Cementitious reagent and method of manufacturing and use thereof

Abstract

Cementitious reagent materials produced from globally abundant inorganic feedstocks are described. Methods for making such cementitious reagent materials and forming the reagent materials into microspheroidal glassy particles are also described. Apparatus, systems, and methods for thermally chemically producing glassy cementitious reagents having a spheroidal morphology are also described. The apparatus, systems, and methods utilize a flying melt / quench technique such that the solid particles flow in a suspended manner, are melted in a suspended manner, and then are quenched in a suspended manner. The cementitious reagents can be used in concrete to significantly reduce CO2 emissions associated with cement production.

Description

Technical Field

[0001] The invention belongs to the technical field of cement reagents, and relates to a cement reagent, a manufacturing method thereof and an application thereof.

[0002] Cross-reference to related applications:

[0003] This application claims priority to U.S. Provisional Application No. 62 / 867,480, filed on June 27, 2019, U.S. Provisional Application No. 63 / 004,673, filed on April 3, 2020, and U.S. Provisional Application No. 63 / 025,148, filed on May 14, 2020, the disclosures of which are incorporated herein by reference in their entireties. Background Art

[0004] The field of the present disclosure relates to cementitious agents, and more particularly, to the production of relatively homogeneous cementitious agent materials and cementitious materials from abundant, heterogeneous raw materials.

[0005] Concrete has played an important role in civilization for millennia and remains the most commonly used building material. Cement is the essential binding component of concrete, allowing the flowable concrete paste to harden into a useful composite material at ambient temperature. Many binder chemistries have been successfully used to make concrete, but Portland cement and its variants have been the dominant concrete binder for nearly 200 years. Despite advances in production efficiency and material properties, Portland cement chemistry presents significant and inherent problems that cannot be addressed at any reasonable cost using current methods.

[0006] Portland cement production is a CO₂-intensive process, responsible for approximately 8% of global anthropogenic CO₂ emissions. Some estimates project cement demand to increase by 12–23% by 2050. However, according to the UN IPCC's 2018 climate report, growing absolute demand for cement is inconsistent with the need for complete economic decarbonization by 2050, which is required to avoid the catastrophic impacts of climate change, particularly as absolute production volumes are increasing. Therefore, there is an urgent need to significantly reduce cement's specific CO₂ emissions.

[0007] One way the industry is attempting to reduce CO emissions from cement is by developing geopolymer cements, which are typically inorganic polymers of aluminosilicates cured through a geopolymerization process. Currently used commercially relevant geopolymer cements require access to several specific solid reagents (typically: metakaolin (MK-750), ground granulated blast furnace slag (GGBFS), and fly ash). However, these reagents cannot meet the global shift to low-CO cement because supply is relatively limited geographically and in volume compared to the vast demand for cement. Furthermore, the cost of transporting these products from production sites is significant compared to their market value.

[0008] Cementitious agents can be used for both hydraulic cements and geopolymer cements. Geopolymer agents and supplementary cementitious materials (SCMs) are typically selected from several common cementitious materials: by-product ash from combustion (e.g., fly ash), slag by-products (e.g., ground granulated blast furnace slag), calcined clays (e.g., metakaolin), and natural pozzolans (e.g., volcanic ash). These materials are typically substantially non-crystalline and are sometimes reactive in cementitious systems (e.g., in geopolymer systems).

[0009] Because most of the SCMs used in mixed hydraulic cement are industrial by-products (such as coal combustion or production of high-quality iron), their material properties are the result of industrial by-products and are not specially customized as high-quality cement reagents. Therefore, these materials lack any guarantee of ideal or even consistent composition and quality, and their suitability as cement reagents varies from plant to plant and changes over time. There is also no control of the production location, and the concrete industry lacks the control of the future availability of these vital cement materials. If the production location can be selected based on market needs, then it will be more advantageous, particularly because the transportation of cement materials is very expensive.

[0010] Fly ash is a partially vitreous aluminosilicate by-product of coal combustion. It is often used as an admixture in hydraulic cement mixtures to improve fluidity and produce a pozzolanic reaction to improve the properties of concrete, including strength, resistance to alkali-silica reactions, etc. Unfortunately, only certain coals and combustion processes produce fly ash of acceptable quality for concrete (e.g., ASTM Type C and Type F ash, or CSA Type C, Type CI, and Type F ash). The ash is not produced as an optimal SCM; instead, it is optimized for power generation and preventing polluting combustion: the consistency of the by-product ash cannot be guaranteed. Other issues for the future of fly ash in concrete include the significant reduction in regional availability due to the transition from coal energy to natural gas in many markets. Therefore, the introduced carbon will negatively affect the air entrainment in the concrete during post-combustion, and the recovery of ash from the accumulation will increase costs and must be tested to verify the quality every time.

[0011] Ground granulated blast furnace slag (GGBFS) is a glassy CaO-SiO2 by-product of iron production in blast furnaces. Concrete incorporating GGBFS exhibits many favorable properties, including improved chemical durability, whiteness, reduced heat of hydration, reduced CO2 traces, and other beneficial properties. Unfortunately, due to the small number of blast furnaces operating in most markets, the supply of blast furnace slag is quite limited. As a result, GGBFS is in high demand as a high-quality SCM, with prices similar to those of cement itself. Furthermore, limited geographic supply leads to shortages or at least high transportation costs in many local concrete markets. Finally, iron production and the resulting blast furnace slag supply are not directly linked to concrete demand, making the supply, local availability, and market price of these important admixtures largely a matter of chance.

[0012] Natural pozzolans are siliceous or aluminosiliceous materials capable of participating in a pozzolanic reaction with Ca(OH)2. These include mined or calcined pozzolans, diatomaceous earth, kaolin and other clays, MK-750, and other natural minerals and rocks, which react with lime to produce hydrated calcium silicate compounds. Natural pozzolans can be very effective SCMs in concrete, however, they require mining of non-renewable resources, and pozzolans typically require considerable transportation distances, as deposits are not very common. Furthermore, natural materials often require extensive processing, such as calcination, to enhance the reactivity of the natural pozzolans.

[0013] Fly ash (typically with low CaO content, as Type F), GGBF, and certain natural and processed “pozzolans” (e.g., volcanic ash, zeolites, and MK-750) are also common geopolymer reagents and are similarly disadvantageously limited in terms of supply, geographic availability, price, quality, and consistency for their use in geopolymer binders and cements.

[0014] To overcome certain limitations in the supply of these existing SCM and geopolymer reagents, several attempts have been made to improve traditional methods. Despite some improvements, these artificial products or compositions still have many drawbacks, such as regarding the reactivity and chemistry of the chemical reagents used for geopolymers (e.g., optimizing the reagents to subsequently produce highly coordinated, branched, and three-dimensional alkali / alkaline earth aluminosilicate polymers). They also require expensive laboratory-grade reagents and cannot simply use globally abundant raw materials.

[0015] Furthermore, previously manufactured vitreous cement agents have angular or fibrous particle morphologies. Consequently, cement pastes made from such agents require large amounts of water and have relatively poor workability (e.g., having excessive yield stress or above-optimum plastic viscosity), which are obstacles to their use in practical concrete applications.

[0016] Combustion ashes and silica fume generally do not have angular particle morphology. However, these are not available in sufficient quantities, do not have the proper chemical properties, and / or are too expensive to support a large-scale shift to high SCM blended hydraulic or geopolymer cements.

[0017] Thus, there is a need for a cement reagent that addresses existing workability problems with a similar degree of effectiveness as superplasticizers and water reducers in equivalent Portland cement mix design. There is also a need for a method of reducing CO2 emissions in Portland cement production, particularly a need for an engineered cement reagent with low or zero process CO2 emissions that can be used as an auxiliary cement material in hydraulic cements and / or a solid geopolymer reagent.

[0018] There is also a need for a cement reagent that can be universally produced from globally abundant raw materials, is reactive in cement systems, and provides workable low yield stress cement mixtures.

[0019] Further, there is a need to produce cement reagents where production locations can be selected based on market needs. There is a particular need for non-angular particles or microspheroidal glassy particles that can be used in cement reagents, geopolymer reagents, auxiliary cement materials (SCMs), cement mixtures, and concrete.

[0020] There is also a need to economically produce such microspheroidal glassy particles, for example, by using globally abundant raw materials. There is also a need for apparatuses, systems, and methods of flight melting / quenching where solid particles flow in a suspension, are melted in a suspension, and are quenched in a suspension.

[0021] The present invention addresses these and other needs, which will become apparent from the following disclosure and description of the features of the present invention.

[0022] The primary cement used in concrete today is a hydrated solidified calcium silicate product known as Portland cement. Unfortunately, the manufacture of Portland cement clinker results in CO2 emissions (from heating limestone), which has global implications (about 3-5%, not counting fuel-derived GHG emissions). The process is carried out in a rotary kiln, with raw meal flowing countercurrent to the kiln burner. The process is very energy intensive, consuming about 3-5 GJ / ton, of which about 1.5 GJ / ton is used for calcining limestone alone. Among the few viable strategies to reduce the environmental impact of cement, geopolymer chemistry offers a globally viable alternative cement with improved environmental and material properties. The inconsistent supply and limited geographical availability of traditional geopolymer reagents such as fly ash and slag limit the standardization and adoption of geopolymer concrete. On the other hand, the increasing demand for supplementary cementitious materials (SCMs) in hydraulic cements (to improve material and environmental performance) further strains the demand for these materials.

[0023] As mentioned above, various attempts have been made to manufacture cementitious agents. However, these methods have serious drawbacks that have prevented economical production of vitreous cementitious agents.

[0024] For example, in existing academic research on cement reagents (a natural extension of traditional glassmaking technology), high-temperature refractory-lined furnaces and crucibles have been used to directly contain the glass melt. However, the solid refractory materials in the crucible and the surrounding conventional furnaces require low heating and cooling rates (about 10-50°C / min) to avoid thermal shock cracking. Traditional melting furnaces have high thermal mass, which makes maintenance difficult and costly due to long startup and shutdown cycles. It is preferred to avoid refractory materials that need to directly contact the melt to avoid complexity, wear and considerable startup and shutdown times.

[0025] The quenching of molten glass for cementitious agents (e.g., blast furnace slag) previously required water, which is expensive, inhibits heat recovery, can have negative environmental consequences, and can require increased complexity in solid / liquid separation. Consequently, melt quenching methods are wasteful and slow, reducing reactivity. Air quenching methods for cooling the melt are either too slow or require very specific chemistry to ensure a low melt viscosity of about 1 Pa*s or less, which is not feasible for most desired feedstock materials.

[0026] Previous glassmaking methods required expensive particle size reduction (grinding) of the glassy product (usually before and after heat treatment).

[0027] Therefore, there remains a need for a convenient and economical method of making vitreous cement agents from globally abundant raw materials.

[0028] There is also a need to minimize energy consumption and handle very high and variable melt viscosities without the need for flux.

[0029] There is also a need for methods of producing microspherical glassy particles and apparatus and systems for producing such microspherical glassy particles.

[0030] The present invention addresses these needs and other needs, which will become apparent from a reading of the disclosure and description of the features of the invention that follows. Summary of the Invention

[0031] Embodiments are particularly directed to an alternative cementitious material (ACM) that, in some embodiments, comprises solid microspherical glassy particles having one or more of the following properties: an average roundness (R) > 0.8; and less than about 40% of the particles having an angular morphology (R < 0.7).

[0032] In some embodiments, the particles have an average roundness (R) of at least 0.9. In embodiments, less than about 30% of the particles, or less than about 25% of the particles, or less than about 20% of the particles, or less than about 15% of the particles, or less than about 10% of the particles have an angular morphology (R < 0.7).

[0033] In some embodiments, the particles comprise an average oxide of Formula 1:

[0034] (CaO,MgO) a (Na2O, K2O) b (Al2O3,Fe2O3) c (SiO2) d [Formula 1];

[0035] wherein a is from about 0 to about 4, b is from about 0.1 to about 1, c is 1, and d is from about 1 to about 20.

[0036] In some embodiments, the particles further comprise one or more of the following properties: (i) an X-ray amorphous solid content of 45% to 100%, preferably 90 to 100%; and (ii) (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 The molar composition ratio of .

[0037] According to another aspect, some embodiments relate to a cementitious agent comprising a mixture of microspheroidal glassy particles as defined herein.

