Glassy solids, methods for making same, and uses thereof

Abstract

The present invention relates to a glassy solid obtained by carbonation of a solid glassy precursor having an SiO2 content of at least 65% by weight. The present invention further relates to a mechanochemically carbonated glassy solid and a method for producing the same. The present invention further relates to the use of the (mechanochemically carbonated) glassy solid, for example as a filler. The present invention further relates to a composition containing the (mechanochemically carbonated) glassy solid and an additional material selected from the group consisting of asphalt, cement, geopolymers, polymers, and combinations thereof. The present invention also relates to a method for producing concrete.

Description

[Technical Field]

[0001] Technical Field The present invention relates to a glassy solid obtained by carbonation of a solid glassy precursor. The present invention further relates to a mechanochemically carbonated glassy solid and a method for producing the same. The present invention further relates to the use of the (mechanochemically carbonated) glassy solid, for example as a filler. The present invention further relates to a composition containing the (mechanochemically carbonated) glassy solid and an additional material selected from the group consisting of asphalt, cement, geopolymers, polymers, and combinations thereof. The present invention also relates to a method for producing concrete. [Background technology]

[0002] Background technology Concrete is a composite material containing a matrix of aggregate (typically a rock-based material) and a binder (typically Portland cement or asphalt) that holds the matrix together. Concrete is one of the most frequently used building materials and is said to be the second most widely used material on Earth after water.

[0003] To reduce the cost of concrete and the CO2 emissions generated by global cement production, numerous research efforts have been made to identify inexpensive materials that can be used as fillers or alternative binders to replace binder components without adversely affecting the properties of concrete. Such secondary cementitious materials are of interest to a wide range of industries.

[0004] An example of a widely used cement filler is limestone. A comprehensive overview of fillers in cementitious materials can be found in John, Vanderley M., et al. "Fillers in cementitious materials—Experience, recent advances and future potential." Cement and Concrete Research 114 (2018): 65-78.

[0005] Portland cement production contributes approximately 8% of global carbon dioxide emissions. According to Vanderley et al., traditional mitigation strategies for CO2 emissions in the cement industry are insufficient to ensure the necessary mitigation in a scenario where cement demand increases. Currently, cement production is increasing due to a combination of increasing urbanization and the replacement of aging infrastructure. Therefore, cement industry leaders have considered the adoption of carbon capture and storage (CCS) as an inevitable solution, despite its high cost and environmental risks.

[0006] Therefore, there remains a need for the development of affordable filler technologies that can combine both the CO2 emission reductions achieved through reduced cement production and those achieved through carbon capture technologies, without negatively affecting the properties of concrete.

[0007] Korean Patent Application Publication No. 20110017279 discloses direct carbonation of glass with the specific goal of CO2 sequestration. To this end, a specific borosilicate glass with a relatively low silicon dioxide content and a high alkaline earth metal oxide content (containing 15-55 mol% SiO2, 10-40 mol% B2O3, and 10-40 mol% CaO, SrO, BaO, or MgO) is produced, which is then subjected to an aqueous carbonation process. Korean Patent Application Publication No. 20110017279 relies on a new specific type of glass produced by melting at 1000-1400°C for the purpose of CO2 capture, which makes it very energy inefficient. Summary of the Invention [Problem to be solved by the invention]

[0008] It is an object of the present invention to provide an improved filler for cement, geopolymer, or asphalt binders.

[0009] It is a further object of the present invention to provide an improved filler for cement, geopolymer, or asphalt binder that is inexpensive to produce.

[0010] It is a further object of the present invention to provide an improved filler for cement, geopolymer, or asphalt binder produced using CO2 capture technology.

[0011] It is a further object of the present invention to provide an improved filler for cement, geopolymer, or asphalt binder that improves properties such as compressive strength, strength activity index, and / or water demand of the resulting concrete. [Means for solving the problem]

[0012] Summary of the Invention The inventors believe that they have succeeded for the first time in carbonating a solid glassy precursor having an SiO content of at least 65 wt.% (relative to the total weight of the glassy precursor). Thus, in a first aspect, the present invention provides a glassy solid obtainable by carbonation of a solid glassy precursor, said glassy precursor having an SiO content of at least 65 wt.%, preferably at least 70 wt.% (relative to the total weight of the glassy precursor).

[0013] In another aspect, the present invention provides a method for producing a mechanochemically carbonated glassy solid, comprising the steps of: a) providing a feedstock comprising or consisting of a solid glassy precursor; b) providing a gas comprising CO2; c) introducing the raw material and the gas into a mechanical stirring unit; and d) subjecting the raw material to a mechanical stirring operation in the presence of the gas in the mechanical stirring unit to obtain a mechanochemically carbonated glassy solid; The present invention provides a method comprising:

[0014] Since the raw material is preferably a solid, preferably the present invention provides a method for producing a mechanochemically carbonated glassy solid, comprising the steps of: a) providing a solid feedstock comprising or consisting of a solid glassy precursor; b) providing a gas comprising CO2; c) introducing the solid feedstock and the gas into a mechanical stirring unit; and d) subjecting the solid raw material to a mechanical stirring operation in the presence of the gas in the mechanical stirring unit to obtain a mechanochemically carbonated glassy solid; The present invention provides a method comprising:

[0015] This method can be applied to various types of glassy precursors and advantageously yields unique mechanochemically carbonated glassy solids.

[0016] In another aspect, the present invention provides mechanochemically carbonated glassy solids obtainable by the methods for making mechanochemically carbonated glassy solids described herein.

[0017] As shown in the accompanying examples, it has been found that the use of such carbonated glassy solids, particularly the mechanochemically carbonated glassy solids described herein, as fillers in cement surprisingly increases the compressive strength of the resulting concrete beyond that achieved when pure cement is used. Furthermore, the setting time for strength development is significantly improved (reduced) compared to when non-carbonated glass is used as a filler. Additionally, much larger amounts of the glassy solids can be used as fillers while the properties of the concrete remain acceptable or even improved.

[0018] Furthermore, it has been found that the durability of concrete produced using the carbonated glassy solids is significantly improved. Without wishing to be bound by any theory, the inventors believe this is due to improved hydration at the microscale and submicroscale, reduced chloride permeability, reduced concrete porosity, and / or passivation of free lime. Furthermore, the increased oxygen content compared to the untreated precursor or raw material is believed to improve dispersibility in polar solvents and compatibility with materials containing epoxy or carboxyl functionality.

[0019] Additionally, as shown in the accompanying examples, water demand is reduced compared to pure cement and compared to cement filled with uncarbonated glass. This is particularly surprising considering the smaller particle size of mechanochemically carbonated glass compared to uncarbonated glass. A reduction in particle size is generally associated with an increase in water demand. A reduction in water demand compared to untreated raw materials or pure cement can contribute to improved properties such as workability, compressive strength, permeability, waterproofing, durability, weather resistance, drying shrinkage, and cracking potential. For these reasons, limiting and controlling the amount of water in concrete is important for both workability and service life. Thus, the present invention allows for better control of water demand. Without wishing to be bound by any theory, the inventors believe that the method of the present invention may reduce the amount of devitrified (i.e., crystallized) domains, thereby increasing the overall amorphous content of the glassy material. This is believed to improve water demand. Without wishing to be bound by any theory, it is believed that the mechanochemical process of the present invention increases the amorphous content as analyzed by XRD, and maintains at least some crystalline domains that may be present in the raw materials through an internal structure in a microcrystalline form that maintains a more typical disordered structure. This disordered macrostructure therefore provides greater reactivity and improves the hydration of the cement.

[0020] Additionally, because the production of the mechanochemically carbonated glassy solids relies on inexpensive CO2 capture technology platforms that can operate with dilute CO2 streams, such as those directly dependent on point source emissions from combustion plants, it can be produced in an economically viable manner, providing a filler that combines both the CO2 emission reductions achieved through reduced cement production and the CO2 emission reductions achieved through CO2 sequestration. Thus, the carbonated glassy solids of the present invention, and particularly the mechanochemically carbonated glassy solids of the present invention, combine unique mechanical properties with cost-effective CO2 capture technology, making them excellent fillers for many applications.

[0021] In another aspect, the present invention provides a composition containing a carbonated glassy solid as described herein, particularly a mechanochemically carbonated glassy solid as described herein, and an additional material selected from the group consisting of asphalt, geopolymer, cement, polymer, and combinations thereof.

