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
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/26—Carbonates
• • 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
  • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B18/04—Waste materials; Refuse
  • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
  • C04B18/061—Ashes from fluidised bed furnaces
• • 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
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/02—Treatment
  • C04B20/023—Chemical treatment
• • 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
  • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
• • 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
  • 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
  • C04B28/06—Aluminous 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
  • 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
  • C04B28/06—Aluminous cements
  • C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
• • 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
  • C04B7/00—Hydraulic cements
  • C04B7/02—Portland cement
• • 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
  • C04B2111/00017—Aspects relating to the protection of the environment

Definitions

• the subject of the present invention is new binders with a low carbon balance comprising carbonated biomass ashes as well as the building materials prepared from said binders.
• binders in particular hydraulic binders, and in particular that of cements, essentially consists of calcining a mixture of judiciously chosen and dosed raw materials, also referred to by the term “raw”. Firing this cru gives an intermediate product, clinker, which, ground with calcium sulphate and any mineral additions, will give cement.
• the type of cement manufactured depends on the nature and proportions of the raw materials as well as the firing process. There are several types of cement: Portland cements (which represent the vast majority of cements produced in the world), aluminous cements (or calcium aluminate), natural quick cements, sulpho-aluminous cements, cements sulpho-belitic and other intermediate varieties.
• Portland type cements are obtained from Portland clinker, obtained after clinkering at a temperature of around 1450°C of a raw material rich in calcium carbonate in a kiln.
• the production of one tonne of Portland clinker is accompanied by the emission of large quantities of CO2 (approximately 0.8 to 0.9 tonnes of CO2 per tonne of cement in the case of a clinker).
• decarbonation is a chemical reaction that takes place when limestone, the main raw material for the manufacture of Portland cement, is heated at high temperature. The limestone is then transformed into quicklime and CO2 according to the following chemical reaction:
• the described process involves using recycled concrete fines comprising supplying recycled concrete fines with dgo 1000 ⁇ m to stockpiles or a silo as a feedstock, rinsing the feedstock to provide carbonaceous material, removing of the carbonaceous material and the cleaned exhaust, and the deagglomeration of the carbonaceous material to form the additional cementitious material, as well as the use of stockpiles or a silo containing a feedstock of recycled concrete fines with dgo 1000 pm for the cleaning of CO2-containing exhaust gases and the simultaneous production of additional cementitious material.
• this process requires the carbonated product to be dried before it can be used.
• Biomass ash i.e. ash obtained from the combustion of biomass such as wood, so-called annual plants, agricultural residues, paper and sludge from wastewater treatment plants (or sludge from STEP ) are valued through their use in different fields.
• biomass ash is used in particular to stabilize foundation soils, for the treatment of liquid effluents or even as a secondary raw material in ceramic products or as a mineral filler in bituminous coating.
• the carbonation of biomass ashes allows their use as a cement additive without this reducing the workability of the cement or concrete finally prepared.
• the carbonated biomass ashes do not behave like simple fillers but participate in the increase in performance of the binder, which makes it possible to significantly increase the rate of substitution of said binder in comparison with conventional filler, thus making it possible to significantly reduce the carbon footprint of the construction material finally prepared while maintaining mechanical properties, and in particular medium and long-term compressive strengths compatible with intended uses.
• carbonated biomass ash as a cementitious substitute therefore makes it possible to lower the carbon footprint associated with the production of the construction material not only by the capture of CO2 by the biomass ash, but also by the significant reduction in the quantity of clinker to be produced to obtain said building material.
• the subject of the present invention is a binder comprising at least 1% of carbonated biomass ash.
• carbonated biomass ashes in the binders of the invention makes it possible to significantly increase the rate of substitution of cement in comparison with conventional fillers, and therefore to significantly lower the carbon footprint of the construction material finally prepared from said binder, and while maintaining workability and mechanical properties, and in particular medium and long-term compressive strengths compatible with the uses envisaged.