[0038] According to another specific aspect, some embodiments of the present invention are directed to cementitious agents comprising a mixture of microspherical glassy particles, the particles comprising one or more of the following properties: (i) an average roundness (R) > 0.8; (ii) less than about 20% of the particles having an angular morphology (R < 0.7); (iii) an oxide of formula 1 as defined above; (iv) an X-ray amorphous solid content of 45% to 100%, preferably 90% to 100%; and (v) (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 and (vi) a low calcium content of less than about 10wt% CaO, or an intermediate calcium content of about 10-20wt% CaO, or a high calcium content of greater than 30wt% CaO.

[0039] In some embodiments, the cementitious agent is in the form of a non-crystalline solid. In some embodiments, the cementitious agent is in the form of a powder. In some embodiments, the particle size distribution (i.e. surface area mean or Sauter mean diameter) of D[3,2] is about 20 pm or less, more preferably 10 pm or less, or most preferably 5 pm or less. In one embodiment, the mixture of microspheroidal glassy particles of the cementitious agent comprises oxides of formula 1 as defined above. In some embodiments, the cementitious agent comprises less than about 10 wt% CaO. In some embodiments, the cementitious agent comprises more than about 30 wt% CaO. In some embodiments, the cementitious agent is about 40-100% X-ray amorphous, preferably about 80% X-ray amorphous, 90% X-ray amorphous and up to about 100% X-ray amorphous, and in some embodiments, 100% non-crystalline.

[0040] According to some embodiments, the geopolymer binder comprises a cementitious agent as defined herein. According to another specific aspect, some embodiments of the present application relate to a supplementary cementitious material (SCM) comprising a cementitious agent as defined herein, for example a SCM comprising at least 20 wt% of a cementitious agent.

[0041] According to another specific aspect, some embodiments relate to a solid concrete comprising a cementitious agent as defined herein.

[0042] According to another specific aspect, some embodiments relate to the use of a microspheroidal glassy particle as defined herein, and the use of a cementitious agent as defined herein, for the manufacture of a geopolymer binder or cement, a hydraulic cement, a supplementary cementitious material (SCM) and / or a solid concrete.

[0043] According to another specific aspect, some embodiments relate to a method of producing a cementitious agent from an aluminosilicate material, comprising the steps of: (i) providing a solid aluminosilicate material; (ii) flyer melting / quenching the solid aluminosilicate material to melt the material into a liquid and then quenching the liquid to obtain a melted / quenched powder comprising solid microspheroidal glassy particles; thereby obtaining a cementitious agent having the powder of microspheroidal glassy particles.

[0044] In some embodiments, the method further comprises the step (iii) of grinding the powder of microspheroidal glassy particles into a finer powder. In one embodiment, the powder has a particle size distribution of D[3,2] of about 20 pm or less, more preferably 10 pm or less, or most preferably 5 pm or less.

[0045] In some embodiments, the cementing agent obtained by the method comprises one or more of the following properties: is reactive in a cement system and / or a geopolymer system; provides a workable geopolymer cement mixture with a low yield stress of less than 25 Pa when the cement paste has an oxide molar ratio of H2O / (Na2O, K2O) < 20; requires a water content in the cement paste such that the oxide molar ratio H2O / (Na2O, K2O) < 20; and provides a cement paste with higher workability than an equivalent paste having a substantially angular morphology at the same water content.

[0046] In some embodiments, the method further comprises the step of adjusting the composition of the non-ideal solid aluminosilicate material to the desired content of elements Ca, Na, K, Al, Fe and Si. In one embodiment, the adjusting comprises blending the non-ideal aluminosilicate material with a composition adjusting material to achieve the desired ratio with respect to one or more of the elements Ca, Na, K, Al, Fe and Si.

[0047] In some embodiments, the method further comprises the step of sizing the solid aluminosilicate material to obtain a powder of aluminosilicate particles of a desired size. In some embodiments, the method further comprises the step of discarding undesirable waste material from the solid aluminosilicate material.

[0048] In some embodiments, the fly-melting comprises heating at a temperature above the liquidus temperature to obtain a liquid. In some embodiments, the temperature is between about 1000-1600 °C, or between about 1300-1550 °C.

[0049] In some embodiments, the method further comprises the step of adding a fluxing agent material to the solid aluminosilicate material to lower its melting point and / or induce a greater enthalpy, volume or depolymerization of the liquid. In some embodiments, the fluxing agent material is mixed with the solid aluminosilicate material prior to or during the melting.

[0050] In some embodiments, the fly-melting / quenching comprises reducing the temperature of the liquid below the glass transition temperature to obtain a solid. In some embodiments, the fly-melting / quenching comprises reducing the temperature of the liquid to below about 500 °C, or preferably below about 200 °C or lower. In some embodiments, reducing the temperature of the liquid comprises quenching at a rate of about 10 2 Ks -1 to about 10 6 Ks -1 , preferably at a rate of > 10 3.5 Ks -1 In some embodiments, the quenching comprises cold air, steam or water. In one embodiment, the method further comprises separating the quenched solid particles from the hot gas in a cyclone.

[0051] In some embodiments, the method of producing a cement reagent from aluminosilicate material further comprises reducing the particle size of the solid microspheroidal glassy particulate powder. In some embodiments, reducing the particle size comprises crushing and / or pulverizing the powder in a ball mill, roll mill, vertical roll mill, or the like.

[0052] According to another aspect, some embodiments relate to an apparatus for producing microspheroidal glassy particles, the apparatus comprising a burner, a melting chamber, and a quenching chamber. The melting chamber and the quenching chamber can be completely separate, or can be respectively a first portion and a second portion of the same chamber.

[0053] The apparatus can be configured such that the solid particles flow in suspension in the apparatus, are suspended melted, and then are suspended quenched.

[0054] In some embodiments, the burner provides a flame that heats the suspended solid particles to a heating temperature sufficient to substantially melt the solid particles into a liquid. In some embodiments, the burner comprises a gas-fueled flame that carries aluminosilicate feedstock particles into the melting / quenching chamber. The gas can comprise an oxidizer gas and a combustible fuel. In some embodiments, the burner comprises at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a solar concentrator furnace.

[0055] In some embodiments, the quenching chamber of the apparatus comprises a cooling system for providing cold air within the quenching chamber that shock cools the melted particles into solid microspheroidal glassy particles. In some embodiments, the cooling system comprises a liquid cooling loop positioned around the quenching chamber.

[0056] In some embodiments, the apparatus further comprises a cyclone separator to collect the microspheroidal glassy particles. According to some embodiments, a method of producing a cement reagent from aluminosilicate material comprises the steps of: (i) providing a solid aluminosilicate material; (ii) flight melting / quenching the solid aluminosilicate material to melt the material into a liquid and then quenching the liquid to obtain a melted / quenched powder comprising solid microspheroidal glassy particles; thereby obtaining a cement reagent having the microspheroidal glassy particulate powder.

[0057] According to some embodiments, a method of producing microspheroidal glassy particles comprises the steps of: providing a flight melting / quenching apparatus comprising a burner, a melting chamber, and a quenching chamber; providing solid particles; flowing the solid particles in suspension in a gas combusted by the burner; heating the solid particles in the melting chamber to a heating temperature above the liquidus to obtain suspended liquid particles; and shock cooling the suspended liquid particles to a cooling temperature below the liquidus to obtain a powder comprising solid microspheroidal glassy particles.

[0058] In some embodiments of these methods, the solid particles comprise an aluminosilicate material. In some embodiments of these methods, the heating temperature is about 1000-1600° C. or about 1300-1550° C. In some embodiments of these methods, the cooling (quenching) temperature is less than about 500° C., or less than about 200° C.

[0059] In some embodiments of these methods, quenching comprises providing cool air within the quenching chamber. In some embodiments, these methods further comprise collecting the powder with a cyclone separator.

[0060] Further aspects of some embodiments of the invention relate to the use of an apparatus as defined herein, in particular an apparatus comprising at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner and a solar concentration furnace, for producing microspheroidal glassy particles using in-flight melting / quenching.

[0061] A further aspect of some embodiments of the invention relates to the use of an apparatus as defined herein, in particular an apparatus comprising at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner and a solar concentration furnace, for producing cementitious agents from aluminosilicate materials using on-the-fly melting / quenching.

[0062] Other aspects, advantages and features of the present invention will become more apparent upon reading the following non-limiting description of preferred embodiments, which are exemplary and should not be construed as limiting the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] A better understanding of the features, advantages and principles of the present disclosure will be obtained by referring to the following detailed description and accompanying drawings, which set forth illustrative embodiments.

[0064] Figure 1 is a flow chart for producing a cementitious agent starting from a solid aluminosilicate material, according to some embodiments.

[0065] Figure 2 is a set of four ternary CaO, MgO-SiO2-(Na2O, K2O)-(Al2O3, Fe2O3) composition diagrams according to some embodiments.

[0066] Figure 3 According to some embodiments, using Figure 2 The same material composition data drawn in the three-dimensional quaternion diagram in the (CaO, MgO)-(Al2O3, Fe2O3)-(Na2O, K2O)-(SiO2) space.

[0067] Figure 4This is a particle size distribution graph comparing the angular and spherical particle size distributions of commercially available natural volcanic glass powder (angular) and the particles prepared in Example 1 (spherical). The volume percentage of particles below a given diameter is presented as a function of particle diameter in micrometers (x-axis) (y-axis). Electron micrographs demonstrate the particle morphology of the samples.

[0068] Figure 5 is a graph comparing the particle roundness (R) distribution of various powders according to some embodiments; before (501) and after (502) treatment according to Examples 1-8 (211-218, 519, 520 are defined below). Figure 6 and Figure 7 In the micrograph of the same powder shown, the circularity was corrected by aspectratio according to the method of Takashimizu and Liyoshi (Takashimizu, Y., Liyoshi, M. (2016). New parameter of roundness R: circularity corrected by aspectratio. Progress in Earth and Planetary Sciences 3, 2. https: / / doi.org / 10.1186 / s40645-015-0078-x ), the R value was determined using image analysis, and more accurate data are listed in Table 17. For convenience, two types of F fly ash samples are also included, 519 (B-FA) commercially sold beneficiated fly ash, and 520 (LFA) unbeneficiated fly ash directly from coal-fired power plants.

[0069] Figure 6 Electron micrographs of unprocessed particles (501) and processed particles (502) from various materials (211-218 as defined below) as described in Examples 1 to 8. The field of view is 140 μm wide.

[0070] Figure 7 Images of two types of Type F fly ash: one directly from a coal-fired power plant in Nova Scotia (L-FA; 520) and another commercial fly ash that has been finely refined to remove activated carbon and other contaminants (B-FA; 519). The field of view is 140 μm wide.

[0071] Figure 8 FIG. 1 is a schematic process flow diagram of a system for producing glassy microspherical cement agents according to one embodiment of the present invention.

[0072] Figure 9A and 9B A photograph and corresponding diagram, respectively, of a burner flame (bottom) entering a melting / quenching chamber (top) with entrained aluminosilicate feedstock particles according to one embodiment of the present invention.

[0073] Figure 10 is a schematic diagram of an improved flight melting plant according to one embodiment of the present invention, the plant including a heat recovery loop for minimizing energy input and CO2 emissions.

[0074] Figure 11 Some examples are shown, along with ternary phase diagrams of new compositions close to Si, Al, Fe, Ca+Mg, and Na+K.

[0075] Figure 12 The ternary phase diagram of the new composition is illustrated from the perspective of Si; according to some embodiments.

[0076] Figure 13 The ternary phase diagram of the new composition is illustrated from the perspective of Al; according to some embodiments.

[0077] Figure 14 The ternary phase diagram of the new composition is illustrated from the perspective of Fe; according to some embodiments.

[0078] Figure 15 The ternary phase diagram of the new composition is illustrated from the perspective of Ca+Mg; according to some embodiments.

[0079] Figure 16 is a schematic flow chart describing a process for manufacturing alternative cement concrete using relatively small decentralized flying micro-kilns according to some embodiments;

[0080] Figure 17 is a schematic diagram illustrating conventional cement and aggregate distribution in a modern centralized Portland cement kiln supply chain according to some embodiments;

[0081] Figure 18 According to some embodiments, the transportation advantages of deploying alternative cementitious material (ACM) micro-kilns at aggregate quarries using a new decentralized approach are described.

[0082] Figure 19 According to some embodiments, the advantages of transporting alternative cementitious material (ACM) micro-kilns in a new dispersion method deployed in concrete batching plants are described.

[0083] Figure 20 is a schematic diagram illustrating the advantages of locating small-scale kilns for transporting alternative cementitious materials (ACM) at independent locations near aggregate quarries and concrete batching plants in a new decentralized approach, according to some embodiments.