[0022] In another aspect, the present invention provides a method for making the compositions described herein, comprising: (i) providing a carbonated glassy solid as described herein, particularly a mechanochemically carbonated glassy solid as described herein; (ii) providing an additional material selected from the group consisting of asphalt, geopolymer, cement, polymer, and combinations thereof; and (iii) combining the carbonated glassy solid of step (i) with the material of step (ii); The present invention provides a method comprising:

[0023] In another aspect, the present invention provides a method for producing concrete or mortar, comprising the steps of: (i) providing a carbonated glassy solid as described herein, particularly a mechanochemically carbonated glassy solid as described herein, and an additional material selected from the group consisting of asphalt, cement, geopolymer, and combinations thereof, optionally in the form of a composition as described herein; (ii) providing construction aggregates; and (iii) contacting, preferably mixing, the carbonated glassy solid and additional material of step (i) with the construction aggregate and optional water of step (ii); The present invention provides a method comprising:

[0024] In another aspect, the present invention provides a concrete or mortar obtainable by the method for making concrete described herein.

[0025] In another aspect, the present invention provides a method for producing a carbonated glassy solid as described herein, in particular a mechanochemically carbonated glassy solid as described herein, as a filler, preferably in a material selected from the group consisting of asphalt, geopolymers, cement, mortar, polymers, and combinations thereof; · As a partial replacement for asphalt, geopolymer, or cement in concrete or mortar; · To increase the compressive strength of concrete or mortar; · To improve the durability of concrete or mortar; · To reduce the expansion of concrete; · To improve the durability of concrete or mortar by reducing chloride permeability and / or porosity; To improve the strength activity index of concrete or mortar; and / or To reduce the water demand of concrete or mortar, Preferably, To simultaneously improve the strength activity index of concrete and reduce the water demand of concrete; or ·To simultaneously improve the strength activity index of mortar and reduce the water demand of mortar; Provide use. DETAILED DESCRIPTION OF THE INVENTION

[0026] Description of the embodiment As used herein, the word "comprise" and its variations, such as "comprises" and "comprising," are to be interpreted in an open and inclusive sense, meaning that the described embodiment includes the recited features but does not exclude the presence of other features unless it renders the embodiment impracticable.

[0027] As used herein, the terms "one embodiment," "particular embodiment," "embodiment," and the like should be interpreted to mean that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment. Thus, the appearances of such terms in various places throughout this specification do not necessarily all refer to the same embodiment. Furthermore, particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. For example, certain features of the present disclosure that are described herein in the context of separate embodiments are expressly contemplated as being combined in a single embodiment.

[0028] As used herein, the singular forms "a," "an," and "the" should be construed to include plural referents unless the content clearly dictates otherwise. It should also be noted that the term "or" is generally used in its broadest sense, i.e., to mean "and / or," unless the content clearly dictates otherwise.

[0029] Throughout this specification, references to compounds that are salts should always be taken to include the anhydrous form of the compound as well as solvates (especially hydrates).

[0030] The term "solid vitreous precursor" as used herein should be interpreted to include any amorphous solid material, typically obtained by melt casting. The solid vitreous precursor is preferably silica-based (i.e., a solid material containing SiO). The solid vitreous precursor is preferably transparent. In all embodiments of the invention described herein, the solid vitreous precursor is preferably in the form of a monolithic glass, such as a fusion-cast monolithic glass. The solid vitreous precursor is preferably essentially free of crystalline phases. In some embodiments, the amount of crystalline phase, as determined by X-ray diffraction, is less than 5% by volume, preferably less than 2% by volume, and more preferably less than 1% by volume of the solid vitreous precursor or solid raw material. A phase is considered crystalline if the intensity of its reflection is more than 10% higher than the background.

[0031] As used herein, the term "carbonated glassy solid" is used to refer to a glassy solid obtained by any process of direct carbonation, including dry carbonation and aqueous carbonation. Thus, the expression "carbonated glassy solid" as used herein, unless otherwise specified (e.g., by specifying a "mechanochemically carbonated glassy solid"), is understood to encompass a carbonated glassy solid obtained by dry mechanochemical carbonation, an aqueous carbonation process, or any other carbonation route described herein.

[0032] As used herein, the term "mechanochemically carbonated glassy solid" is used to refer to a glassy solid obtained by the mechanochemical carbonation method of the present invention.

[0033] According to the present invention, the BET surface area referred to herein is determined at a temperature of 77 K using a sample mass of 0.1 to 0.5 g. The BET surface area referred to herein is determined using nitrogen. A preferred analytical method for determining the BET surface area involves heating the sample to 400°C for a desorption cycle prior to surface area analysis. A suitable and therefore preferred analytical instrument for determining the BET surface area is a Micromeritics Gemini VII 2390 surface analyzer, preferably equipped with a Micromeritics FlowPrep 060 flow gas degassing unit.

[0034] As used herein, TGA refers to thermogravimetric analysis, a technique known to those skilled in the art. A preferred TGA configuration in the context of the present invention is a Setaram TAG 16 TGA / DSC dual chamber balance using 0.1-2 mg samples. In accordance with the present invention, TGA is performed in an inert atmosphere such as nitrogen or argon.

[0035] According to the present invention, particle size distribution characteristics such as D10, D50, and D90, as well as specific surface area (unless explicitly stated to be BET surface area) referred to herein are determined by measuring with a laser light scattering particle size analyzer utilizing Fraunhofer light scattering theory, such as a Brookhaven laser particle size analyzer, model Microbrook 2000LD, or other instrument with equivalent or greater sensitivity, and reporting the data using a volume-equivalent sphere model. As known to those skilled in the art, D50 is the median diameter by mass, i.e., the diameter at which 50% of the sample's mass is made up of smaller particles. Similarly, D10 and D90 represent the diameter at which 10% or 90% of the sample's mass is made up of smaller particles.

[0036] The total carbon (TC) content referred to herein is preferably determined according to the method described in Soil Sampling and Methods of Analysis, 2nd Ed., CRC Press (2008), pp. 244 et seq., which is incorporated by reference. The total carbon (TC) content is always expressed herein as a weight percent based on the total weight of the composition being measured, i.e., the total weight of the solid vitreous precursor or the total weight of the carbonated vitreous solid.

[0037] In accordance with the present invention, the compressive strength, strength activity index, and water demand referred to herein are determined in accordance with ASTM C311 / C311 M-22. As will be apparent to those skilled in the art, in conducting these tests, a vitreous precursor or carbonated glass of the present invention was used in place of the "fly ash or natural pozzolan" specified in the standard.

[0038] For purposes of this disclosure, the ideal gas law is assumed so that volume percent of a gas is considered to be equivalent to mole percent.

[0039] Carbonated glassy solid As shown in the accompanying examples, the inventors have found that (i) glassy precursors with high silica content (such as soda-lime glass) can be efficiently carbonated, and (ii) the corresponding carbonated glassy solid can be provided in a form that exhibits excellent performance in concrete. Accordingly, in a first aspect, the present invention provides a carbonated glassy solid obtained by carbonation of a solid glassy precursor, said glassy precursor having an SiO2 content of at least 65 wt% (based on the total weight of the glassy precursor).

[0040] Properties of carbonated glassy solids In a preferred embodiment, the carbonated glassy solid meets the strength requirements set forth in ASTM C618-12a(2012) and / or CSA A3001-18(2018).

[0041] In an embodiment, the carbonated glassy solid is 0.3 m 2 / g or more, preferably 0.5m 2 / g or more, more preferably 0.8m 2 For example, a carbonated glassy solid has a specific surface area of at least 0.3 m 2 / g, at least 0.35m 2 / g, at least 0.40m 2 / g, at least 0.45m 2 / g, at least 0.50m 2 / g, at least 0.55m 2 / g, at least 0.70m 2 / g, at least 0.65m 2 / g, at least 0.70m 2 / g, at least 0.75m 2 / g, at least 0.8m 2 / g, at least 0.85m 2 / g, at least 0.90m 2 / g, at least 0.95m 2 / g, at least 1.0m 2 / g.

[0042] In a preferred embodiment, the carbonated glassy solid is 50 ml 2 / g or less, preferably 30m 2 / g or less, more preferably 10m 2 For example, carbonated glassy solids have a specific surface area of up to 50 m 2 / g, up to 48m 2 / g, up to 46m 2 / g, up to 44m 2 / g, up to 42m 2 / g, up to 40m 2 / g, up to 38m 2 / g, up to 36m 2 / g, up to 34m 2 / g, up to 32m 2 / g, up to 30m 2 / g, up to 28m 2 / g, up to 26m 2 / g, up to 24m 2 / g, up to 22m2 / g, up to 20m 2 / g, up to 18m 2 / g, up to 16m 2 / g, up to 14m 2 / g, up to 12m 2 / g, up to 10m 2 / g, up to 8m 2 / g, up to 6m 2 / g, up to 4m 2 / g, up to 2m 2 / g.

[0043] In a more preferred embodiment, the carbonated glassy solid is 5 ml 2 / g, preferably less than 3m 2 / g, more preferably less than 2m 2 For example, a carbonated glassy solid has a specific surface area of less than 5.0 m 2 / g, less than 4.5m 2 / g, less than 4.0m 2 / g, less than 3.5m 2 / g or less, 3.0m 2 / g or less, 2.5m 2 / g or less, 2.0m 2 / g or less, 1.5m 2 / g or less.

