenth aspects having a water: cement ratio that is reduced by from about 5% to about 40% when compared to an otherwise identical composition lacking a multifunctional additive comprising a sugar oxidation product.
  • a sixteenth aspect which is the composition of any of the tenth through fifteenth aspects having a set time that is increased by from about 20% to about 200% when compared to the set time observed for an otherwise identical cementitious composition lacking a multifunctional additive comprising a sugar oxidation product.
  • a seventeenth aspect which is the composition of any of the tenth through sixteenth aspects having a permeability that is decreased by from about 5% to about 50% when compared to an otherwise identical cementitious composition lacking a multifunctional additive comprising a sugar oxidation product.
  • An eighteenth aspect which is the composition of any of the tenth through seventeenth aspects having an increase in slump of from about 0.5 inches (in.) to about 9 in. when compared to an otherwise identical cementitious composition lacking a multifunctional additive comprising a sugar oxidation product.
  • a nineteenth aspect which is the composition of any of the tenth through eighteenth aspects having a thickening time that is increased by from about 5% to about 400% when compared to an otherwise identical cementitious composition lacking a multifunctional additive comprising a sugar oxidation product.
  • a twentieth aspect which is the composition of any of the tenth through nineteenth aspects having a compressive strength of from about 500 psi to about 8000 psi when set
  • CAHF formulations of the type disclosed herein were evaluated as concrete additives or admixtures.
  • the first formulation was designated, LG60, and was a mixture of sodium gluconate, gluconic acid, and water with a solids amount of 60 weight percent.
  • the second formulation was designated GOGA, which was mixture of gluconic acid, glucaric acid, and water with a solids amount of 40 weight percent.
  • CAHF chemical vapor deposition
  • the CAHF formulations investigated contained as indicated below: LAFARGE ALPENA Type II low alkali 0.54% 517 cement (LA Cement), ST MARY'S Type II Medium Alkali cement (MA Cement), Agg. Resources Midway PIT 2NS SAND (Sand), CARMEUSE L & ST. CEDARVILLE #67 stone (Stone), LG60, GOGA and water.
  • Cement compositions were produced according to ASTM C1810, Method B. The various compositions that were evaluated are listed in Table 1 for low alkali cement and Table 2 for medium alkali cement.
  • Table 1 and Table 2 'oz/cwt' stands for ounces of admixture per 100 lbs of cement. Slump, set time, and compression strength were measured according to ASTM C31 , ASTM C403, and ASTM C39 (on 4"X8" cylinders), respectively. Table 1
  • CAHF CAHF containing cement compositions investigated contained as indicated below: HOLCIM ST GENEVIEVE PLT. Type II Cement (Cement); Agg. Resources Midway PIT 2NS (Sand); STONECO Ottawa Lake 1/2" Limestone (Limestone); BASF MASTERAIR VR, air entrainer; LG60; GOGA and water.
  • Cement compositions were produced according to ASTM C1810, Method B. The various cement compositions that were evaluated are listed in Table 3. In Table 3, 'oz/cwt' stands for ounces of admixture per 100 lbs of cement.
  • the corrosion performance is characterized by measuring electrical conductivity (pS/cm 2 ) according to ASTM G180 and a lower value means a cement composition with higher corrosion resistance.
  • CAHF-containing cement compositions investigated contained as indicated below: LAFARGE ALPENA Type IL (10) (Cement); AGG. RESOURCES MIDWAY PIT 2NS sand (Sand); CARMEUSE L & ST. CEDARVILLE #67 stone (Stone); LG60; 53% calcium/sodium lignosulfonate (Ligno); LG60 blend - 16% LG60 + 4% triethanolamine + 1 % sodium thiocyanate + 3% com syrup; Ligno blend - 30% Ligno + 5% triethanolamine + 5% com syrup and water.
  • CAHF-containing cement compositions were produced according to ASTM C1810, Method B. The various compositions that were evaluated are listed in Table 4. In Table 4 'oz/cwt' stands for ounces of admixture per 100 lbs of cement. Slump, air entrainment, and compression strength were measured according to ASTM C31 , ASTM C231 , and ASTM C39 (on 4"X8" cylinders), respectively.
  • compositions containing the CAHF LG60 displayed comparable water reduction to lignosulfonate which lead to lower air entrainment (lower porosity) and higher compressive strength.
  • the result demonstrates the CAHF is an effective water reducer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Un additif de ciment multifonctionnel comprend (i) un dérivé de sucre comprenant de l'acide glucarique, de l'acide gluconique, de l'acide glucuronique, des produits d'oxydation du glucose, des disaccharides de produits d'oxydation d'acide gluconique, des disaccharides oxydés, de l'acide uronique, de l'acide aldarique, de l'acide galactonique, de l'acide galactarique, de la glucodialdose d'acide glutamique, du 2-cétoglucose, des sels de ceux-ci, des lactones de ceux-ci, ou une combinaison de ceux-ci et (ii) un solvant. Une composition comprenant (a) un matériau cimentaire (b) un additif multifonctionnel comprenant un produit d'oxydation de sucre et (c) un solvant, l'additif multifonctionnel comprenant un produit d'oxydation de sucre étant un mélange de deux composés choisis dans le groupe constitué essentiellement de dextrose, de glucose, de fructose, de saccharose, d'acide glucarique, de glucodialdose, d'acide gluconique, d'acide érythorbique, d'acide galactarique, d'acide galacturonique, d'acide galactonique et de 2-cétoglucose.
PCT/US2024/019954 2023-03-14 2024-03-14 Additifs de ciment multifonctionnels et procédés pour leur utilisation Ceased WO2024192251A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025010374A3 (fr) * 2023-07-03 2025-04-24 Solugen, Inc. Additifs d'origine biologique destinés à être utilisés avec des fibres

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4466834A (en) * 1983-01-03 1984-08-21 W. R. Grace & Co. Corrosion inhibiting additive for cement compositions
WO2000044487A1 (fr) * 1999-01-29 2000-08-03 W. R. Grace & Co.-Conn. Composition a base de derives du sucre pour modifier les proprietes du ciment et des compositions cimentaires, et procedes de fabrication
US20150010969A1 (en) * 2012-02-24 2015-01-08 Asahi Kasei Chemicals Corporation Method for Producing Glucaric Acid
WO2022010962A1 (fr) * 2020-07-09 2022-01-13 Solugen, Inc. Additifs multifonctionnels de ciment et procédés pour leur utilisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4466834A (en) * 1983-01-03 1984-08-21 W. R. Grace & Co. Corrosion inhibiting additive for cement compositions
WO2000044487A1 (fr) * 1999-01-29 2000-08-03 W. R. Grace & Co.-Conn. Composition a base de derives du sucre pour modifier les proprietes du ciment et des compositions cimentaires, et procedes de fabrication
US20150010969A1 (en) * 2012-02-24 2015-01-08 Asahi Kasei Chemicals Corporation Method for Producing Glucaric Acid
WO2022010962A1 (fr) * 2020-07-09 2022-01-13 Solugen, Inc. Additifs multifonctionnels de ciment et procédés pour leur utilisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025010374A3 (fr) * 2023-07-03 2025-04-24 Solugen, Inc. Additifs d'origine biologique destinés à être utilisés avec des fibres

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