[0084] Further details of the invention and its advantages, in accordance with some embodiments, will become apparent from the detailed description included below. DETAILED DESCRIPTION

[0085] The following detailed description provides a better understanding of the features and advantages of the application described in the present disclosure according to embodiments disclosed herein. While the detailed description includes many specific embodiments, these embodiments are provided by way of example only and should not be construed as limiting the scope of the application disclosed herein.

[0086] In the description of the following embodiments, reference is made to the accompanying drawings which form a part hereof, and in which are shown by way of illustration embodiments of the embodiments of the application. It is to be understood that other embodiments can be made without departing from the scope of the disclosed application.

[0087] Microspherical glass particles

[0088] Some embodiments relate to the production and use of solid microspheroidal glassy particles. As explained in more detail below, related aspects relate to cementitious reagents comprising a mixture of such microspheroidal glassy particles or a plurality of such microspheroidal glassy particles.

[0089] According to the present application, the solid microspheroidal glassy particles are notably round particles of high sphericity.

[0090] As used herein, the terms “roundness” and the corresponding unit “R” refer to the roundness as defined by Takashimizu and I Lyoshi (2016). The values required to calculate R can be determined by image analysis on appropriate photomicrographs of the powder. R (roundness) provides a convenient roundness quantitative measure that is highly correlated with Krumbein’s “roundness” (Krumbein, W. C. (1941) Measurement and geological significance of shape and roundness of sedimentary particles. Journal of Sedimentary Petrology 11 : 64-72. https: / / doi.org / 10.1306 / D42690F3-2B26-HD7-8648000102C1865D).

[0091] In some embodiments, the average roundness (R) of the microspheroidal glassy particles is at least 0.9 (standard deviation < 0.15).

[0092] In some embodiments, the bulk roundness (R) of the microspheroidal glassy particles is at least 0.8 (standard deviation < 0.15).

[0093] In some embodiments, the bulk roundness (R) of the microspheroidal glassy particles is at least 0.7, or 0.6, or 0.5 (standard deviation < 0.15).

[0094] In some embodiments, the mixture of microspherical glassy particles comprises less than about 50% of the particles, or less than about 40% of the particles, or less than about 30% of the particles, or less than about 25% of the particles, or less than about 20% of the particles, or less than about 15% of the particles, or less than about 10% of the particles having an angular morphology (e.g., R < 0.7).

[0095] In some embodiments, the mixture or plurality of microspherical glassy particles is provided in a powder form comprising a particle size distribution with a D[3,2] of about 20 μm or less, more preferably about 10 μm or less, or most preferably about 5 μm or less.

[0096] In some embodiments, the microspheroidal glassy particles are non-crystalline solids.

[0097] In some embodiments, the microspherical glassy particles comprise an oxide of Formula 1: (CaO, MgO) a (Na2O, K2O) b (Al2O3,Fe2O3) c (SiO2) d [Formula 1], wherein a is about 0 to about 4, b is about 0.1 to about 1, c is 1, and d is about 1 to about 20.

[0098] In some embodiments, the microspherical glassy particles include one or more of the following properties: (i) an X-ray amorphous solid content of 45% to 100%, preferably 90 to 100%; and (ii) (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 The molar composition ratio of .

[0099] In some embodiments, the microspherical glassy particles are 40% to 100% X-ray amorphous, more preferably about 80% to about 100% X-ray amorphous, and in some embodiments, 100% non-crystalline.

[0100] In some embodiments, the particles comprise less than about 10 wt% CaO.

[0101] In some embodiments, the particles comprise greater than about 30 wt% CaO.

[0102] In some embodiments, the particles comprise Si / (Fe 3+ ,Al) has a molar composition of 1-20 and a high calcium content, with a CaO content of about 10 to about 50 weight %, preferably about 20 to 45 weight %.

[0103] In some embodiments, the particles comprise Si / (Fe 3+ ,Al) molar composition is 1-2 and moderate calcium content, CaO content is about 10 to about 20 weight percent.

[0104] As described below, microspherical glassy particles can be advantageously produced from globally abundant inorganic raw materials such as aluminosilicate materials. As used herein, the term "aluminosilicate material" refers to a material comprising aluminum or aluminum and iron and silicon dioxide selected from natural rocks and minerals, dredged materials, mining waste comprising rocks and minerals, waste glass, aluminosilicate-containing contaminated materials, and aluminosilicate industrial by-products. The aluminosilicate material according to the present invention is preferably in the form of a crystalline solid (e.g., at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or 100% by weight of a crystalline solid). In some embodiments, the aluminosilicate material comprises at least 2 wt% (Na2O, KO), or at least 3 wt% (Na2O, KO), or at least 4 wt% (Na2O, KO), or at least 5 wt% (Na2O, KO), at least 6 wt% (Na2O, KO), or at least 7 wt% (Na2O, KO), or at least 8 wt% (Na2O, KO), or at least 10 wt% (Na2O, KO), or at least 12 wt% (Na2O, KO), or at least 15 wt% (Na2O, KO), or at least 20 wt% (Na2O, KO).

[0105] In some cases, the inorganic feedstock is heterogeneous and the glassy particles produced are more homogeneous than the feedstock, as shown by partial homogenization during melting. That is, more than 10% of the produced particles fall within the new intermediate formulation range.

[0106] In some embodiments, the aluminosilicate material is selected from dredged sediments, demolished concrete, mine waste, glacial clays, glacial sediments, river sediments, rocks and mineral mixtures, such as rocks and mineral mixtures composed of some or all of the elements Ca, Mg, Na, K, Fe, Al, and Si. These aluminosilicate materials are widely abundant in many different geographic regions.

[0107] As described below, the elemental composition of the feedstock can be analyzed and optimized for the desired use.The feedstock can be analyzed to determine the feedstock elemental composition by quantitative or semi-quantitative methods such as XRF, XRD, LIBS, EDS, wet chemical analysis, and various other existing methods.

[0108] As described below, microspheroidal glassy particles can be produced using a process or method for in-flight thermochemical processing, such as in-flight melting / quenching and / or suspension melting, for melting the starting inorganic material into a liquid and then quenching the liquid into solid particles. As used herein, the term "in-flight melting / quenching" or "suspension melting" refers to a process in which solid particles are flowed in a suspension, melted in the suspension, and then quenched in the suspension to obtain a powder.

[0109] In some embodiments, the term "microspherical glassy particles" includes particles as defined above that are present in a powder obtained directly from an in-flight melting / quenching process. In some embodiments, the term "microspherical glassy particles" refers to particles obtained after grinding or milling (e.g., jaw crusher, impact mill, etc.) of a powder obtained after an in-flight melting / quenching process.

[0110] As described below, the microspherical glassy particles have many uses, including, but not limited to, as or in the preparation of a cementitious agent, as or in the preparation of a geopolymer binder or cement, as or in the preparation of a hydraulic cement, as or in the preparation of supplementary cementitious materials (SCMs), and in the preparation of solid concrete.

[0111] A further use could be as a fertilizer or soil conditioner, for example as a replacement for "rock dust".

[0112] cement materials

[0113] Some embodiments described herein relate to cementitious agent powders comprising microspheroidal glassy particles as defined herein.

[0114] Some embodiments also relate to geopolymer binders or cements, hydraulic cements, supplementary cementitious materials, hydraulic concrete mixes, and solid concrete powders comprising the microspheroidal glassy particles as defined herein.

[0115] Particle morphology has a considerable impact on the physical properties and handling of cement slurries. Therefore, the highly rounded morphology of the particles according to the present invention advantageously provides increased workability, fluidity, and / or reduced water requirements for geopolymer cement mixtures. In particular, having high roundness reduces the yield stress and viscosity of the cement mixture by reducing interparticle friction. Additionally, the spherical morphology reduces water requirements by improving packing for a given particle size distribution.

[0116] like Figure 2 and 3As shown, the composition of the cement reagent according to an embodiment of the present invention is different from that of existing cement materials. In fact, considering the element groups (CaO, MgO), (Al2O3, Fe2O3), (Na2O, K2O) and (SiO2) of the three-phase composition, the position occupied by the embodiment of the cement reagent 201 in these figures is different from that of fly ash (C and F) 202, ground blast furnace slag (GGBS or GGBF) 203, metakaolin 204 and Portland cement 205. Examples of specific raw material compositions are shown in Figure 2 : Volcanic pumice 211 (Example 1), basalt 212 (Example 2), second basalt 213 (Example 3), coal tailings sample 214 (Example 4), dredged sediment 215 (Example 5), copper porphyry flotation tailings 216 (Example 6), demolished concrete 217 (Example 7), sphalerite aggregate crushing dust 218 (Example 8).

[0117] Advantageously, cement reagents are prepared from globally abundant rocks, minerals, and compounds of suitable composition. In this way, it is not necessary to transport the abundant raw materials to distant processing equipment or cement plants. In some cases, cement plants are built at the raw material location.

[0118] In some embodiments, the cementitious agent comprises a mixture of microspheroidal glassy particles as defined herein, and further comprises one or more of the following properties: (i) in the form of a non-crystalline solid; (ii) in the form of a powder; (iii) comprising a particle size distribution with D[3,2] of about 20 μm or less, more preferably 10 μm or less, or most preferably 5 μm or less; (iv) comprising an oxide of formula 1 as defined above; (v) having an X-ray amorphous solid content of 45% to 100%, preferably 90 to 100%; (vi) (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 (vii) containing less than about 10 wt% CaO; (viii) containing greater than about 30 wt% CaO; (ix) containing 1-20 Si / (Fe 3+ ,Al) molar composition and a CaO content of about 10-50 wt%, preferably about 20-45 wt%; (x) containing 1-20 Si / (Fe 3+,Al) molar composition and a CaO content of about 10-20 weight percent; (xi) is 40-100% X-ray amorphous, more preferably greater than 80%, greater than 90%, and in some cases, up to about 100% X-ray amorphous, and in some cases, is 100% non-crystalline; (xii) comprises a particle size distribution with a D[3,2] of about 20 μm or less, more preferably about 10 μm or less, or most preferably about 5 μm or less.

[0119] In some cases, the CaO content is less than about 30 wt. % to reduce the CO2 impact of the cement by avoiding decomposition of carbonate-derived calcium.

[0120] In some embodiments, the cementitious agent comprises less than about 10% by weight of CaO. In some embodiments, the cementitious agent comprises greater than about 30% by weight of CaO. In some cases, the composition of the cementitious agent with respect to Na, K, and Ca can be varied to achieve certain advantages depending on the binder requirements. For example, a cementitious agent having less than about 10% by weight of CaO is suitable for use in heat-curing geopolymers and as a fly ash replacement. Alternatively, a cementitious agent having greater than about 30% by weight of CaO is hydraulically settable and can be added to geopolymer resins to allow ambient temperature curing of the geopolymer cement and directly replace blast furnace slag in blended Portland cement.

[0121] In some embodiments, the cementitious agent is Si / (Fe 3+ A low-calcium cementitious agent having a molar composition of 1-20 (A, Al) and a CaO content of about 10% by weight or less. Preferably, such a cementitious agent is 40-100% X-ray amorphous, more preferably about 80%-100% X-ray amorphous, and in some embodiments, is 100% amorphous. Such a low-calcium cementitious agent may have numerous commercial applications, for example, as a pozzolan admixture in hydraulic cements, and / or as an agent in geopolymer binders and cements.

[0122] In some embodiments, the cementitious agent is a high calcium content cementitious agent with a Si / (Fe 3+ The present invention relates to a cementitious agent comprising a calcium carbonate (CaO) composition of 1-20, and a CaO content of about 10-50% by weight, preferably about 20-45% by weight. Preferably, the cementitious agent is 40-100% X-ray amorphous, more preferably about 80-100% X-ray amorphous, and even more preferably 100% amorphous. The high-calcium cementitious agent has many commercial applications, such as as a hydraulic admixture in mixed hydraulic cements and / or as an agent in geopolymer binders and cements.

[0123] In some embodiments, the cementitious agent is an intermediate calcium-containing cementitious agent with a Si / (Fe3+ ,Al) has a molar composition of 1-20 and a CaO content of about 10-20 wt%. Preferably, this cementitious agent is about 40-100%, preferably about 80%-100% X-ray amorphous, and even more preferably 100% amorphous. This intermediate calcium-containing cementitious agent has many commercial applications, for example as a cementitious agent with desirable intermediate hydraulic and pozzolanic properties, particularly in ambient-setting geopolymer applications.