[0044] The inventors have observed that carbonated glassy solids having a specific surface area within a particular range provide surprising carbonation results when compared to the untreated precursor. Thus, in accordance with a highly preferred embodiment of the present invention, the carbonated glassy solids have a specific surface area of 0.3 to 50 m. 2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.8 to 50m 2 / g specific surface area, e.g., 0.3 to 50 m 2 / g, preferably 0.3 to 30m 2 / g, more preferably 0.3 to 10m 2 Specific surface area in the range of 0.5~50m / g 2 / g, preferably 0.5 to 30m 2 / g, more preferably 0.5 to 10m 2Specific surface area in the range of 0.8~50m / g 2 / g, preferably 0.8 to 30m 2 / g, more preferably 0.8 to 10m 2 Specific surface area in the range of 0.3~5.0m / g 2 / g, preferably 0.3 to 3.0 m 2 / g, more preferably 0.3 to 2.0m 2 Specific surface area in the range of 0.5~5.0m / g 2 / g, preferably 0.5 to 3.0 m 2 / g, more preferably 0.5 to 2.0 m 2 Specific surface area in the range of 0.8~5.0m / g 2 / g, preferably 0.8 to 3.0 m 2 / g, more preferably 0.8 to 2.0 m 2 / g range.

[0045] Without wishing to be bound by any theory, the inventors believe that the increase in specific surface area provided by the dry mechanochemical carbonation process of another aspect of the invention (described elsewhere herein) is associated with the observed beneficial properties, such as superior strength activity index and reduced water demand. Accordingly, embodiments of the invention provide carbonated glassy solids as described herein obtained by simultaneous carbonation and increase in specific surface area of a solid glassy precursor, wherein the ratio of the specific surface area of the carbonated glassy solid to the specific surface area of the solid glassy precursor is at least 5:1, preferably at least 7:1, and more preferably at least 10:1.

[0046] Without wishing to be bound by any theory, the inventors believe that the increased BET surface area provided by the dry mechanochemical carbonation process of another aspect of the invention (described elsewhere herein) is associated with the observed beneficial properties, such as superior strength activity index and reduced water demand. Accordingly, embodiments of the invention provide carbonated glassy solids as described herein obtained by the simultaneous carbonation and BET surface area increase of a solid glassy precursor, wherein the ratio of the BET surface area of the carbonated glassy solid, preferably the mechanochemically carbonated glassy solid, to the BET surface area of the glassy precursor is at least 4:1, preferably at least 8:1, and more preferably at least 15:1.

[0047] Without wishing to be bound by any theory, the inventors believe that the increase in BET surface area provided by the dry mechanochemical carbonation process of another embodiment of the present invention (which is described elsewhere herein) can be primarily attributed to an increase in the number of pores observed due to a decrease in the average pore width and an increase in the total pore surface area. Thus, in embodiments of the present invention, there is provided a carbonated glassy solid obtained by simultaneous carbonation and BET surface area increase of a clay precursor, wherein the BJH desorption cumulative surface area of the pores of the carbonated glassy solid, preferably the mechanochemically carbonated glassy solid, is at least 110%, preferably at least 120%, more preferably at least 150% of the BJH desorption cumulative surface area of the pores of the solid glassy precursor, and the desorption average pore width (4V / A by BET) of the carbonated glassy solid, preferably the mechanochemically carbonated glassy solid, is not more than 90%, preferably not more than 85%, more preferably not more than 80% of the desorption average pore width (4V / A by BET) of the solid glassy precursor.

[0048] In an embodiment of the invention, the carbonated glassy solid has one, two, or three, preferably three, of the following characteristics: D10 in the range of 0.005 to 5 μm, preferably 0.01 to 2 μm, most preferably 0.1 to 1.5 μm; D50 in the range of 0.1 to 50 μm, preferably 0.5 to 25 μm, most preferably 1 to 10 μm; D90 in the range of 0.5 to 100 μm, preferably 1 to 50 μm, most preferably 5 to 25 μm.

[0049] In an embodiment of the present invention, there is provided a carbonated glassy solid as described herein obtained by simultaneous carbonation and size reduction of a solid glassy precursor, wherein the ratio of D50 of the carbonated glassy solid, preferably the mechanochemically carbonated glassy solid, to D50 of the glassy precursor is less than 0.5:1, preferably less than 0.1:1, more preferably less than 0.05:1.

[0050] In an embodiment of the invention, the carbonated glassy solid has a total carbon content of at least 0.1 wt.%, preferably at least 0.15 wt.%, more preferably at least 0.2 wt.%.

[0051] In an embodiment of the invention, the carbonated glassy solid has a strength activity index (SAI) at 7 days of at least 60%, preferably at least 80%.

[0052] In an embodiment of the invention, the carbonated glassy solid has a strength activity index (SAI) at 28 days of at least 80%, preferably at least 100%.

[0053] In an embodiment of the invention, the carbonated glassy solid has a water demand of less than 96%, preferably less than 95%.

[0054] The inventors have found that preferred methods for producing carbonated glassy solids described elsewhere herein, particularly methods performed on solid raw materials, do not result in significant loss of sodium from the precursor. Accordingly, in embodiments of the present invention, the sodium content of the carbonated glassy solid is at least 3.75 wt. % (based on the total weight of the carbonated glassy solid), preferably at least 7.5 wt. % (based on the total weight of the carbonated glassy solid). In embodiments of the present invention, there are provided carbonated glassy solids as described herein, obtained by carbonation of a glassy solid precursor, wherein the ratio of the sodium content of the carbonated glassy solid, preferably the mechanochemically carbonated glassy solid, to the sodium content of the glassy precursor is in the range of 0.8 to 1.2, preferably in the range of 0.9 to 1.1, and more preferably in the range of 0.92 to 1.05.

[0055] Characterization of glassy solid precursors In an embodiment, the solid vitreous precursor comprises recycled glass, preferably recycled soda-lime glass, more preferably recycled soda-lime container glass or sheet glass, and most preferably recycled soda-lime container glass. A typical example is a soda-lime glass bottle or jar that has been used and then crushed or ground to form recycled or waste particulate glass material, which can be carbonated to form the carbonated vitreous solid of the present invention.

[0056] In an embodiment of the present invention, the solid glassy precursor comprises: an SiO2 content of at least 70% by weight (based on the total weight of the glassy precursor); and / or a combined amount of alkaline earth metal oxides and hydroxides of less than 20% by weight (relative to the total weight of the glassy precursor), preferably less than 15% by weight (relative to the total weight of the glassy precursor); It has.

[0057] In a preferred embodiment of the present invention, the solid glassy precursor comprises an SiO2 content of at least 70% by weight (based on the total weight of the glassy precursor); a B2O3 content of at least 5 wt.-% (relative to the total weight of the glassy precursor), preferably at least 7 wt.-% (relative to the total weight of the glassy precursor); and a combined amount of alkaline earth metal oxides and hydroxides preferably less than 4 wt. % (relative to the total weight of the glassy precursor), preferably less than 1 wt. % (relative to the total weight of the glassy precursor); Such glasses correspond to borosilicate glasses.

[0058] In a preferred embodiment of the present invention, the glassy precursor comprises an SiO2 content of at least 70% by weight (based on the total weight of the glassy precursor); a Na2O content of at least 5 wt.-% (relative to the total weight of the glassy precursor), preferably at least 10 wt.-% (relative to the total weight of the glassy precursor); and a combined amount of alkaline earth metal oxides and hydroxides of preferably at least 5 wt. % (relative to the total weight of the glassy precursor), preferably at least 10 wt. % (relative to the total weight of the glassy precursor); Such glasses correspond to soda-lime glasses.

[0059] Without wishing to be bound by any theory, it is believed that the presence of at least some alkaline earth metal oxide or hydroxide promotes carbonation. Thus, according to some embodiments or preferred embodiments of the present invention, the solid vitreous precursor described herein has a combined amount of alkaline earth metal oxide and hydroxide of at least 0.01 wt.%, preferably at least 0.05 wt.%. It will therefore be understood that, according to some (preferred) embodiments, the solid vitreous precursor has a combined amount of alkaline earth metal oxide and hydroxide in the range of 0.01 to 20 wt.%.

[0060] METHOD FOR PRODUCING MECHANOChemically CARBONATED VITRUS SOLIDS AND MECHANOChemically CARBONATED VITRUS SOLIDS OBTAINED THEREFROM Without wishing to be bound by any theory, the inventors believe that the dry mechanochemical carbonation process of the present invention imparts unique and desirable properties to the carbonated glass obtained thereby. For example, the unique surface area and pore characteristics provided by the dry mechanochemical carbonation process of the present invention are believed to be important for realizing the surprising performance of the material in, for example, concrete.