• biomass ash means any mainly basic residue from the combustion of various organic plant materials, natural and non-fossil such as wood, so-called annual plants, agricultural residues, paper and sludge from wastewater treatment plants (or WWTP sludge) containing less than 11% total carbon, less than 4% inorganic carbon, and at least 1% Na2 ⁇ D equivalent.
• the biomass ashes additionally contain at least one of the following phases: whitlockite, hydroxyapatite, tremolite and/or tricalcium phosphate;
• carbonated biomass ash means any biomass ash which, after having been brought into contact with a gas stream enriched in CO2, retains part of it and contains more than 4% of inorganic carbon;
• aluminous cement means any cement, amorphous or not, obtained by firing a mixture of limestone and bauxite and containing at least 5% CA monocalcium aluminate;
• prompt natural cement means any hydraulic binder with rapid setting and hardening in accordance with standard NF P 15-314: 1993 in force on the date of the present invention.
• “prompt natural cement” designates a cement prepared from a clinker comprising: from 0% to 20% of C 3 S; from 40% to 60% of C 2 S; from 7% to 12% of C 4 AF; from 2% to 10% of C 3 A; from 10% to 15% CaCOs (calcite); from 10% to 15% of Cas(SiO 4 )2CO3 (spurrite); from 3% to 10% of sulphate phases: yeelimite C 4 A3$, langbeinite (K2Mg2(SO 4 )3, anhydrite (CaSO 4 ); and from 10% to 20% of lime, periclase, quartz and/or a or more amorphous phases;
• Portland cement means any Portland clinker-based cement classified as CEM (I, II, III, IV or V) according to standard NF EN 197-1;
• sulfoaluminous cement means any cement prepared from a sulfoaluminous clinker containing from 5% to 90% of 'yeelimite' C 4 A3$ phase, from a source of sulfate, and, optionally, a limestone addition;
• binder means any hydraulic or acali-activated binder
• activated alkali binder means any aggregate-free mixture composed of a mineral precursor (generally blast furnace slag or metakaolins) and an alkaline activator. If the precursor is a calcined clay powder, the alactiactive binder is then referred to as “geopolymer”.
• hydroaulic binder means any binder free of aggregates which reacts with water to form new phases called hydrates, such as for example a cement;
• loss on ignition means the cumulative content of bound water, organic matter, CO2 of carbonates (calcareous loads and carbonated part of the material) and any oxidizable elements.
• the loss on ignition is determined by calcination in air at a temperature of (950 +/- 25°C) according to the method described in standard NF EN 196-2 (classification index P 15-472) - Methods of cement testing - Part 2: Chemical analysis of cements; And
• construction material means mortar or concrete.
• mineralogical components of the cement
• - C represents CaO
• - A represents Al2O3
• the "inorganic carbon content” or “TIC” corresponds to the quantity (% w/w) of inorganic carbon contained in an entity (e.g carbonated biomass ash) relative to the total weight of said entity (e.g. said carbonated biomass ash).
• CHS Carbon Hydrogen Sulfur
• CT TOC+C+TIC
• the proportions expressed in % correspond to mass percentages relative to the total weight of the entity (eg clinker or cement) considered.
• the present invention therefore relates to a binder comprising at least 1% of carbonated biomass ash.
• the subject of the present invention is a binder as defined above having the following characteristics, chosen alone or in combination: the binder contains at least 5% of carbonated biomass ash; preferably the binder contains at least 6% carbonated biomass ash; more preferably the binder contains at least 7% carbonated biomass ash; more preferably the binder contains at least 8% carbonated biomass ash; more preferably the binder contains at least 9% carbonated biomass ash; most preferably, the binder contains at least 10% carbonated biomass ash; the binder contains up to 45% carbonated biomass ash; preferably the binder contains up to 40% carbonated biomass ash; most preferably, the binder contains up to 35% carbonated biomass ash; carbonated biomass ash contains at least 4.5% inorganic carbon; preferably the carbonated biomass ash contains at least 5% inorganic carbon; most preferably, the carbonated biomass ash contains at least 5.5% inorganic carbon; the binder contains 15% to 99% hydraulic binder or alkali-activated binder; preferably the binder contains
• the binder according to the present invention can be prepared according to any process known to those skilled in the art.