[0124] In some embodiments, the Na, K content of the cementitious reagent is optimized. This can be advantageous for SCM applications, where free lime in the hydraulic cement will be exchanged for soluble alkali and coordinated with sialate molecules derived from the cementitious reagent to produce a degree of relatively stable alkaline aluminosilicate polymerization, which greatly improves the chemical properties of traditional hydraulic cements. In embodiments, since geopolymer reagents with significant Na, K content require less soluble silicate hardener than would otherwise be required, the soluble silicate requirement (and cost) of the geopolymer mix design is reduced.

[0125] Preparation method

[0126] The microspheroidal glassy particles defined herein, and compositions comprising the microspheroidal glassy particles, such as cementitious agents, geopolymer binders or cements, hydraulic cements, supplementary cementitious materials (SCMs), and concretes, can be prepared using any suitable method or process.

[0127] Figure 1 Illustrative steps required to produce a cementitious agent from an aluminosilicate material according to some embodiments are shown. Briefly, a finely divided aluminosilicate material powder is selected 101 and analyzed 102 to assess its chemical composition. The raw material can be analyzed to determine its elemental composition using any suitable quantitative or semi-quantitative method, such as XRF, XRD, LIBS, EDS, wet chemical analysis, and various other conventional methods.

[0128] If the selected composition is unacceptable, the material can optionally be adjusted, blended (e.g., in a container prior to thermochemical processing), such as by adding composition conditioning material 104 (see below) or sorted 103, and any undesirable waste material can be discarded.

[0129] The resulting solid aluminosilicate material, comprising a powder of the desired composition, is then heated 106 to melt the individual particles or particle agglomerates into a liquid suspension. The liquid particles in suspension are then quenched 107 to obtain a powder comprising solid microspherical glassy particles. The powder is then optionally crushed and / or pulverized (partially or completely) 108 if desired to reduce particle size and / or optimize reactivity and obtain a cementitious agent 109.

[0130] With respect to the addition of composition adjusting material 104, as used herein, the term "composition adjusting material" refers to any solid or liquid material whose composition is suitable for preferentially changing the bulk or surface composition of the aluminosilicate material, involving one or more of the elements Ca, Na, K, Al, Fe and Si.

[0131] Composition-adjusting materials for introducing calcium (Ca) may include calcium salts, including CaCO3, Ca(OH)2, CaO, CaCl2, CaF2, calcium silicate minerals and compounds, calcium aluminum silicate minerals and compounds, waste Portland cement products, waste hydraulic cement products, wollastonite, anorthite and other calcite group mineral compositions.

[0132] Composition-adjusting materials for introducing aluminum (Al) can be composed of aluminous rocks, minerals, soils, sediments, byproducts, and compounds, including one or more of kaolinite, halloysite, and other aluminum-rich / alkali-poor clay minerals, Al2SiO5 polymorphs, chlorite, hydrotalcite, garnet, corundum, mullite, anorthite, diaspore, boehmite, gibbsite, nepheline, and other feldspars. Other materials that can be used include aluminum metal, bauxite, alumina, and red mud (alumina refining residue).

[0133] Composition-adjusting materials for introducing iron (Fe) can include iron-rich rocks, minerals, soils, sediments, byproducts and compounds, such as olivine, chlorite minerals (biotite, clinochlore, etc.), pyroxene, hornblende, goethite, hematite, magnetite, ferrihydrite, lepidocrocite and other iron oxyhydroxide compositions, iron-rich clays and phyllosilicate minerals, iron ore tailings and elemental iron.

[0134] Regarding heating 106, heating is performed to reach a heating temperature above the liquidus temperature to obtain a liquid, for example, about 1000-1600° C., or about 1300-1550° C. Any suitable method or device can be used to heat and obtain the liquid, including but not limited to flying melting (i.e., suspension melting). This can be achieved by using a flying melting device equipped with, for example, one or more plasma torches, oxygen-fuel burners, air-fuel burners, biomass burners, or solar concentrating furnaces.

[0135] Typically, furnace temperatures of 1000-1600°C, most typically 1300-1550°C, are required to quickly obtain the desired liquid phase particles in suspension. In embodiments, the apparatus is selected so that melting is as rapid as possible. Examples of suitable on-the-fly melting apparatus and methods are described herein.

[0136] With respect to quenching 107, in some embodiments, the quenching step comprises lowering the temperature of the liquid to below the glass transition temperature, for example, at about 500°C or less, or preferably below about 200°C or less. In embodiments, the quenching is performed rapidly, i.e., the temperature is increased at about 10 2 Ks -1 -10 6 Ks -1 The rate (preferably >10 3.5 Ks -1 Any suitable method can be used for quenching, including but not limited to contacting the molten material with a sufficiently cold air flow, steam or water to produce an amorphous solid. If desired, a fluxing material can be added to the solid aluminosilicate material to lower its melting point and / or induce liquid depolymerization. The fluxing material can be mixed with the solid aluminosilicate material before or during heating / melting. Common fluxing materials that can induce depolymerization and / or lower melting temperatures in the melt include CaF2, CaCO3, waste glass, cullet, glass frit, alkali-containing minerals (such as feldspar, zeolite, clay and feldspar minerals), borates, halogen compounds (salts containing fluoride and chloride) and calcium salts.

[0137] With respect to the optional crushing and / or pulverizing step 108, this can be performed using any suitable method or equipment, including but not limited to a ball mill, a roller mill, and a vertical roller mill. Preferably, the particle size is reduced to obtain a fine powder that can be used in cement applications. Obtaining a finer powder can be used to increase the surface area and provide a faster reaction rate, as described in Example 9. One skilled in the art will be able to determine the size of particles required for a particular need, taking into account the economic trade-offs between loss of spherical morphology / workability, grinding costs, and final performance requirements. In an embodiment, the powder has a particle size distribution with D[3,2] of about 10 μm or less, or preferably 5 μm or less. Such a particle size is generally desired to ensure adequate reactivity and consistent material properties.

[0138] Applications of Aluminosilicate Materials

[0139] As described herein, some embodiments relate to the use of aluminosilicate materials to produce solid microspheroidal glassy particles and amorphous cementitious agents as defined herein.

[0140] Another aspect is the use of in-flight thermochemical processing of aluminosilicate materials to produce solid microspheroidal glassy particles and / or solid cementitious agents. The glassy particles and solid cementitious agents described herein can be advantageously used as a replacement supplementary cementitious material (SCM) in blended hydraulic cements and / or geopolymer solid agents in geopolymer binders (thus eliminating the need for some or all of MK-750, fly ash, GGBFS, and other common solid agents).

[0141] Another related aspect is the use of an aluminosilicate material for producing at least one of a supplementary cementitious material (SCM) and a geopolymeric agent comprising solid microspheroidal glassy particles and / or a non-crystalline cementitious agent, as defined herein.

[0142] Uses of microspherical glass particles and cement reagents

[0143] One aspect of the embodiments relates to the broad relevance of the solid microspherical glassy particles and cementitious agents described herein. Suitable compositions of engineering cementitious agents can be used interchangeably in geopolymer cements and hydraulic cements (ie, cements that react with water) in significant proportions.

[0144] Thus, some embodiments include geopolymer cements and hydraulic cements comprising at least 5 weight percent, or at least 10 weight percent, or at least 15 weight percent, or at least 20 weight percent, or at least 25 weight percent, or at least 30 weight percent, or at least 40 weight percent, or at least 50 weight percent, or at least 60 weight percent, or at least 70 weight percent, or at least 80 weight percent, or at least 90 weight percent, or more of solid microspherical glassy particles and / or cementitious agents.

[0145] According to some aspects, some embodiments described herein relate to a supplementary cementitious material (SCM) comprising a cementitious agent as defined herein. In some embodiments, the SCM comprises from about 5% to about 50% by weight (preferably at least 20% by weight) of solid microspherical glassy particles and / or a cementitious agent as defined herein.

[0146] According to another aspect, some embodiments described herein are directed to a supplementary cementitious material (SCM) comprising one or more of the following properties: comprising less than about 35 wt% CaO, having an appreciable content of Na+K (e.g., at least 2 wt%, preferably at least 5 wt%) and Al content (e.g., at least 5 wt%), and being in a non-crystalline solid form.

[0147] According to another aspect, some examples of the present invention include: embodiments relate to solid concrete comprising solid microspherical glassy particles and / or cementitious agents as defined herein, i.e., comprising from about 5% to about 50% by weight (preferably at least 10%, or at least 20%, at least 30%, or at least 40% by weight) of solid microspherical glassy particles and / or cementitious agents as defined herein.

[0148] According to another aspect, some embodiments relate to solid geopolymer concrete comprising from about 5% to about 50% by weight (preferably at least 10%, or at least 20%, at least 30%, or at least 40% by weight) of solid microspherical glassy particles and / or a cementitious agent as defined herein.

[0149] Those skilled in the art will appreciate that embodiments of the present invention advantageously provide methods for producing versatile low-CO cementitious reagents from abundant, inexpensive natural materials. Another significant advantage is the production of a single reagent that meets the regulatory standards of today's alternative SCMs while also meeting the needs of the growing geopolymer market. Furthermore, the cementitious reagent is formed from different heterogeneous raw materials, and through the described method, a more uniform reagent material suitable for use as a cementitious reagent is produced.

[0150] It will be appreciated that one advantage of the systems and methods described herein is that control of the final composition of cement reagents is provided, thereby producing reagents with predictable compositions, which is very important for industry. Such customized compositions are not available in other existing cement reagents because they are typically obtained from industrial by-products. According to the embodiments described herein, local raw materials can be modified, if necessary, to standardize the performance of a given application. For example, in the SCM for portland cement, it may be desirable to limit alkali content, but in geopolymer systems, it may be desirable to have a high alkali content and reduce the needs for alkali metal silicate hardeners. In both cases, it may be necessary to change the composition to limit the composition variability of the raw materials.

[0151] Another significant issue with geopolymer reagent chemistry is the variable calcium content. Adjustment of calcium content and calcium-containing phases are important variables for adjusting the rate of strength gain and final material properties of geopolymer cements under varying temperature conditions. The methods described herein allow for the design of certain advantageous compositions of microspherical cement reagents, which is currently not possible with by-product-based cement reagents.

[0152] In-flight melting equipment, methods and systems

[0153] Embodiments also relate to apparatus, systems, and related methods for the thermochemical production of glassy cement reagents having a spherical morphology.

[0154] According to some embodiments, an apparatus is configured for on-the-fly melting / quenching. According to some embodiments, for example Figure 9A and 9B , apparatus 900 includes: a burner 809; and a melting chamber combined with a quenching chamber 902. In some embodiments, the melting chamber and the quenching chamber can each be a first portion of the same chamber 902. In some embodiments, the melting chamber and the quenching chamber are separate, continuous chambers.

[0155] As shown, the apparatus 900 is configured for on-the-fly melting / quenching. Aluminosilicate feedstock particles 903 enter the melting / quenching chamber (top, 902) and are suspended in a flame 901 that burns an oxidant gas 807 and a combustible fuel 808. As the aluminosilicate feedstock particles 903 are heated above the liquidus transition and eventually melt, the particles are entrained into the oxidant gas by a venturi ejector and flow in suspension toward the melting / quenching chamber 902 during combustion. The gas may include an oxidant gas, including but not limited to oxygen, air mixed with a combustible fuel, including but not limited to propane, methane, liquid hydrocarbon fuels, coal, synthesis gas, biomass, coal-water slurry, and mixtures thereof. Preferably, the flame 901 is stabilized by an annular quench air stream 904 that protects the melting / quenching chamber 902 and prevents particles from adhering to the inner wall 905 of the melting / quenching chamber 902.

[0156] In the apparatus 900, as the suspension becomes turbulent at the end of the melting / quenching chamber 902, the molten particles are then quenched by cooling in air. Cooling / quenching of the molten particles can be provided by cooling quenching air directly introduced into the melting / quenching chamber 902 and / or by an optional cooling system, such as a liquid cooling circuit (not shown) surrounding the quenching portion of the melting / quenching chamber 902. The molten particles can be quenched or cooled into an amorphous solid powder, and a powder comprising microspherical glassy particles can be produced. The apparatus can also include an optional cyclone separator that operates under the suction of a centrifugal blower to collect a powder (not shown) comprising microspherical glassy particles.

[0157] Apparatus 900 or similar devices may be used in various systems to produce glassy microspherical cementitious agents. Figure 8 One embodiment of a schematic process flow diagram of an exemplary system 800 for producing glassy microspheroidal cementitious agent, which in some cases produces microspheroidal glassy agent powder 109, is shown.