[0061] In a further aspect, the present invention provides a method for producing a mechanochemically carbonated glassy solid, comprising the steps of: a) providing a feedstock comprising or consisting of a solid glassy precursor; b) providing a gas comprising CO2; c) introducing the raw material and the gas into a mechanical stirring unit; and d) subjecting the raw material to a mechanical stirring operation in the presence of the gas in the mechanical stirring unit to obtain a mechanochemically carbonated glassy solid; The present invention provides a method comprising:

[0062] The feedstock is preferably a solid feedstock, and as such the present invention preferably provides a method for producing a mechanochemically carbonated glassy solid, comprising the steps of: a) providing a solid feedstock comprising or consisting of a solid glassy precursor; b) providing a gas comprising CO2; c) introducing the solid feedstock and the gas into a mechanical stirring unit; and d) subjecting the solid raw material to a mechanical stirring operation in the presence of the gas in the mechanical stirring unit to obtain a mechanochemically carbonated glassy solid; The present invention provides a method comprising:

[0063] Process Description The term "solid feedstock" should be interpreted as a solid material consisting of or including a solid vitreous precursor. The solid vitreous precursor can be mixed with other materials (e.g., fly ash) to form the solid feedstock. Preferably, however, the solid feedstock consists essentially of the solid vitreous precursor and optional water, which allows the process conditions to be optimized to achieve the desired carbonated glass properties without considering the properties of other materials present in the feedstock.

[0064] Given the guidance provided in this disclosure, it is within the ability of one skilled in the art to adjust the relevant process parameters to obtain mechanochemically carbonated glassy solids having the properties enumerated herein.

[0065] The gas provided in step (b) may be any gas stream containing CO2, such as ordinary air, a waste gas stream having a low CO2 concentration, or a concentrated CO2 stream.

[0066] In an embodiment of the methods described herein, the gas provided in step (b) is ordinary air.

[0067] In a highly preferred embodiment of the method described herein, the gas provided in step (b) is flue gas, particularly flue gas from fossil fuel combustion, wood pellet combustion, biomass combustion, or municipal waste combustion. The fossil fuel combustion may be coal, petroleum coke, oil, natural gas, shale oil, bitumen, tar sands oil, or heavy oil combustion, or any combination thereof. The flue gas may optionally be treated to reduce its water content, SO2 content, and / or NOx content.

[0068] The CO concentration in the gas provided in step (b) is preferably at least 0.1% by volume, more preferably at least 0.5% by volume. Typical CO concentrations in flue gases range from 1 to 15% by volume, e.g., 2 to 10% by volume, so the gas provided in step (b) preferably has a CO concentration in the range of 1 to 15% by volume, e.g., 2 to 10% by volume. In alternative embodiments of the invention, the gas provided in step (b) comprises at least 80% by volume of CO, preferably at least 95% by volume. In some embodiments of the invention, the gas provided in step (b) comprises at least 80% by volume of CO, preferably at least 95% by volume of CO, and less than 1000 ppm (v / v) of HO, preferably less than 100 ppm (v / v) of HO. In some embodiments, the gas provided in step (b) comprises at least 0.1% by volume of CO and 5 to 25% by volume of HO. For example, in the case of exhaust gas, the gas provided in step (b) preferably comprises CO in the range of 1-15 vol%, e.g., 2-10 vol%, and HO in the range of 5-25 vol%, e.g., 15-20 vol%. The gas is typically not in a supercritical state, as supercritical conditions are not required for the mild mechanochemical carbonation process of the present invention. Therefore, in any embodiment of the present invention, it is highly preferred that the gas is not in a supercritical state.

[0069] In some embodiments of the present invention, the methods described herein are provided with the proviso that the temperature and pressure during step (d) are less than the saturated vapor pressure of water at the temperature in the mechanically stirred unit.

[0070] The phrase "in the presence of said gas" in step (d) should be interpreted to mean that when step (d) is initiated, the atmosphere within the mechanically stirred unit consists essentially of the gas provided in step (b). Those skilled in the art will understand that the composition of the gas will change as the reaction progresses unless the reactor (mechanically stirred unit) is continuously purged or refilled.

[0071] Typically, step (d) can be carried out at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure. Typically, step (d) is preferably carried out at atmospheric pressure or above. Thus, step (d) is preferably carried out at a pressure of at least about 100 kPa (e.g., at least 101.325 kPa). In a preferred embodiment of the present invention, step (d) is carried out at a pressure greater than about 300 kPa (e.g., 303.975 kPa), preferably greater than about 600 kPa (e.g., 607.95 kPa). In an alternative embodiment of the present invention, step (d) is carried out at a pressure less than about 100 kPa (e.g., at least 101.325 kPa), for example, less than 50 kPa or less than 10 kPa. Those skilled in the art will appreciate that the pressure of the gas will change (if not actively maintained) as the reaction progresses. In these embodiments, it should be understood that when step (d) is initiated, the pressure within the mechanical stirring unit is as defined herein. In some embodiments, throughout most or substantially all of step (d), the pressure within the mechanical agitation unit is as defined herein.

[0072] In highly preferred embodiments of the methods described herein, step (d) is carried out at a pressure below the critical pressure of carbon dioxide. Furthermore, the inventors have discovered that very high pressures are not required to produce the carbonated glassy solids of the present invention, allowing the method to be carried out in a very energy-efficient manner. Accordingly, step (d) is preferably carried out at a pressure below 10,000 kPa, preferably below 5,000 kPa, more preferably below 2,500 kPa, and most preferably below 1,000 kPa. Those skilled in the art will appreciate that the gas pressure will change (if not actively maintained) as the reaction progresses. In these embodiments, it should be understood that the pressure within the mechanically agitated unit is as defined herein at at least one point during step (d), e.g., when step (d) is initiated. In some embodiments, the pressure within the mechanically agitated unit is as defined herein throughout most or substantially all of step (d).

[0073] In a highly preferred embodiment of the method described herein, step (d) is carried out at a temperature below 150°C, preferably below 100°C, preferably below 90°C, more preferably below 80°C, and most preferably below 75°C to promote carbonation. In a highly preferred embodiment of the invention, step (d) is carried out at a temperature in the range of 45-85°C, preferably 55-70°C. In a preferred embodiment of the invention, no active heating is performed, and the temperature increase is due to friction from mechanical agitation or the exothermic reaction that occurs during mechanochemical carbonation. The temperature is preferably determined by the solid material in the reactor (i.e., the mechanical agitation unit) during processing.

[0074] In an embodiment of the invention, step (d) is carried out for at least 1 minute, preferably at least 30 minutes, such as at least 1 hour, at least 4 hours, or at least 8 hours.

[0075] In a preferred embodiment of the present invention, step (d) is substantially free of CO2 solubilizers, such as glycerin (propane-1,2,3-triol), which function to increase the solubility of carbon dioxide in aqueous solutions and allow for the formation of carbonate concentrations for sequestering carbon dioxide.

[0076] The low temperature requirements of the process mean that no fossil fuels are required and, where the friction generated by mechanical agitation is insufficient to reach a target temperature such as above 45°C, it is feasible to use electrical heating means (or low calorific value green fuel sources) to provide heat, thus avoiding fossil fuels throughout the production chain.

[0077] As with any chemical process, the appropriate reaction time will depend largely on the desired degree of carbonation, the desired surface area, and the applied pressure, temperature, and mechanochemical agitation, and can be readily determined by periodically sampling the material and following the progress of the reaction via, for example, BET analysis, specific surface area, particle size analysis, and total carbon determination as described herein.

[0078] The inventors have further found that the mechanochemical carbonation processes described herein can be advantageously carried out without the use of an additional oxidizing agent, such as an acid. Accordingly, the mechanochemical carbonation processes described herein are preferably carried out without the use of a strong acid, and preferably without the use of an additional oxidizing agent other than the gas provided in step (b).

[0079] In a preferred embodiment of the present invention, the mechanical agitation operation in step (d) comprises grinding, milling, mixing, stirring (such as low-speed or high-speed stirring), shearing (such as high-torque shearing), shaking, blending, pulverizing, powdering, crushing, disintegration, fluidized bed, or ultrasonic treatment, preferably grinding, milling, mixing, stirring (such as low-speed or high-speed stirring), shearing (such as high-torque shearing), or ultrasonic treatment. The inventors have found that the mechanochemical carbonation process is accelerated when the mechanochemical agitation operation in step (d) is carried out in the presence of grinding or milling media, preferably balls or beads. Preferred materials are stainless steel or aluminum oxide. In such a highly preferred embodiment, the mechanical agitation operation may simply be rotation of a mechanical agitation unit containing the solid raw materials, grinding or milling media, and gas. For example, the grinding or milling media can be made from steel (e.g., AISI H13, modified H10), aluminum oxide, chrome white cast iron (e.g., ASTM A532), molybdenum steel (e.g., AISI M2, M4, M-42), chromium-based steel (e.g., H11, H12, H13 CPM V9, ZDP-189), or other media with a target HRC hardness of 60. Such grinding media can be utilized with or without surface treatments such as nitriding and carburizing. This can be conveniently performed in a rotating drum. It will be appreciated that the products obtained by the process of the present invention, when performed in a rotating drum, may also be obtained using alternative grinding or milling techniques known to those skilled in the art.