• the binder according to the present invention can in particular be prepared by simple mixing in a grinder or a mixer of a hydraulic binder or an alkali-activated binder with the carbonated biomass ashes, or else by mixing in a grinder or mixer a clinker, gypsum (and optionally limestone filler or any known additive) and carbonated biomass ash.
• the carbonated biomass ashes can be obtained according to any method known to those skilled in the art.
• a process for the preparation of carbonated biomass ash comprising the following steps: introduction of the biomass ash into a reactor of the rotating drum, mixer, container or fluidized bed type; bringing the ashes into contact with a source of CO2 such as exhaust gases from a cement works or a thermal power plant; and recovering the carbonated biomass ash obtained.
• the binder according to the present invention can be used to prepare a building material.
• the present invention also relates to a construction material comprising a binder as defined previously.
• Different carbonated biomass ashes are obtained by placing a mixture of approximately 250 g of ashes obtained by combustion of different biomasses and 15% by mass of water ashes in a hermetically sealed bowl which is itself fixed on the base of a heated mixing robot.
• compositions and characteristics of the biomass ashes used (Ashes 1 to 4) before carbonation are reported in Table 1 below, in comparison with the composition and characteristics of the fly ashes (non-carbonated) usually used in the cement industry.
• the reactor is equipped with a cup containing water to regulate the relative humidity in the reactor.
• the temperature of the bowl is maintained at 55°C.
• the cover of the bowl is equipped with 2 orifices which allow the injection of a gas and its evacuation.
• the gas is injected for a mixing time of 1 hour and consists of 100% CO 2 .
• the thus carbonated biomass ash has the following characteristics (Table 2), in comparison with non-carbonated biomass ash.
• a reference Portland cement of class CEM I 52.5 R is mixed with different quantities of non-carbonated or carbonated ash from example 1.
• compositions of binders 2 to 5 (binders according to the invention) and 6 to 9 (binders prepared from non-carbonated ashes) thus obtained are reported in Tables 3.1, 3.2 and 3.3 below.
• a spreading measurement was carried out in accordance with standard EN 1015-3 on 3 mortars manufactured according to standard 196-1 by mixing 450g of binder 1, 4 or 8, 1350g of sand and 225g of water.
• the compressive strength of the binders obtained in example 2 was measured on prismatic specimens of standardized mortar (4x4x16cm3), at different times (1, 2, 7 and 28 days) according to standard EN 196-1.
• binders according to the invention i.e. binders 4 and 5
• binders 4 and 5 have acceptable performances with regard to those observed for the reference CEM I at all deadlines. We thus note a maintenance of mechanical performance in the short, medium and long term at an acceptable level.
• coal-type fly ashes whose composition is reported in Table 1 are carbonated according to the protocol of Example 1.
• Binder 10 is obtained by mixing a reference Portland cement of class CEM I 52.5 R with the carbonated ash thus obtained in a proportion (% w/w) 75/25.
• the binder 11 is obtained by carbonation according to the protocol of Example 1 of a 75/25 (% w/w) mixture of a reference Portland cement of the CEM I 52.5 R class with the ashes of paper n °4 of Example 1 (non-carbonated ash). 5.3 - Comparative results
• binder 11 The workability of binder 11 is evaluated according to the protocol of example 3.
• the mortar prepared from binder 11 is too dry and therefore has no spreading, making it impossible to use.
• the compressive strengths of binders prepared from fly ash from coal combustion are significantly lower than the compressive strengths of binders prepared from carbonated biomass ash at 2, 7 and 28 days.
• the results obtained for binder 11 are extremely low (loss of more than 50% in performance compared to the 100% Portland reference) and render this binder unusable.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Environmental & Geological Engineering (AREA)
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• Curing Cements, Concrete, And Artificial Stone (AREA)
• Processing Of Solid Wastes (AREA)

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• 2022
  • 2022-02-17 FR FR2201385A patent/FR3132710A1/fr active Pending
• 2023
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