[0158] exist Figure 8In an embodiment of the present invention, the system 800 includes a grinding circuit 801 to obtain an aluminosilicate raw material powder 101. The coarse aluminosilicate raw material 802 is fed into a jaw crusher or impact mill 803 to produce a feed 804 of suitable size to allow fine grinding in a ball mill 805. The resulting product is a finely divided aluminosilicate raw material powder 101.

[0159] The finely divided aluminosilicate feedstock powder 101 is then entrained in an oxidant gas (e.g., oxygen) 807 and mixed with a combustible fuel (e.g., propane) 808 in a burner 809 equipped with a liquid cooling circuit 810 to extend torch life. Ambient temperature quench air 811 is introduced, preferably near the burner 809, and flows downwardly to the exterior of the melting / quenching chamber 812 walls to prevent molten particles from adhering to the walls of the burner 809. Wall cooling can be provided by the quench air and / or by an optional liquid cooling circuit 813. When the suspension becomes turbulent at the end of the melting / quenching chamber, the molten particles are quenched by the cooled quench air. A cyclone separator 814, operating under the suction of a centrifugal blower 815, can be used to collect the microspherical glassy reagent powder 109.

[0160] Figure 9 equipment and Figure 8 The system was successfully used to produce solid microspherical glassy particles and cementitious agents containing the particles, as defined herein and described in the following examples. The operating parameters involved the approximately stoichiometric combustion of propane and oxygen (the exact mass ratio was not measured). Powdered raw material 101 entered the burner from a pneumatic disperser fed by a vibrating feeder. The suspension of raw material and combustion air consisted of approximately equal masses of oxygen and powdered raw material; for example, 1 gram of aluminosilicate raw material was suspended in 1 gram of oxygen.

[0161] Those skilled in the art will appreciate that the apparatus, systems and parameters shown are one of many potentially useful apparatuses and systems encompassed by the present invention. For example, in an alternative embodiment, the solid particles are suspended in a carrier gas and heated by one or more energy sources. The energy for melting can be provided by one or a combination of suitable high-temperature heat sources, such as plasma (arc discharge or inductive coupling), electric induction heating, resistance heating, microwave heating, solar radiation, or heat from a chemical reaction (e.g., combustion). Several of these energy sources can reduce the CO2 footprint of the method, but the cost of CO2 emissions must be weighed against the unique cost of each energy source. In many jurisdictions today, the cheapest energy sources are based on combustible hydrocarbon fuels. Therefore, the choice of energy is primarily determined by the price and cost of CO2 emissions in a given jurisdiction. Current economic and political factors dictate that, preferably, the solid particles are suspended in a gas so that combustion heats the solid particles to a temperature above the liquid phase transition.

[0162] Although oxy-fuel burners are used in the examples provided, those skilled in the art will appreciate that the choice of burner fuel is secondary as long as sufficient heating occurs. Any heat source from combustion, plasma, concentrated solar, nuclear, etc. is possible.

[0163] In some embodiments, air-fuel burners are preferred to avoid the cost of oxygen enrichment. When burning only air containing about 23 wt% oxygen with a fuel (e.g., propane or methane), the air-fuel ratio is much higher (~4-5 times) to maintain near-stoichiometric combustion. A higher air-fuel ratio results in a lower flame temperature. Therefore, it is preferred to adjust the feedstock powder mass flow rate accordingly to ensure that the particles are heated above their solidus, and preferably close to or above their liquidus temperature (1000-1600°C, and typically greater than 1200°C).

[0164] Figure 10 Another embodiment of an apparatus and system for in-flight melting / quenching according to embodiments described herein is shown. Feedstock 101 passes through valve 1002 and enters cyclone separator 1003, where it is preheated by heat exchange with hot gases. Valve 1004 meters feedstock powder into hot gases (e.g., combustion air) flowing through conduit 1025. Combustion air and feedstock suspension are delivered through burner 1005, where combustible gas is introduced through conduit 1006. A cylindrical melting chamber 1007 is configured to receive a hot gas stream (e.g., combustion gas) that entrains aluminosilicate particles in various stages of melting particles 1008. Melting chamber 1007 includes a cylindrical shell 1009 of a suitable material, such as steel, and an inner lining of a suitable refractory material 1010. Melting chamber 1007 is also protected internally by a stream of cold air (primary quench air) 1011 injected from an upper distribution ring 1012. The cooling air flows within the melting chamber 1007 in a laminar or swirling flow 1013 around the inner chamber walls without significantly mixing with the central flow of molten suspended particles 1008. This flow also protects the inner refractory lining 1010 and limits heat losses.

[0165] The molten particles 1008 then enter a quench chamber or quench zone 1014 where the particles interact with primary quench air 1013 and optional secondary quench air 1015 which passes through a distributor 1016 and is injected 1017 into the quench chamber 1014 .

[0166] The quenched hot solid particles 1018 flow in suspension through tube 1019 and are separated from the hot gases in cyclone 1020. The hot solid glassy particles pass through valve 1021, exchange heat with cool combustion air 1024, and are separated in combustion air preheating cyclone 1022. Valve 1023 regulates the pressure and allows collection of microspherical glassy product 109. Cyclones 1003, 1020, and 1022 also function as solid / gas heat exchangers, an important heat recovery loop that increases the energy efficiency of the process. In cyclone 1020, hot gases from melting chamber 1007 are separated from the solids, and these gases preheat the cooler raw material powder 101 before separation in cyclone 1003. The heat-exchanged exhaust gases 1027 are directed to a suitable exhaust system (e.g., a baghouse and blower) or are passed to further heat exchange cyclones. In the cyclone 1022, the hot quenched particles 1018 exchange heat with cool combustion air 1024, and the preheated combustion air is used to transport the preheated feedstock powder into the melting chamber 1007, thereby significantly reducing the energy that must be added to achieve melting of the suspended particles.

[0167] Example

[0168] Example 1: Reducing Yield Stress Using Synthetic Spherical Particles

[0169] To demonstrate the improvement in the viscosity of geopolymer cement mixtures, the following method was used. Commercially available powdered volcanic glass powder, having an oxide composition of SiO2-73.77%; Al2O3-11.82%; Fe2O3-1.42%; MgO-0.1%; CaO-0.28%; Na2O-4.22%; and K2O-4.09%, had a D[3,2] average particle size of 10 μm and an angular morphology typical of finely ground powders. Sample 402 of the volcanic glass powder ( Figure 4 ) to produce an optimally melted / quenched powder 403 having an average particle size D[3,2] of 11 μm and a substantially spherical morphology with a roundness R>8 (see Figure 4 ). More specifically, by Figure 8and the apparatus shown in Figure 9 for processing natural volcanic glass powder (angular morphology). The burner was a commercial oxy-propane burner model QHT-7 / hA from Shanghai Welding and Cutting Tool Factory with a modified powder feed, the burner was fired into a steel melt chamber with water-cooled walls, and the particle temperature exceeded the average liquidus temperature of the material, about 1300°C as estimated from the composition data. The reasons for exceeding the liquidus temperature are i) the microspherical morphology produced by surface tension in the liquid phase, ii) the uniform composition (under backscattered electron imaging) and iii) the absence of unmelted or partially melted particles in the final reagent. In this experiment, the burner was not tightly sealed to the melt chamber, so the cooled quenching air was allowed to rush along the walls of the melt chamber, only after sufficient residence time to allow melting and then quenching the molten entrained powder. As Figure 8 As shown, the quenched hot powder was separated from the hot combustion gases by a cyclone separator and the glass powder was collected for testing. The product obtained in this example was a highly spherical synthetic glass (d[3,2] = 11 μm) with the same composition and almost the same particle size distribution as the raw material ( Figure 4 ).

[0170] The microspherical mineral glass powder has a Si / (Al,Fe 3+ ) moles, (Ca, Mg) 0.12 (Na,K) 0.89 ·(Al,Fe 3+ )1·Si 19.68 The cement reagent has a molar composition of 0.28 wt% CaO (CaO, 0.38% MgO).

[0171] This experiment compared two geopolymer reagents with particles of equal composition and nearly equal size distribution (confirmed by laser diffraction particle size analysis, Figure 4 ). The only variable that was varied was the particle morphology.

[0172] The powders were mixed separately as a geopolymer binder paste using the following optimized mix design, using a mix for angular volcanic glass with minimal water usage ("Mix A"):

[0173] 99.5 g of a mixture containing 1.77 mol of water, 0.12 mol of Na₂O + K₂O, 0.82 mol of SiO₂, and 0.08 mol of Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was cement reagent glass or volcanic glass. The source of the SiO₂ was also cement reagent or volcanic glass and potassium silicate. The sources of potassium oxide were potassium silicate and potassium hydroxide. The molar ratios of the oxides in each mixture are listed in Table 1 below.

[0174] Spherical mixture A was too fluid when mixed in the same mass ratio as angular mixture A, which had very poor processability even at a very high water content of 40 wt% HO. Surprisingly, spherical mixture B, containing only 15 wt% HO, had excellent processability, as shown by a low yield stress of ~6 Pa.

[0175] The glassy spherical powder was remixed with the same amount of solid reagents, but with a lower ratio of silicate hardener to water ("Mixture B"):

[0176] A mixture (79 g) containing 0.73 mol of water, 0.11 mol of Na₂O + K₂O, 0.8 mol of SiO₂, and 0.08 mol of Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was spherical cement reagent. The source of the SiO₂ was also spherical cement reagent and potassium silicate. The source of potassium oxide was potassium silicate and potassium hydroxide. The molar ratios of the oxides in each mixture are listed in Table 1 below.

[0177] The approximate yield stress of angular powder mix A (spread radius 24 mm) and spherical powder mix B (spread radius 60 mm) was determined using a micro-cone slump test (as described in Tan et al. 2017). Angular powders produce non-shear flowable materials with a yield stress of approximately 425 Pa or greater (calculated using the slump flow equation 10 as described in Pierre, A., Lanos, C., & Estelle, P. (2013). Extension of spread-slump formulae for yield stress evaluation. Applied Rheology, 23(6), 36-44). Surprisingly, the spherical mixture had only 41% of the molecular water content of the angular mixture (including water in the soluble silicate hardener), but produced an easily pourable resin fluid with a yield stress of only about 6.5 Pa (calculated using the extended flow equation 2 in Tan, Z., Bernal, SA, & Provis, JL (2017). Reproducible mini-slump test procedure for measuring the yield stress of cementitious pastes. Materials and Structures, 50(6), 235)).

[0178] Table 1 Oxide molar ratio of the mixture

[0179]

[0180] The angular mixture A and the spherical mixture B were heated and cured in a sealed container at 80° C. for 6 hours. The angular paste hardened poorly, probably due to the high water content, while the spherical paste hardened into a ceramic-like solid with a fine glossy surface.

[0181] Example 2: Basalt "FC"

[0182] Oligocene basalt was sampled in Vancouver, British Columbia. The mineralogy of the rock is dominated by plagioclase, diopside, and clay-like phases that are likely weathering products (Table 2, determined by XRD with Rietveld refinement). The major element oxide compositions are provided in Table 3.

[0183] Table 2 Basalt mineralogy

[0184]

[0185] Table 3 Oxide composition of basalt "FC" (XRF)

[0186]

[0187] The basalt was crushed in a jaw crusher, then pulverized in a disc mill and further ground in a ring mill to a powder with an average particle size of approximately 10 μm. The powder was fed through a vitrification device that heated the material to approximately 1450°C via a liquidus transition, followed by a rapid quenching step. The resulting glass was 96.7% X-ray amorphous (Table 4).

[0188] Table 4 XRD-Rietveld analysis of basalt glass (corundum nails)

[0189]

[0190] Si / (Al,Fe 3+ ) is 6.93 in moles, and the molar composition of the cement reagent is (Ca, Mg) 3.15 (Na,K) 0.21 ·(Al,Fe 3+ )1·Si 6.93 , the CaO content is 9.51 wt% (CaO, MgO is 17.3%).

[0191] The individual particles were observed to be highly spherical, with an average circularity R>0.8 (as defined previously) and a D[3,2] of 10.5 μm.

[0192] A mixture (131 g) containing 1.31 mol of water, 0.1 mol of Na₂O + K₂O, 0.88 mol of SiO₂, and 0.24 mol of Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was the basalt microsphere powder prepared above. The source of the SiO₂ was also basalt powder and potassium silicate. The source of the potassium oxide was potassium silicate and potassium hydroxide. The molar ratios of the oxides are listed in Table 5.