[0080] In a preferred embodiment of the present invention, step (d) is carried out in the presence of a catalyst, preferably a metal oxide catalyst such as a transition metal oxide catalyst. Examples of suitable catalysts are selected from the group consisting of iron oxide, cobalt oxide, ruthenium oxide, titanium oxide, nickel oxide, aluminum oxide, and combinations thereof.

[0081] Thus, as can be appreciated from the above, in a highly preferred embodiment of the present invention, step (d) comprises grinding, milling, mixing, stirring (such as slow or high speed stirring), shearing (such as high torque shear), shaking, blending, micronizing, pulverizing, crushing, disintegrating, fluidized bed or sonicating in the presence of grinding or milling media and a metal oxide catalyst, preferably grinding, milling, mixing, stirring (such as slow or high speed stirring), shearing (such as high torque shear) or sonicating.

[0082] The inventors have found that it is advantageous in terms of the efficiency of mechanochemical carbonation (e.g., reaction time, CO2 absorption, particle size reduction) to employ a medium as described herein above that includes the metal oxide catalyst (e.g., as a coating), and / or to employ a mechanical stirring unit (or part thereof) that includes (or includes as a coating) the metal oxide catalyst on one or more surfaces that come into contact with the feedstock, e.g., during step (d). As explained elsewhere herein, the mechanical stirring operation may simply be the rotation of a mechanical stirring unit that includes the solid feedstock or solid glassy precursor for mechanochemical carbonation, grinding or milling media, metal oxide catalyst, and gas. This can be conveniently performed in a rotating drum.

[0083] As will be apparent from the present specification, in a highly preferred embodiment, step (d) is a substantially dry process. While the presence of some moisture is acceptable and beneficial to carbonation efficiency, it is highly preferred that step (d) is not carried out with an aqueous solution or slurry. The inventors have found that performing step (d) on a solid is significantly more energy efficient (since there is no need to subsequently remove the water) and imparts unique properties to the resulting carbonated glassy solid, resulting in a material that is substantially different from, for example, aqueous carbonated materials. This is also reflected in their unique properties when used, for example, as a filler in concrete.

[0084] According to a highly preferred embodiment of the present invention, the feedstock provided in step (a) is a solid feedstock. The solid feedstock provided in step (a) highly preferably has a moisture content of less than 30 wt. %, preferably less than 20 wt. %, more preferably less than 15 wt. % (based on the total weight of the solid feedstock). From the standpoint of carbonation efficiency, the solid feedstock preferably has a moisture content of at least 2 wt. %, preferably at least 5 wt. %, more preferably at least 10 wt. % (based on the total weight of the solid feedstock). At a moisture content of less than 30 wt. % (based on the total weight of the solid feedstock), the feedstock remains solid and behaves like a solid. In some embodiments of the present invention, the solid feedstock may have a moisture content of less than 10 wt. %, less than 5 wt. %, or less than 2 wt. % (based on the total weight of the solid feedstock). The solid feedstock preferably has a moisture content as defined herein at at least one point during step (d), for example, when step (d) is initiated. In some embodiments, the moisture content of the feedstock remains as defined herein throughout most or substantially all of step (d).

[0085] Based on the guidance provided herein, it is within the ordinary skill of one of ordinary skill in the art to adjust the moisture content of the feedstock, for example, by spraying an aqueous composition such as water onto the solid feedstock prior to and / or during step (d).

[0086] In another embodiment, the feedstock provided in step (a) is an aqueous slurry, solution, or suspension, such as an aqueous slurry. The feedstock aqueous slurry, solution, or suspension provided in step (a) can have a water content of more than 50 wt. % (based on the total weight of the feedstock aqueous slurry, solution, or suspension), for example, more than 70 wt. %. The feedstock aqueous slurry, solution, or suspension preferably has a water content as defined herein at at least one point during step (d), for example, at the start of step (d). In some embodiments, the water content of the feedstock aqueous slurry, solution, or suspension is as defined herein throughout most or substantially all of step (d).

[0087] In some embodiments, step (d) is followed by a dehydration step to reduce the water content of the resulting mechanochemically carbonated glassy solid.

[0088] In particular, the inventors have found that it is important that step (d) is carried out in a manner that results in some degree of carbonation, size reduction, and / or surface area increase during step (d), i.e., the combination of carbonation and mechanical agitation. This results in a material that is significantly different from, for example, material that has been ground and then carbonated. To achieve these effects, it is preferred that step (a) of the method comprises providing a solid feedstock as described hereinabove, and that step (d) is carried out on the solid feedstock provided in step (a).

[0089] Thus, in a highly preferred embodiment, the following features: the ratio of the total carbon content of the mechanochemically carbonated glassy solid obtained in step (d) to the total carbon content of the solid glassy precursor of step (a) is at least 1.5:1, preferably at least 2:1, more preferably at least 3:1; the ratio of D50 of the mechanochemically carbonated glassy solid obtained in step (d) to D50 of the solid glassy precursor of step (a) is less than 0.5:1, preferably less than 0.1:1, more preferably less than 0.05:1; the ratio of the specific surface area of the glassy solid to the specific surface area of the solid glassy precursor is at least 3:1, preferably at least 6:1, more preferably at least 10:1, and in some embodiments of the invention the ratio of the specific surface area of the glassy solid to the specific surface area of the solid glassy precursor is at least 15:1; The method of the present invention is provided wherein carbonation, size reduction, and / or surface area increase is effected during step (d) so as to have one, two, or all three of the following, preferably all three:

[0090] Those skilled in the art will appreciate that since the material of step (a) is fed to step (d), this means that carbonation, size reduction, and / or the surface area as defined above is achieved during step (d).

[0091] Without wishing to be bound by any theory, the inventors believe that the increase in BET surface area provided by the dry mechanochemical carbonation process is associated with the observed beneficial properties, such as superior strength activity index and reduced water demand. Accordingly, in an embodiment of the present invention, there is provided a process in which carbonation and an increase in BET surface area are provided during step (d) such that the ratio of the BET surface area of the mechanochemically carbonated glassy solid to the BET surface area of the glassy precursor is at least 4:1, preferably at least 8:1, and more preferably at least 15:1.

[0092] The inventors have found that the preferred methods for producing carbonated glassy solids described herein, particularly those performed with solid feedstocks, do not result in significant loss of sodium from the precursor. Accordingly, embodiments of the present invention provide methods in which the ratio of the sodium content of the carbonated glassy solid, preferably a mechanochemically carbonated glassy solid, to the sodium content of the glassy precursor is in the range of 0.8 to 1.2, preferably in the range of 0.9 to 1.1, and more preferably in the range of 0.92 to 1.05.

[0093] In a particularly preferred embodiment of the method of the present invention, the BJH desorption cumulative surface area of the pores of the carbonated glassy solid obtained in step (d) is at least 110%, preferably at least 120%, more preferably at least 150% of the BJH desorption cumulative surface area of the pores of the solid glassy precursor, and the desorption average pore width (4V / A by BET) of the carbonated glassy solid obtained in step (d) is 90% or less, preferably 85% or less, more preferably 80% or less of the desorption average pore width (4V / A by BET) of the solid glassy precursor.

[0094] In an embodiment of the present invention, the method described herein does not include a solid-liquid separation step selected from filtration, decantation, and gravitational separation (e.g., using a cyclone) after step (d), and preferably, the method of the present invention does not include any solid-liquid separation step after step (d).

[0095] In an embodiment of the present invention, the method described herein does not include a size selection step such as a screening step or a sieving step after step (d).

[0096] Properties of the glassy solid precursor used in the mechanochemical carbonation method of the present invention In a preferred embodiment of the method described herein, the solid glassy precursor for mechanochemical carbonation is a particulate solid material such as a powder.

[0097] In a preferred embodiment of the method described herein, the solid glassy precursor has a specific surface area of less than 0.5 m 2 / g, preferably less than 0.2 m 2 / g, more preferably less than 0.1 m 2 / g and is a particulate solid material.