[0193] Table 5 Oxide molar ratio

[0194]

[0195] A micro-slump cone test was performed on the geopolymer cement paste, resulting in a flow diameter of 98.4 mm and a calculated yield stress of 21.7 Pa. 110 g of sand was added to the paste, which was then sealed and cured at 80°C for 6 hours. The compressive strength of the mortar sample cube was determined to be 19 MPa.

[0196] Example 3: Basalt "BD"

[0197] Commercially available powdered basalt "BD" has the oxide composition provided in Table 6, as shown below.

[0198] Table 6 Oxide composition of basalt "BD" (XRF)

[0199]

[0200] The powder was fed through a vitrification unit that heated the material to approximately 1450°C through a liquidus phase change, followed by a rapid quenching step. For most particles, successful melting through the liquidus phase was demonstrated by a highly spherical bulk particle morphology.

[0201] Microsphere basalt reagent powder "BD" Si / (Al,Fe 3+ ) is 7.84, and the molar number of the cement reagent is (Ca, Mg) 2.66 (Na,K) 0.23 ·(Al,Fe 3+ )1·Si 7.84 , CaO is 9.66 wt% (CaO, MgO is 14.04%). By laser diffraction measurement, it was observed that the individual particles were highly spherical and smooth, with a roundness R greater than 0.8 and a D[3,2] of 8.0 μm.

[0202] A 116 g mixture containing 1.53 mol water, 0.09 mol Na₂O + KO, 0.75 mol SiO₂, and 0.17 mol Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was the microspherical basalt powder prepared above. The sources of the SiO₂ were also basalt powder and potassium silicate. The sources of potassium oxide were potassium silicate and potassium hydroxide. The molar ratios of the oxides are provided in Table 7.

[0203] Table 7 Oxide molar ratio

[0204]

[0205] 110 g of sand was added to the mixture, and the samples were cast into cubic molds and then sealed and cured for 6 hours at 80° C. From the three samples, the average compressive strength of the mortar was determined to be 27.4 MPa with a standard deviation of 2.22 MPa.

[0206] Example 4: Coal tailings

[0207] A coal tailings sample obtained from Cape Breton, NS consisted of approximately 60% residual coal and 40% mineral material. The inorganic portion had an oxide composition as provided in Table 8 below.

[0208] Table 8 Oxide composition of coal tailings (XRF)

[0209]

[0210] Dried coal tailings, with a measured D[3,2] of 9.9 μm, were fed through a vitrification unit that burned excess coal and heated the inorganic material to approximately 1450°C via a liquid phase change, followed by a rapid quenching step. The coal portion of the feedstock added considerable energy to the process: compared to "inert" basalt processed at the same mass flow rate, the flame power for the coal tailings was increased by at least 46%.

[0211] The successful melting of the inorganic particles through the liquid phase is evidenced by the highly spherical bulk particle morphology with an average roundness (R) > 0.8 and a D[3,2] of 11.2 μm.

[0212] Molar number of micro-spherical coal tailings reagent powder Si / (Al,Fe 3+ ) Test 5.66, the molar composition of cement reagent is (Ca, Mg) 0.38 (Na,K) 0.10 ·(Al,Fe 3+ )1·Si 5.66 , CaO content is 1.7 wt% (CaO, MgO is 2.56%).

[0213] A mixture (45 g) containing 0.57 mol of water, 0.04 mol of Na₂O + KO, 0.42 mol of SiO₂, and 0.12 mol of Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was the coal tailings microsphere powder prepared above. The sources of the SiO₂ were also coal tailings powder and sodium silicate. The sources of the sodium oxide were sodium silicate and sodium hydroxide. The molar ratios of the oxides are provided in Table 9 below.

[0214] Table 9 Oxide molar ratio

[0215]

[0216] The mixture was cast into a cubic mold and then sealed and cured for 6 hours at 80° C. The sample was demoulded and found to have a ceramic-like surface with a compressive strength of 21 MPa and gloss.

[0217] Example 5: Dredging Sediment

[0218] Sediment samples were obtained from the central Vancouver Harbor, British Columbia, to represent an example of dredged sediment. The samples had the oxide compositions provided in Table 10.

[0219] Table 10 Sediment oxide composition (XRF)

[0220]

[0221] The sample was dried and found to have a mass median diameter D50 of 47 μm. Next, the sample was sieved to remove particles that did not pass 75 μm.

[0222] This powder is fed through a vitrification unit that heats the material to approximately 1450°C via a liquidus phase change, followed by a rapid quenching step.

[0223] Most of the particles successfully melted through the liquid phase as evidenced by the highly spherical bulk particle morphology. The microsphere precipitant powder had a Si / (Al,Fe) ratio of 11.49. 3+ ) molar number, the molar composition of cement reagent is: (Ca, Mg) 1.55 (Na,K) 0.51 ·(Al,Fe 3+ )1·Si 11.49 and 4.42 wt% CaO (CaO, MgO is 7.14%).

[0224] The individual particles are highly spherical and smooth, with an average roundness (R) > 0.8 and a D[3,2] of 11.8 μm.

[0225] 98 g of a mixture containing 0.89 mol water, 0.09 mol Na₂O + K₂O, 0.8 mol SiO₂, and 0.13 mol Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was the microspherical sediment powder prepared above. The source of the SiO₂ was also sediment powder and potassium silicate. The sources of potassium oxide were potassium silicate and potassium hydroxide. The molar ratios of the oxides are provided in Table 11.

[0226] Table 11 Oxide molar ratio

[0227]

[0228] 110 g of sand was added to the mixture, and the sample was cast into a cubic mold, which was then sealed and cured for 6 hours at 80° C. The compressive strength of the mortar cube was determined to be 25 MPa.

[0229] Example 6: Copper Mine Tailings

[0230] Copper porphyry flotation tailings samples were obtained from Argentina to represent an example of globally abundant aluminosilicate waste. The samples had the oxide compositions provided in Table 12.

[0231] Table 12 Sediment oxide composition (XRF)

[0232]

[0233] The sample was sieved to remove particles that did not pass 75 μm. The powder was fed into a vitrification device that heated the material to approximately 1450°C via a liquid phase change, followed by a rapid quenching step. For most particles, successful melting through the liquid phase was demonstrated by the highly spherical bulk particle morphology.

[0234] The micro-spherical tailings reagent powder has a Si / (Al,Fe 3+ ) moles, the molar composition of cement reagent is (Ca, Mg) 0.6 (Na,K) 0.5 ·(Al,Fe 3+ )1·Si 14.2 and 1.94 wt% CaO (CaO, MgO is 4.87%).

[0235] The individual particles are highly spherical and smooth, with an average roundness (R) greater than 0.8 and a D[3,2] of 11.4 μm.

[0236] A mixture (103.6 g) containing 0.76 mol of water, 0.11 mol of Na₂O + K₂O, 1.04 mol of SiO₂, and 0.13 mol of Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was the microsphere tailings powder prepared above. The source of the SiO₂ was also the tailings powder and potassium silicate. The sources of potassium oxide were potassium silicate and potassium hydroxide. The molar ratios of the oxides are provided in Table 13 below.

[0237] Table 13 Oxide molar ratio

[0238]

[0239] 110 g of sand was added to the mixture, and the sample was cast into a cubic mold, which was then sealed and cured for 6 hours at 80° C. The compressive strength of the mortar cube was determined to be 18 MPa.

[0240] Example 7: Waste concrete

[0241] Structural concrete cores were sampled from a mid-rise condominium construction site in Vancouver, British Columbia. The material had the oxide composition provided in Table 14.

[0242] Table 14 Oxide composition of structural concrete (XRF)

[0243]

[0244] The sample was sieved to remove particles that did not pass 75 μm. The powder was fed into a vitrification apparatus that heated the material to approximately 1450°C via a liquidus phase change, followed by a rapid quenching step.

[0245] For most particles, successful melting through the liquid phase was evidenced by a highly spherical bulk particle morphology.

[0246] The microspherical concrete reagent powder has a Si / (Al,Fe 3+ ) moles, the molar composition of cement reagent is (Ca, Mg) 3.06 (Na,K) 0.7 ·(Al,Fe 3+ )1·Si 12.3 and 12.55 wt% CaO (CaO, MgO 13.97%).

[0247] The individual particles were highly spherical and smooth, with an average roundness (R) greater than 0.8 and a D[3,2] of 10.0 μm.

[0248] A 100 g mixture containing 1.27 mol of water, 0.08 mol of Na₂O + K₂O, 0.73 mol of SiO₂, and 0.13 mol of Al₂O₃ + Fe₂O₃ was prepared. The source of the Al₂O₃ + Fe₂O₃ was the microspherical concrete powder prepared above. The sources of SiO₂ were also concrete powder and potassium silicate. The sources of potassium oxide were potassium silicate and potassium hydroxide. The molar ratios of the oxides are provided in Table 15 below.

[0249] Table 15 Oxide molar ratio

[0250]

[0251] 100 g of sand was added to the mixture, and the sample was cast into a cubic mold, which was then sealed and cured for 6 hours at 80° C. The compressive strength of the mortar cube was determined to be 27 MPa.

[0252] Example 8: Quarried Aggregates

[0253] Granodiorite crusher dust from an aggregate quarry near Vancouver, Canada, was sampled for the following experiments. The sample's oxide composition (SEM-EDX) was approximately SiO₂ -73%; Al₂O₃ -15%; Fe₂O₃ -3%; MgO -0%; CaO -2%; Na₂O -3%; and K₂O -4%. The rock was further crushed and ground to a fine powder that completely passed 75 μm.

[0254] The resulting powder was processed through an in-flight vitrification device, which heats the material to approximately 1450°C via a liquidus phase change, followed by a rapid quenching step.

[0255] Most particles successfully melted through the liquid phase, as evidenced by the highly smooth and spherical bulk particle morphology.

[0256] The individual particles are highly spherical and smooth, with an average roundness (R) greater than 0.8 and a D[3,2] of 9.3 μm. The microspherical granodiorite glass reagent powder has a Si / (Al,Fe) ratio of 16.0. 3+ ) moles, the molar composition of cement reagent is (Ca, Mg) 2.5 (Na,K) 4.4 ·(Al,Fe 3+ )1·Si 16。0 , CaO is 2 wt% (CaO, MgO are 2%).

[0257] A 105 g mixture containing 1.53 mol water, 0.1 mol Na2O + K2O, 0.93 mol SiO2, and 0.12 mol Al2O3 + Fe2O3 was prepared. The source of the Al2O3 + Fe2O3 was the microsphere aggregate powder prepared above. The source of the SiO2 was also aggregate powder and potassium silicate. The sources of potassium oxide were potassium silicate and potassium hydroxide. The molar ratios of the oxides are provided in Table 16.

[0258] Table 16 Oxide molar ratio

[0259]

[0260] The mixture was cast as a paste into a cubic mold and then sealed and cured at 80 degrees Celsius for 24 hours. The compressive strength of the paste cubes was determined to be 11 MPa, indicating that the material gained strength through thermal curing as expected. The lower relative strength compared to other examples using a relatively inert filler (quartz at temperatures above 1600°C) can be explained by the omission of sand (such as in the mortar) and the higher content of unfused quartz minerals.

[0261] Overview of Examples 1-8

[0262] Table 17 below summarizes the main findings of Examples 1-8 and also provides a comparison of the performance of two fly ashes: a commercially available Type F fly ash (B-FA) that has been selected, and a Type F fly ash sampled directly from a coal-fired power plant in NovaScotia, Canada. Figure 5 shown.

[0263] Table 17 Summary of Examples 1-8

[0264]

[0265] R - circularity (unitless), as defined by Takashimizu and Iiyoshi (2016), n - number of particles analyzed.

[0266] Example 9: Using a synthetic binder as an alternative SCM

[0267] The microspheroidal basalt sample "BD" from Example 3 above was pulverized in a ring mill for 5 minutes to break up the coarsest particles, thereby increasing the reactive surface area. Laser diffraction analysis determined the D[3,2] particle size to be 3.6 μm. Interestingly, the small spheres, <10 μm, tended to act as ball bearings in the mill and resisted breakage. The strength activity index of the reagent was compared with that of commercially available high-quality Type F fly ash, which has an oxide composition of SiO₂ - 52.09%; Al₂O₃ - 18.58%; Fe₂O₃ - 4.25%; MgO - 2.98%; CaO - 10.25%; Na₂O - 6.03%; and K₂O - 1.72%.

[0268] According to ASTM C618, 50 mm cubes were cast from a control mix of portland cement, portland cement with fly ash (20% and 40% replacement), and portland cement with cementitious agent BD powder (also 20% and 40% replacement). Table 18 provides the compressive strength results at 7 and 28 days. The performance of the BD mix at 20% replacement was comparable to that of commercial Type F fly ash, and the strength activity index was acceptable. The BD mix was easy to process and mixed without trouble. It is noteworthy that both the BD agent and fly ash produced very useful mortar strengths of greater than 40 MPa after 28 days at 40% replacement of portland cement. Therefore, the BD cementitious agent can be considered a suitable fly ash replacement in terms of compressive strength.

[0269] Table 18 Strength of Portland cement with cement-based agent BD powder

[0270]

[0271] cement materials

[0272] According to some embodiments, new methods of production and use of cementitious agents, geopolymeric agents, and supplementary cementitious materials (SCMs) offer significant advantages over known methods and formulations.

[0273] According to some embodiments, the cement reagent comprises an oxide represented by Formula 1:

[0274] (CaO,MgO) a (Na2O, K2O) b (Al2O3,Fe2O3) c (SiO2) d [Formula 1]

[0275] wherein a is from about 0 to about 4,

[0276] b is from about 0.1 to about 1,

[0277] c is 1, and

[0278] d is from about 1 to about 15.

[0279] Advantageously, the cementitious agents according to the present invention are formulated from abundant rocks, minerals and compounds of suitable composition. Preferably, the CaO content is less than about 30% by weight to reduce the CO2 impact of the cement.

[0280] In some embodiments, the cementitious agent is in the form of a non-crystalline solid.In embodiments, the cementitious agent is in the form of a powder comprising a D50 (median diameter) of about 20 μm or less, or preferably 10 μm or less.

[0281] In an embodiment, the cementitious agent comprises at least one of the following properties: an X-ray amorphous solid content of 45% to 100%, preferably 90 to 100%; and (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 The molar composition ratio of .

[0282] In some embodiments, the cementitious agent comprises less than about 10% by weight of CaO. In another embodiment, the cementitious agent comprises greater than about 30% by weight of CaO. The composition of the cementitious agent with respect to Na, K, and Ca can be varied to achieve certain advantages depending on the binder requirements. For example, a cementitious agent having less than about 10% by weight of CaO is suitable for use in heat-curing geopolymers and as a fly ash replacement. Alternatively, a cementitious agent having greater than about 30% by weight of CaO is hydraulically settable and can be added to geopolymer resins to allow ambient temperature curing of the geopolymer cement and directly replace blast furnace slag in blended Portland cement.

[0283] In some embodiments, the cementitious agent is Si / (Al,Fe 3+ A low-calcium cementitious agent having a molar composition of 1-20 and a CaO content of about 10% by weight or less. Preferably, such a cementitious agent is 40-100% X-ray amorphous, more preferably about 80%-100% X-ray amorphous, and in some embodiments is 100% amorphous. Such low-calcium cementitious agents may have numerous commercial applications, for example, as pozzolanic admixtures in hydraulic cements, and / or as agents in geopolymer binders and cements.

[0284] In another embodiment, the cementitious agent is a high calcium content cementitious agent with a Si / (Fe 3+The present invention relates to a cementitious agent comprising a calcium carbonate (CaO) composition of 1-20, and a CaO content of about 10-50% by weight, preferably about 20-45% by weight. Preferably, the cementitious agent is 40-100% X-ray amorphous, more preferably about 80-100% X-ray amorphous, and even more preferably 100% amorphous. The high-calcium cementitious agent has many commercial applications, such as as a hydraulic admixture in mixed hydraulic cements and / or as an agent in geopolymer binders and cements.

[0285] In another embodiment, the cementitious agent is an intermediate calcium-containing cementitious agent with a Si / (Fe 3+ ,Al) has a molar composition of 1-20 and a CaO content of about 10-20 wt%. Preferably, this cementitious agent is about 40-100%, preferably about 80%-100% X-ray amorphous, and even more preferably 100% amorphous. This intermediate calcium-containing cementitious agent has many commercial applications, for example as a cementitious agent having desirable intermediate hydraulic and pozzolanic properties.

[0286] An important advantage of optimizing the Na / K ratio in the cementitious reagent according to the present invention is that: 1) with SCM applications, the free lime in the hydraulic cement will be exchanged for soluble alkali and coordinated with sialate molecules derived from the cementitious reagent to produce a degree of relatively stable alkali aluminosilicate polymerization that greatly improves the chemical properties of conventional hydraulic cements; and 2) geopolymer reagents having significant Na,K content require less soluble silicate hardener than would otherwise be required, thereby reducing the soluble silicate requirements (and cost) of geopolymer mix designs.

[0287] Preparation method

[0288] In some embodiments, aluminosilicate materials are selected as raw materials for producing cementitious agents. Figure 1 Illustrative steps required to produce a cementitious agent from aluminosilicate materials according to one embodiment of the present invention are shown.

[0289] Briefly, an aluminosilicate material is selected 101 and its chemical composition is analyzed 102. The raw material can be analyzed to determine the elemental composition of the raw material by any suitable quantitative or semi-quantitative method such as XRF, XRD with Rietveld refinement, LIBS, EDS, wet chemical analysis, and various other known methods.

[0290] If the selected composition is unacceptable, the material is adjusted, blended (e.g., in a vessel prior to thermochemical treatment), or sorted 103, for example, by adding a composition adjusting material 104. As used herein, the term "composition adjusting material" refers to any solid or liquid material whose composition is suitable for preferentially altering the bulk or surface composition of the aluminosilicate material with respect to one or more of the elements Ca, Na, K, Al, Fe, and Si.

[0291] As described above, composition-adjusting materials for introducing calcium (Ca) may include CaCO3, Ca(OH)2, CaO, CaCl2, calcium silicate minerals and compounds, calcium aluminum silicate minerals and compounds, waste Portland cement products, wollastonite, anorthite, and other calcite-group mineral compositions.

[0292] As described above, the composition-adjusting material for introducing aluminum (Al) can be composed of aluminous rocks, minerals, soils, sediments, by-products, and compounds, including one or more of kaolinite, halloysite, and other aluminum-rich / alkali-poor clay minerals, Al2SiO5 polymorphs, chlorite, hydrotalcite, garnet, corundum, mullite, anorthite, diaspore, boehmite, gibbsite, nepheline, and other feldspars. Other materials that can be used include aluminum metal, bauxite, alumina, and red mud (alumina refining residue).

[0293] As described above, composition-adjusting materials for introducing iron (Fe) may include iron-rich rocks, minerals, soils, sediments, by-products and compounds, such as olivine, chlorite minerals (biotite, clinochlore, etc.), pyroxene, hornblende, goethite, hematite, magnetite, ferrihydrite, lepidocrocite and other iron oxyhydroxide compositions, iron-rich clays and phyllosilicate minerals, and elemental iron.

[0294] Sorting 105 can also be used as a composition adjustment method 103 and any unwanted waste material can be discarded.

[0295] The resulting solid aluminosilicate material comprising the desired composition is then heated 106. Heating is performed to a temperature above the liquidus temperature to obtain a liquid, for example, at about 1000-1600°C or about 1300-1550°C. Any suitable method or apparatus may be used to heat and obtain the liquid, including but not limited to on-the-fly melting and / or batch melting. This may be achieved using, for example, a plasma furnace, an oxyfuel furnace, an electric arc furnace, a reverberatory furnace, a rotary kiln, and / or a solar concentrator furnace. Typically, a furnace temperature of 1000-1600°C, most typically 1300-1550°C, is required to obtain the desired liquid phase.

[0296] If desired, a fluxing material may be added to the solid aluminosilicate material to lower its melting point and / or induce depolymerization of the liquid. The fluxing material may be mixed with the solid aluminosilicate material prior to heating (e.g., a vessel) or during heating. Common fluxing materials that may induce depolymerization and / or lower melting temperatures in the melt include CaF2, CaCO3, waste glass, cullet, glass frit, alkali-containing minerals (e.g., feldspar, zeolites, clays, and feldspathic minerals), borates, halogen compounds (salts containing fluoride and chloride), and calcium salts.

[0297] Next, the aluminosilicate liquid is quenched 107 to obtain a solid. In embodiments, the quenching step comprises lowering the temperature of the liquid to a temperature significantly below the glass transition, such as 500°C or less, or preferably below 200°C or less. In embodiments, the quenching is performed rapidly, i.e., the temperature is increased at a rate of about 10 2 Ks -1 -10 6 Ks -1 The rate (preferably >10 3.5 Ks -1 Any suitable method may be used for quenching, including but not limited to contacting the molten material with a sufficiently cold stream of air, steam, or water to produce an amorphous solid.

[0298] Next, solid is crushed and / or pulverized to reduce particle size 108 and obtain cement reagent 109.This can use any suitable method or equipment to carry out, including but not limited to ball mill, roller mill and vertical roller mill.Preferably, reduce particle size to obtain the fine powder that can be used for cement application.In embodiments, powder comprises D50 (median diameter) be about 20 μ m or less, or preferably 10 μ m or less particle size distribution.Usually expect such particle size and the consistency to guarantee enough reactivity and material properties.

[0299] Uses of cement reagents

[0300] A related aspect relates to the broad relevance of the cementitious agents described herein. Suitable compositions of engineering cementitious agents can be used. Geopolymer cements and hydraulic cements (i.e., cements that react with water) are interchangeably present in significant proportions.

[0301] Thus, embodiments described herein include geopolymer cements and hydraulic cements comprising at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or more of the cementing agents described herein.

[0302] According to another aspect, some embodiments relate to a supplementary cementitious material (SCM) comprising a cementitious agent as defined herein. In some embodiments, the SCM comprises from about 5% to about 50% by weight (preferably at least 20% by weight) of a cementitious agent as defined herein.

[0303] According to another aspect, some embodiments are directed to a supplementary cementitious material (SCM) comprising one or more of the following properties: comprising less than about 35 wt% CaO, having a substantial Na / K content (e.g., at least 2 wt%, preferably at least 5 wt%) and Al content (e.g., at least 5 wt%), and being in an amorphous solid form.

[0304] According to another aspect, some embodiments relate to solid concrete comprising a cementitious agent as described herein, ie, comprising from about 5 wt % to about 50 wt % (preferably at least 20 wt %) of a cementitious agent as described herein.

[0305] According to another aspect, some embodiments relate to hybrid hydraulic cements that are distinguishable from Portland cements. For example, according to the present invention, solid 29 Si-NMR spectroscopy can distinguish blended hydraulic cements with low iron content (<5 wt.%) from Portland cements (which have a predominantly CSH binder component) by the amount and type of silica tetrahedral linkages in the cured cement. In fact, the cured Portland cement binder phase is characterized by low coordination and hydration sites (Q1, Q1(OH), Q2, and Q2(OH)), insignificant tetrahedral A1 substitution, and a lack of higher coordination (e.g., no Q3, Q4 sites). Hydraulic cements blended with cementitious agents according to the present invention exhibit these typical CSH-related sites, in addition to the unique characteristics of aluminum substitution (e.g., Q2(1Al)) and a "higher" coordination level (i.e., branching) than Portland cement. For example, the blended hydraulic cement according to the present invention may comprise at least one Q3 coordination level (e.g., (Q3(2Al), Q3(1Al), Q3(0Al)). In embodiments, the hybrid hydraulic cement according to the present invention comprises a measurable proportion (>1 wt%) of three-dimensional crosslinking (Q4 position), which is not known in conventional hydraulic cements. According to another aspect, the present invention is directed to a geopolymer binder comprising a cementitious agent as defined herein, i.e., comprising from about 5 wt% to about 90 wt% (preferably at least 20 wt%, at least 30 wt%, at least 50 wt%, at least 75 wt%) of a cementitious agent as defined herein.

[0306] According to another aspect, some embodiments relate to a solid geopolymer concrete comprising from about 5% to about 50% by weight (preferably at least 20% by weight) of a cementitious agent as defined herein.

[0307] Those skilled in the art will appreciate that the present invention advantageously provides a method for producing a versatile low-CO cementitious agent from abundant, inexpensive natural materials. Another significant advantage is the production of a single agent that meets the specifications of today's alternative SCMs while also meeting the needs of the growing geopolymer market.

[0308] Aluminosilicate materials

[0309] As described herein, some embodiments provide a method for thermochemical processing of aluminosilicate materials to produce solid cementitious reagents that can be advantageously used as a replacement supplementary cementitious material (SCM) in blended hydraulic cements and / or as a geopolymer solid reagent in geopolymer binders (thus eliminating the need for some or all of MK-750, fly ash, GGBFS, and other common solid reagents).