[0098] In an embodiment of the method described herein, the solid glassy precursor for mechanochemical carbonation has one, two, or three, preferably three, of the following characteristics: · D10 within the range of 10 to 200 μm, preferably 20 to 150 μm, most preferably 35 to 60 μm; D50 in the range of 30-500 μm, preferably 50-300 μm, most preferably 80-250 μm; D90 in the range of 100-1000 μm, preferably 125-750 μm, most preferably 150-500 μm.

[0099] In a preferred embodiment of the method described herein, the solid glassy precursor for mechanochemical carbonation is selected from soda-lime glass, lead glass, borosilicate glass, aluminosilicate glass, fused silica glass, and quartz glass, preferably soda-lime glass. In a highly preferred embodiment, the solid glassy precursor for mechanochemical carbonation comprises recycled glass, preferably recycled soda-lime glass, more preferably recycled soda-lime container glass or flat glass, and most preferably recycled soda-lime container glass. "Recycled" as used in this context means that the glass is used rather than virgin material. A typical example is soda-lime glass bottles or jars that are crushed or ground after use to form recycled or waste particulate glass material, which can be used as a raw material for the method of the present invention.

[0100] In an embodiment of the present invention, the solid glassy precursor comprises: an SiO2 content of at least 70% by weight (based on the total weight of the glassy precursor); and / or a combined amount of alkaline earth metal oxides and hydroxides of less than 20% by weight (relative to the total weight of the glassy precursor), preferably less than 15% by weight (relative to the total weight of the glassy precursor); It has.

[0101] In a preferred embodiment of the present invention, the solid glassy precursor comprises an SiO2 content of at least 70% by weight (based on the total weight of the glassy precursor); a B2O3 content of at least 5 wt.-% (relative to the total weight of the glassy precursor), preferably at least 7 wt.-% (relative to the total weight of the glassy precursor); and a combined amount of alkaline earth metal oxides and hydroxides preferably less than 4 wt. % (relative to the total weight of the glassy precursor), preferably less than 1 wt. % (relative to the total weight of the glassy precursor); Such glasses correspond to borosilicate glasses.

[0102] In a preferred embodiment of the present invention, the glassy precursor comprises an SiO2 content of at least 70% by weight (based on the total weight of the glassy precursor); a Na2O content of at least 5 wt.-% (relative to the total weight of the glassy precursor), preferably at least 10 wt.-% (relative to the total weight of the glassy precursor); and a combined amount of alkaline earth metal oxides and hydroxides of preferably at least 5 wt. % (relative to the total weight of the glassy precursor), preferably at least 10 wt. % (relative to the total weight of the glassy precursor); Such glasses correspond to soda-lime glasses.

[0103] Without wishing to be bound by any theory, it is believed that the presence of at least some alkaline earth metal oxide or hydroxide promotes carbonation. Thus, according to some embodiments or preferred embodiments of the present invention, the solid vitreous precursor described herein has a combined amount of alkaline earth metal oxide and hydroxide of at least 0.01 wt.%, preferably at least 0.05 wt.%. It will therefore be understood that, according to some (preferred) embodiments, the solid vitreous precursor has a combined amount of alkaline earth metal oxide and hydroxide in the range of 0.01 to 20 wt.%.

[0104] Properties of the carbonated glassy solid obtained in step (d) In preferred embodiments, the carbonated glassy solid obtained in step (d) meets the strength requirements set forth in ASTM C618-12a(2012) and CSA A3001-18(2018). In certain embodiments, the methods described herein do not include a size separation step, such as a screening or sieving step, after step (d), and the carbonated glassy solid obtained in step (d) meets the strength requirements set forth in ASTM C618-12a(2012) and CSA A3001-18(2018).

[0105] In an embodiment, the carbonated glassy solid obtained in step (d) has a viscosity of 0.3 m 2 / g or more, preferably 0.5m 2 / g or more, more preferably 0.8m 2 For example, a carbonated glassy solid has a specific surface area of at least 0.3 m 2 / g, at least 0.35m 2 / g, at least 0.40m 2 / g, at least 0.45m 2 / g, at least 0.50m 2 / g, at least 0.55m 2 / g, at least 0.70m 2 / g, at least 0.65m 2 / g, at least 0.70m 2 / g, at least 0.75m 2 / g, at least 0.8m 2 / g, at least 0.85m 2 / g, at least 0.90m 2 / g, at least 0.95m 2 / g, at least 1.0m 2 / g.

[0106] In a preferred embodiment, the carbonated glassy solid obtained in step (d) is 50 ml 2 / g or less, preferably 30m 2 / g or less, more preferably 10m 2 For example, the carbonated glassy solid obtained in step (d) has a specific surface area of up to 50 m2 / g, up to 48m 2 / g, up to 46m 2 / g, up to 44m 2 / g, up to 42m 2 / g, up to 40m 2 / g, up to 38m 2 / g, up to 36m 2 / g, up to 34m 2 / g, up to 32m 2 / g, up to 30m 2 / g, up to 28m 2 / g, up to 26m 2 / g, up to 24m 2 / g, up to 22m 2 / g, up to 20m 2 / g, up to 18m 2 / g, up to 16m 2 / g, up to 14m 2 / g, up to 12m 2 / g, up to 10m 2 / g, up to 8m 2 / g, up to 6m 2 / g, up to 4m 2 / g, up to 2m 2 / g.

[0107] In a more preferred embodiment, the carbonated glassy solid obtained in step (d) is 2 / g, preferably less than 3m 2 / g, more preferably less than 2m 2 For example, the carbonated glassy solid obtained in step (d) has a specific surface area of less than 5.0 m 2 / g, less than 4.5m 2 / g, less than 4.0m 2 / g or less, 3.5m 2 / g or less, 3.0m 2 / g or less, 2.5m 2 / g or less, 2.0m 2 / g or less, 1.5m 2 / g or less.

[0108] The inventors have observed that carbonated glassy solids having a specific surface area within a particular range have particular properties in terms of performance, handling, etc., compared to their untreated precursors, and even compared to carbonated materials having other surface areas. Thus, according to a highly preferred embodiment of the present invention, the carbonated glassy solid has a specific surface area of 0.3 to 50 m. 2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.8 to 50m 2 / g specific surface area, e.g., 0.3 to 50 m 2 / g, preferably 0.3 to 30m 2 / g, more preferably 0.3 to 10m 2 Specific surface area in the range of 0.5~50m / g 2 / g, preferably 0.5 to 30m 2 / g, more preferably 0.5 to 10m 2 Specific surface area in the range of 0.8~50m / g 2 / g, preferably 0.8 to 30m 2 / g, more preferably 0.8 to 10m 2 Specific surface area in the range of 0.3~5.0m / g 2 / g, preferably 0.3 to 3.0 m 2 / g, more preferably 0.3 to 2.0m 2 Specific surface area in the range of 0.5~5.0m / g 2 / g, preferably 0.5 to 3.0 m 2 / g, more preferably 0.5 to 2.0 m 2 Specific surface area in the range of 0.8~5.0m / g 2 / g, preferably 0.8 to 3.0 m 2 / g, more preferably 0.8 to 2.0 m 2 / g range.

[0109] In an embodiment of the invention, the carbonated glassy solid obtained in step (d) has one, two or three, preferably three, of the following characteristics: D10 in the range of 0.005 to 5 μm, preferably 0.01 to 2 μm, most preferably 0.1 to 1.5 μm; D50 in the range of 0.1 to 50 μm, preferably 0.5 to 25 μm, most preferably 1 to 10 μm; D90 in the range of 0.5 to 100 μm, preferably 1 to 50 μm, most preferably 5 to 25 μm.

[0110] In an embodiment of the present invention, the carbonated glassy solid obtained in step (d) has a total carbon content of at least 0.1 wt.%, preferably at least 0.15 wt.%, more preferably at least 0.2 wt.%.

[0111] In an embodiment of the present invention, the carbonated glassy solid obtained in step (d) has a Strength Activity Index (SAI) of at least 60%, preferably at least 80%, at 7 days.

[0112] In an embodiment of the present invention, the carbonated glassy solid obtained in step (d) has a Strength Activity Index (SAI) at 28 days of at least 80%, preferably at least 100%.

[0113] In an embodiment of the invention, the carbonated glassy solid obtained in step (d) has a water demand of less than 96%, preferably less than 95%.

[0114] In an embodiment of the invention, the sodium content of the carbonated glassy solid obtained in step (d) is at least 3.75 wt. % (based on the total weight of the carbonated glassy solid), preferably at least 7.5 wt. % (based on the total weight of the carbonated glassy solid).

[0115] Carbonated glassy solids obtained by the methods described herein The inventors have found that the mechanochemical carbonation described herein imparts unique properties to the resulting carbonated glassy solids, resulting in materials that are substantially different from, for example, aqueous carbonated materials. This is reflected in their unique properties when used, for example, as a filler in concrete. In particular, the inventors have found that it is important that step (d) is conducted in a manner that results in some degree of carbonation, size reduction, and / or surface area increase during step (d), i.e., the combination of carbonation and mechanical agitation. This results in materials that are significantly different from, for example, materials carbonated in an aqueous environment, or even materials that have been ground and then carbonated.

[0116] Thus, in another aspect, the present invention provides a mechanochemically carbonated glassy solid obtainable by the method for producing a mechanochemically carbonated glassy solid described herein.

[0117] Compositions containing carbonated glassy solids and methods for making same Thus, in another aspect, the present invention provides a composition comprising a carbonated glassy solid as described herein and an additional material selected from the group consisting of asphalt, geopolymer, cement, polymer, and combinations thereof, preferably cement, more preferably Portland cement, wherein the glassy solid is preferably a mechanochemically carbonated glassy solid as described herein.

[0118] In an embodiment, the additional material is a polymer selected from thermoplastic polymers and thermosetting polymers. In a preferred embodiment, the additional component is selected from epoxide resins, phenol-formaldehyde resins, polyalkylene terephthalates (preferably polyethylene terephthalate), polyalkylene adipate terephthalates (preferably polybutylene adipate terephthalate), polyalkylene isosorbide terephthalates (preferably polyethylene isosorbide terephthalate), polyalkylene aromatic polyamides (preferably polyethylene aromatic polyamides), polyacrylonitrile, polyacetal, polyimides, aromatic polyesters, polyisoprenes (preferably cis-1,4-polyisoprene), polyethylene , polypropylene, polyurethane, polyisocyanurate, polyamide, polyether, polyester, polyhydroxyalkanoate, polylactic acid, polylactic-co-glycolic acid, polyvinylidene fluoride, polyvinyl acetate, polyvinyl chloride, polystyrene, polytetrafluoroethylene, acrylonitrile-butadiene-styrene, nitrile rubber, styrene butadiene, ethylene-vinyl acetate, copolymers thereof, and combinations thereof, more preferably polyolefins such as polypropylene and polyethylene, copolymers thereof, and combinations thereof. As used herein, the term "polymer" includes copolymers, such as block copolymers.

[0119] In a highly preferred embodiment, the additional material is selected from cement, asphalt, geopolymer, or combinations thereof.

[0120] According to the present invention, the cement may be a hydraulic cement or a non-hydraulic cement. In a preferred embodiment, the cement is a hydraulic cement such as Portland cement. In a highly preferred embodiment of the present invention, the cement is one of the cements specified in EN197-1(2011), preferably Portland cement specified in EN197-1(2011).

[0121] In an embodiment of the invention, the composition contains more than 0.1 wt. %, preferably more than 1 wt. %, more preferably more than 5 wt. % of a carbonated glassy solid (relative to the total weight of the composition), and / or more than 0.1 wt. %, preferably more than 1 wt. %, more preferably more than 20 wt. % of an additional material (relative to the total weight of the composition).

[0122] In an embodiment of the invention, the composition contains less than 60 wt. %, preferably less than 50 wt. %, more preferably less than 45 wt. % of a carbonated glassy solid (based on the total weight of the composition), and / or less than 95 wt. %, preferably less than 90 wt. %, more preferably less than 80 wt. % of additional materials (based on the total weight of the composition).

[0123] In an embodiment of the present invention, there is provided a composition in which the weight:weight ratio of carbonated glassy solid to additional material is in the range of 1:9 to 2:1, preferably in the range of 1:8 to 1:1, more preferably in the range of 1:6 to 5:6.

[0124] In an embodiment of the invention, the composition contains 5 to 70 wt. %, preferably 10 to 60 wt. %, more preferably 20 to 50 wt. % of a carbonated glassy solid (based on the total weight of the composition) and 30 to 95 wt. %, preferably 40 to 90 wt. %, preferably 50 to 80 wt. % of additional material (based on the total weight of the composition).

[0125] In an embodiment of the invention, the composition contains less than 5 wt. % water (based on the total weight of the composition), preferably less than 1 wt. %, and more preferably less than 0.1 wt. % water, which may suitably be determined as the mass loss to 120° C. as measured by TGAMS using a temperature trace from room temperature to 800° C. at a rate of 10° C. / min.

[0126] In an embodiment of the present invention, the composition comprises a carbonated glassy solid and an additional material.

[0127] In another aspect, the present invention provides a method for making the compositions described herein, comprising: (i) providing a carbonated glassy solid as described herein, preferably a mechanochemically carbonated glassy solid as described herein; (ii) providing an additional material selected from the group consisting of asphalt, cement, geopolymer, polymer, and combinations thereof; and (iii) combining the carbonated glassy solid of step (i) with the material of step (ii); The present invention provides a method comprising:

[0128] Concrete or mortar containing a composition and a carbonated glassy solid, and method for producing the same In another aspect, the present invention provides a method for producing concrete or mortar, comprising the steps of: (i) providing a carbonated glassy solid as described herein, particularly a mechanochemically carbonated glassy solid as described herein, and an additional material selected from the group consisting of asphalt, cement, geopolymer, and combinations thereof, optionally in the form of a composition as described herein; (ii) providing construction aggregates; and (iii) contacting, preferably mixing, the carbonated glassy solid and additional material of step (i) with the construction aggregate and optional water of step (ii); The present invention provides a method comprising:

[0129] In another aspect, the present invention provides a concrete or mortar obtainable by the method for making concrete described herein.

[0130] In embodiments of the present invention, the construction aggregate is selected from the group consisting of sand, gravel, crushed stone, slag, recycled concrete, clay, pumice, perlite, vermiculite, and combinations thereof. In preferred embodiments, the construction aggregate is one of the aggregates specified in EN 13043 (2002), EN 13383 (2019), EN 12620 (2013), or EN 13242 (2013), preferably the construction aggregate is one of the aggregates specified in EN 12620 (2013).

[0131] In a preferred embodiment of the present invention, step (iii) further comprises contacting, preferably mixing, the carbonated glassy solid and additional material of step (i) with the construction aggregate and water of step (ii). According to the present invention, the carbonated glassy solid and additional material of step (i) and the construction aggregate and water of step (ii) may be contacted, preferably mixed, substantially simultaneously, or may be contacted, preferably mixed, in a stepwise manner, where the composition of step (i) is first contacted, preferably mixed, with water, and then contacted, preferably mixed, with the construction aggregate of step (ii).

[0132] In another aspect, the present invention provides a method for producing a carbonated glassy solid, particularly a mechanochemically carbonated glassy solid, as described herein, as a filler, preferably in a material selected from the group consisting of asphalt, cement, geopolymers, mortar, polymers, and combinations thereof; · As a partial replacement for asphalt, geopolymer, or cement in concrete or mortar; · To increase the compressive strength of concrete or mortar; To improve the durability of concrete or mortar; · To reduce the expansion of concrete; · To improve the durability of concrete or mortar by reducing chloride permeability and / or porosity; To improve the strength activity index of concrete or mortar; and / or To reduce the water demand of concrete or mortar, Preferably, To simultaneously improve the strength activity index of concrete and reduce the water demand of concrete; or ·To simultaneously improve the strength activity index of mortar and reduce the water demand of mortar; Provide use.

[0133] Those skilled in the art will appreciate that embodiments of the invention specifically described herein in relation to (mechanochemically) carbonated glassy solids or compositions, and particularly in relation to the features of the (mechanochemically) carbonated glassy solids or the features of the additional materials, are equally applicable to the methods for making said compositions described herein, the methods for making concrete described herein, and the uses of the (mechanochemically) carbonated glassy solids described herein. [Example]

[0134] Example Particle size distribution and specific surface area measurements were performed on a Brookhaven Laser Particle Sizer, model Microbrook 2000LD, which utilizes Fraunhofer light scattering theory and reports data using the volume-equivalent sphere model.

[0135] Compressive strength, strength activity index, and water demand were measured in accordance with ASTM C311 / C311M-22, and as will be apparent to those skilled in the art, the glass precursor of the present invention and carbonated glass were used in place of the "fly ash or natural pozzolan" specified in the standard when conducting these tests.

[0136] Total carbon content was determined according to the method described in Soil Sampling and Methods of Analysis, 2nd Ed., CRC Press (2008), p. 244 et seq.

[0137] Example 1 Mechanochemically carbonated glassy solids were produced by placing 2.1 kg of solid glassy precursor (crushed recycled soda-lime glass) in a pressure cell containing 150 kg of grinding media (10 mm ceramic ball bearings). The cell was pressurized with concentrated CO2 gas (>95% by volume) to an initial pressure of 441 kPa and rotated on a roller at 38 RPM for 24 hours to produce mechanochemically carbonated glass. The reaction was initiated at room temperature without heating or cooling. The ceramic bearings have an Al2O3 content of 92% by weight, and therefore also function as a catalyst. The properties of the glassy precursor and the resulting mechanochemically carbonated glass are shown in the table below.

[0138] [Table 1]

[0139] As seen from Strength Activity Index (SAI) and water demand measurements, the mechanochemically carbonated glassy solids of the present invention unexpectedly exhibit reduced water demand and increased strength compared to their non-carbonated counterparts, and even compared to a Portland cement control.

[0140] Example 2 Mechanochemically carbonated glassy solids were produced by placing 5.1 kg of glassy precursor in a pressure cell containing 150 kg of grinding media (10 mm ceramic ball bearings). The cell was pressurized with exhaust gas (8-10 vol% CO2, 18-20 vol% H2O, 2-3 vol% O2, 67-72 vol% N2) to an initial pressure of 448 kPa and rotated on a roller at 38 RPM for 3 days to obtain mechanochemically carbonated glass. The reaction was initiated at room temperature without heating or cooling. The ceramic bearings had an Al2O3 content of 92 wt% and therefore also functioned as a catalyst. The properties of the glassy precursor and the resulting mechanochemically carbonated glass are shown in the table below.

[0141] The glassy precursor was waste glass material from hollow microsphere manufacturing and included: (a) 50 wt% to 90 wt% SiO2; (b) 2% to 20% by weight of an alkali metal oxide; (c) 1 wt% to 30 wt% B2O3; (d) 0 wt% to 0.5 wt% sulfur; (e) 0 wt% to 25 wt% of a divalent metal oxide; (f) 0 wt. % to 10 wt. % of a tetravalent metal oxide other than SiO2; (g) 0 wt% to 20 wt% of a trivalent metal oxide; (h) 0% to 10% by weight of an oxide of a pentavalent atom; and (i) 0% to 5% by weight of fluorine.

[0142] [Table 2]

[0143] Example 3 Mechanochemically carbonated glassy solids were produced by placing 5.0 kg of glassy precursor (ground glassy pozzolan) in a pressure cell containing 200 kg of grinding media (10 mm ceramic ball bearings). The cell was pressurized with exhaust gas (8-10 vol% CO2, 18-20 vol% H2O, 2-3 vol% O2, 67-72 vol% N2) to an initial pressure of 414 kPa and rotated on a roller at 38 RPM for 3 days to produce mechanochemically carbonated glass. The reaction was initiated at room temperature without heating or cooling. The ceramic bearings had an Al2O3 content of 92 wt% and therefore also functioned as a catalyst. The properties of the glassy precursor and the resulting mechanochemically carbonated glass are shown in the table below.

[0144] [Table 3]

[0145] As seen from Strength Activity Index (SAI) and water demand measurements, the mechanochemically carbonated glassy solids of the present invention unexpectedly exhibit reduced water demand and increased strength compared to their non-carbonated counterparts, and even compared to a Portland cement control.

[0146] Example 4 Mechanochemically carbonated glassy solids were produced by placing 2.1 kg of glass precursor (oven-dried, ground Ruby Lake glass) in a pressure cell containing 150 kg of grinding media (10 mm ceramic bearings). The cell was pressurized with CO gas (99% by volume) to an initial pressure of 448 kPa and rotated on a roller at 38 RPM for 24 hours to produce mechanochemically carbonated glass. The properties of the glassy precursor and the resulting mechanochemically carbonated glass are shown in the table below.

[0147] [Table 4]

[0148] The measured particle size distributions of the glassy precursor and the resulting mechanochemically carbonated glasses are shown in the table below.

[0149] [Table 5]

[0150] The carbonated glassy solid meets the strength and water requirements specified in ASTM C618 and / or CSA A3001.

Claims

1. A carbonated glassy solid obtained by carbonation of a solid glassy precursor, wherein the glassy precursor contains at least 65% by weight of SiO (relative to the total weight of the glassy precursor). ２ A carbonated glassy solid having a content and a total carbon content of at least 0.1% by weight.

2. The following features: D10 in the range of 0.005 to 5 μm; D50 in the range of 0.1 to 50 μm; D90 in the range of 0.5 to 100 μm; A carbonated glassy solid according to claim 1, having one, two, or three of the above.

3. 0.3m ２ The carbonated glassy solid according to claim 1, having a specific surface area greater than / g.

4. The carbonated glassy solid according to claim 1, having at least 80% of the strength activity index SAI on day 28 as determined according to ASTM C311 / C311M-22.

5. The carbonated glassy solid according to claim 1, having at least 100% of the strength activity index SAI on day 28 as determined according to ASTM C311 / C311M-22.

6. The glassy precursor is - At least 70% by weight of SiO (relative to the total weight of the glassy precursor) ２ Content; and / or - The total amount of alkaline earth metal oxides and hydroxides (relative to the total weight of the glassy precursor) is less than 20% by weight; A carbonated glassy solid according to claim 1, having the properties of the carbonated glassy solid described in claim 1.

7. The carbonated glassy solid according to claim 1, wherein the glassy precursor includes recycled glass.

8. The carbonated glassy solid according to claim 1, wherein the glassy precursor includes recycled soda-lime glass.

9. A carbonated glassy solid according to claim 1, obtained by simultaneous carbonation and size reduction of a solid glassy precursor, wherein the ratio of the D50 of the carbonated glassy solid to the D50 of the glassy precursor is less than 0.5:

1.

10. A method for producing a glassy solid that has been mechanochemically carbonated, a) A step of supplying a solid raw material containing or consisting of a solid glassy precursor; b) At least 0.1 volume% of CO ２ A process of supplying a gas containing; c) A step of introducing the raw materials and the gas into a mechanical stirring unit; and d) A step of obtaining a mechanochemically carbonated glassy solid by performing mechanical stirring operations, including crushing or milling, on the raw material in the presence of the gas within the mechanical stirring unit; A method that includes this.

11. The method according to claim 10, wherein the raw material supplied in step (a) has a water content of less than 30% by weight (relative to the total weight of the solid raw material).

12. The method according to claim 11, wherein the raw material supplied in step (a) has a water content of at least 2% by weight (relative to the total weight of the solid raw material).

13. The method according to claim 10, wherein the glassy precursor is selected from soda-lime glass, lead glass, borosilicate glass, aluminosilicate glass, fused silica glass, and quartz glass.

14. The method according to claim 13, wherein the glassy precursor is selected from soda-lime glass.

15. The method according to claim 10, wherein the gas supplied in step (b) is combustion exhaust gas.

16. The method according to claim 10, wherein the CO2 concentration in the gas supplied in step (b) is in the range of 1 to 15 volume percent.

17. Step (d) is - At a pressure of less than 1000 kPa; and - At temperatures below 150°C; The method according to claim 10, which is carried out.

18. The following features: - The ratio of the total carbon content of the mechanochemically carbonated glassy solid obtained in step (d) to the total carbon content of the solid glassy precursor in step (a) is at least 1.5:1; - The ratio of D50 of the mechanochemically carbonated glassy solid obtained in step (d) to D50 of the solid glassy precursor in step (a) is less than 1.5:1; - The ratio of the specific surface area of ​​the glassy solid to the specific surface area of ​​the solid glassy precursor is at least 3:1; The method according to claim 10, wherein carbonation, size reduction, and / or surface area increase are brought about during step (d) such that one, two, or all three of the above are present.

19. The glassy precursor contains at least 65% by weight of SiO (relative to the total weight of the glassy precursor). ２ The method according to claim 10, comprising the content of the present invention.

20. A mechanochemically carbonated glassy solid obtained by the method described in claim 10.

21. A composition comprising a glassy solid according to any one of claims 1 or 20, and an additional material selected from the group consisting of asphalt, cement, geopolymer, polymer, and combinations thereof.

22. A method for manufacturing concrete, (i) A step of optionally supplying a carbonated glassy solid according to any one of claims 1 or 20 and an additional material selected from the group consisting of asphalt, cement, geopolymer, and combinations thereof, in the form of the composition according to claim 21; (ii) the process of supplying construction aggregates; and (iii) A step of mixing the carbonated glassy solid and the additional material of step (i) with the construction aggregate and water of step (ii); A method that includes this.

23. A carbonated glassy solid according to any one of claims 1 or 20, - As a filler in materials selected from the group consisting of asphalt, geopolymers, cement, mortar, polymers, and combinations thereof; - As a partial substitute for asphalt, geopolymer, or cement in concrete or mortar; - To increase the compressive strength of concrete or mortar; - To improve the durability of concrete or mortar; - To reduce the expansion of concrete; - To improve the durability of concrete or mortar by reducing chloride permeability and / or porosity; - For improving the strength activity index of concrete or mortar; - To reduce the water requirements of concrete or mortar; - To simultaneously improve the strength activity index of concrete and reduce the water requirements of concrete; or - To simultaneously improve the strength activity index of mortar and reduce the water requirements of mortar; use.