[0310] In some cases, the aluminosilicate material is used to produce a non-crystalline cementitious agent as defined herein.In some embodiments, the aluminosilicate material is used to produce a supplementary cementitious material (SCM) and a geopolymer agent.

[0311] As used herein, the term "aluminosilicate material" refers to a material comprising aluminum and / or Fe 3+ and silica selected from the group consisting of natural rocks and minerals, dredged materials, mining wastes containing rocks and minerals, waste glass, contaminated materials containing aluminosilicates, and aluminosilicate industrial byproducts. The aluminosilicate material according to the present invention is preferably in the form of a crystalline solid (e.g., at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or 100 wt% crystalline solid). In some embodiments, the aluminosilicate material comprises at least 2 wt% (Na2O, KO), or at least 3 wt% (Na2O, KO), or at least 4 wt% (Na2O, KO), or at least 5 wt% (Na2O, KO), at least 6 wt% (Na2O, KO), or at least 7 wt% (Na2O, KO), or at least 8 wt% (Na2O, KO), or at least 9 wt% (Na2O, KO), or at least 10 wt% (Na2O, KO).

[0312] KO), or at least 8 wt % (Na2O, KO), or at least 10 wt % (Na2O, KO), or at least 12 wt % (Na2O, KO), or at least 15 wt % (Na2O, KO), or at least 20 wt % (Na2O, KO).

[0313] In some embodiments, the aluminosilicate material is selected from dredged sediments, demolished concrete, mine waste, glacial clays, glacial sediments, river sediments, rocks and mineral mixtures, such as rocks and mineral mixtures composed of some or all of the elements Ca, Na, K, Fe, Al, and Si.

[0314] In some embodiments, aluminosilicate materials are selected as raw materials for producing cementitious agents. The raw materials can be analyzed by quantitative or semi-quantitative methods, such as XRF, XRD with Rietveld refinement, LIBS, EDS, wet chemical analysis, and various other existing methods to determine the elemental composition of the raw materials.

[0315] Example 10: Using dredged sediment

[0316] Sediment samples were taken from the lower tidal Fraser River in Vancouver, British Columbia. The samples consisted of fine sand, silt, and clay size fractions. The mineralogy of the samples is given in Table 19 (determined by XRD with Rietveld refinement), and the oxide compositions of the major elements were estimated from the mineralogy (Table 20).

[0317] Table 19 Mineralogical study of Fraser River sediment samples

[0318]

[0319] Table 20 Oxide composition (estimated based on mineralogy)

[0320]

[0321] The Fraser River Sediment (FRS) was dried, graded, and the fraction passing 120 μm was fed into a vitrification unit that heated the material to approximately 1450°C through the melting point, followed by a quenching step to cool the powder. The resulting FRS-glass powder was ground in a ball mill to a D50 < 20 μm. The X-ray amorphous fraction of the resulting powder was 52%. Mineralogical results estimated the Si / (Al,Fe 3+ ) is 11.46, and the cement reagent has (Ca, Mg) 1.25 (Na,K) 0.34 ·(Al,Fe 3+ )1·Si 11.46 and a CaO content of 3.3 wt. %. This can be identified as a "low-calcium cementitious agent".

[0322] Heat-curing geopolymer binder: Mix 5 parts low-calcium cement reagent with 1 part potassium silicate solution (molar ratio SiO2:K2O = 1.45). Thoroughly mix the paste, place it in a sealed mold, and cure it at 80°C for 4 hours. The resulting hardened paste should achieve a compressive strength of at least 20 MPa in a cylinder compression test.

[0323] Room temperature cured geopolymer binder: 5 parts low calcium cement reagent was mixed with 1 part potassium silicate solution (molar ratio Si02:K20 = 1.45), 1 part water and 1.5 parts finely ground CaSi03. The silicate solution was mixed with the CaSi03powder and allowed to react for 15 minutes. The resulting paste was mixed thoroughly with FRS glass powder and water, then placed in a sealed mold and cured at 20°C for 7 days. The resulting hardened paste achieved a compressive strength of at least 20 MPa in a cylinder compression test.

[0324] Application of room temperature cured SCM in Portland cement: A series of Portland cement mortar cubes were cast from a 50:50 mix of cement and sand. The Portland cement was replaced with low calcium cement reagent at 0%, 20%, 40%, 60% and 80% in the mortar mix. The cubes were cured at 100% humidity for 7 days, and the compressive strength of the cubes is listed in Table 21. Replacement of ordinary Portland cement (“OPC”) up to 60% resulted in a usable compressive strength in many applications, while proportionally reducing the CO2of the mortar.

[0325] Table 21 7-day compressive strength, SCM application

[0326]

[0327] Example 11: Using demolished concrete

[0328] Structural concrete cores were sampled from a 2019 mid-rise residential development in Vancouver, British Columbia. The mineralogical data of the mineral composition of the concrete (including fine and coarse aggregates) is given in Table 22 (XRD refined using Rietveld), and the bulk elemental composition was estimated from the mineralogy in Table 23.

[0329] Table 22 Mineralogy of concrete sample

[0330]

[0331] Table 23 Oxide composition (estimated from mineralogy)

[0332]

[0333] The concrete was crushed and pulverized into a powder with a D50 of about 20 pm. The powder was fed into a vitrification apparatus that heats the material to a melting point of about 1450°C, followed by a quenching step. The resulting glassy particles were finely ground into a powder with a D50 of about 5-15 pm.

[0334] The mineralogy of this powder estimates a molar Si / (Al,Fe 3+ ) of 9.88, with the cement reagent having (Ca,Mg) 2.79 ·(Na,K)0.55 • (Al, Fe 3+ )1• Si 9.88 at a molar composition of 1.0 and a CaO content of 11 wt.%. This can be identified as an "intermediate calcium cement reagent".

[0335] Geopolymer cement cured at ambient temperature: A cement paste was prepared by thoroughly mixing by weight, powdered concrete glass (2.5 parts), potassium silicate solution with a molar ratio of Si02:K20 = 1.45 (0.74 parts) and water (0.08 parts). The paste was then placed in a cylindrical mold and cured at 20 °C. The setting time was estimated by the Vicat needle penetration test. Initial setting occurred at 51 minutes and the final setting time was 195 minutes.

[0336] The compressive strength of a mortar mixture comprising 50:50 geopolymer cement and sand cured in the environment was measured by compressing a cylinder to failure. After 3 days, the compressive strength was about 25 MPa and the tensile strength was about 2 MPa (by the split cylinder method).

[0337] To test high-heat performance, original structural concrete samples and geopolymer cast cylinders of 1 cm diameter were placed in air at 750 °C for 2 hours. The Portland cement concrete burst and turned to powder upon treatment, but the geopolymer mortar cylinders remained intact with no visible cracks or defects.

[0338] The new methods, systems, devices, and formulations presented herein provide many benefits as detailed throughout. In some cases, the new formulations and methods produce granules, powders, or reagents that are particularly useful as a replacement for traditional cement additives in hydraulic or geopolymer cement compositions. The new formulations can comprise a molar composition wherein:

[0339] Si / (Si+Al+Fe+(Ca+Mg)+(Na+K)) = 0.295 to about 0.605

[0340] Al / (Si+Al+Fe+(Ca+Mg)+(Na+K)) = 0.190 to about 0.340

[0341] Fe / (Si+Al+Fe+(Ca+Mg)+(Na+K)) = 0 to about 0.16

[0342] (Ca+Mg) / (Si+Al+Fe+(Ca+Mg)+(Na+K)) = 0 to about 0.215

[0343] (Na+K) / (Si+Al+Fe+(Ca+Mg)+(Na+K)) = 0.04 to about 0.24

[0344] While the new formulation presented herein produces a unique material specifically suited for the purposes described herein, it is difficult to distinguish the material by its individual elemental ranges or areas on a ternary diagram because ternary diagrams are limited to visualizing three components, and all elemental portions of the total composition have interdependent relationships.

[0345] When the geochemical composition is classified as "composition data", a transformation from simplex to Euclidean space (Center Log Ratio Transformation - CLR) is applied to the 7-part composition to preserve the information encoded in the molar composition in a manner that can be handled by standard statistical methods.

[0346] On the CLR representation of the chemical data, a random Forest classification is completed and an 8-rule classification set is extracted from this predictive model (shown below). Using this rule set, fly ash and the raw material compositions are separated, despite the fact that there can be compositional overlap between these materials on a ternary diagram. Such a classification model can be used to accurately represent or classify compositions beyond three dimensions.

[0347] Modeling new formulations and materials

[0348] The glassy reagent ("new raw material", or alternative cementitious material "ACM") differs from fly ash in several important characteristics, such as time-temperature history, manufacturability in almost any location, and relatively low values of problematic heavy metal contaminants. The major elemental chemical composition of the embodiments described herein is also easily statistically distinguished from fly ash using compositional rules. By way of example, a statistical model is constructed using fly ash composition data from the literature and expected suitable raw material compositions as described herein. Classification rules are generated from a subsample as training. The remaining compositions (fly ash and new compositions described herein) are tested to evaluate the accuracy and predictive power of the classification rules. In the following model, 94% of the global composition of 331 fly ashes from the literature were correctly predicted to be fly ash, and the other 6% were classified as "outside the rule set". No fly ash samples were misclassified as the new raw geological material described herein. This model was applied to over 70,000 natural geological material compositions that fit within the disclosed molar composition ranges, and the model predicted the new raw material described herein with a 99% success rate. Less than 1% of the compositions fell into the "outside the rule set" category. Clearly, there is a significant and predictable difference between the new raw material described herein and other byproduct reagents such as fly ash. Individual compositions represented in center log ratio coordinates (CLR) are highly accurate in discriminating the chemical aspects of the glassy particulate from fly ash.

[0349] Application of the model

[0350] The following model is applied:

[0351] 1. Measure the bulk chemical composition of a given glassy sample by any suitable method.

[0352] The mole % of Si, Al, Fe, Ca, Mg, Na and K are also provided.

[0353] 2. Convert the molar data into 7-element CLR coordinates.

[0354] 3. Apply the following conditions in sequence to predict whether the sample is fly ash or Terra reagent.

[0355] Note: If a condition is not met, the next condition is applied. If no condition applies to a given composition, the predicted sample is outside the model's rule set and cannot be confidently predicted.

[0356] rule

[0357] 1. For glassy materials having a bulk CaO oxide equivalent wt% < 35%, and

[0358] 2. Volume mole mol% ratio Si / Al>2.

[0359] It is worth noting that Rule 1 above can be used to exclude slag as a raw material, and Rule 2 can be used to exclude metakaolin, kaolinite, and other 1:1 clay-rich raw materials. The following conditions were applied to the closed, CLR-converted molar sample composition using the logic IF (condition = TRUE), THEN (predict), ELSE (move to the next condition), as shown in Table 24 below:

[0360] Table 24

[0361]

[0362] Figure 11 The region of the new 7-part molar composition in a complete set of ternary phase diagrams is illustrated. The circled region highlights the differences between the new feedstock and global fly ash samples from the literature. As shown, the top row of the four ternary diagrams represents the Si perspective, and the Figure 12 This is shown in more detail in . Figure 11-15 The black outlines of the samples represent the alternative cementitious materials ("ACMs") described herein, which may also be referred to as novel raw materials. The ACM compositions of Examples 1-8 are shown as black dots labeled with numbers corresponding to the example compositions (the numbers and compositions are summarized in Table 17). The gray outlines shown in the figure represent the 90% confidence intervals for the fly ash samples based on 331 unique samples (the same as those classified using the statistical model described above).

[0363] Figure 11The second row of graphs in the table represents the ternary graph from the perspective of Al, and Figure 13 Shown in more detail in .

[0364] Figure 11 The third row in represents the ternary diagram from the Fe perspective, and Figure 14 Shown in more detail in .

[0365] at last, Figure 11 The last row of represents the ternary diagram from the perspective of Ca+Mg, and Figure 15 Shown in more detail in .

[0366] Figure 11-15 The new feedstock is shown as it relates to the overall fly ash composition, and it is clearly shown that the two material populations are highly distinguishable from each other even on an elemental molar ternary plot. The significant overlap between the new feedstock and fly ash is shown to be distinct in the high-dimensional classification model presented herein. The new feedstock, or ACM, described herein is not particularly alkali-resistant, but rather participates in reactions with alkaline hydroxides or lime as reagents.

[0367] Figure 16 A schematic flow diagram of a process 1600 for manufacturing alternative cement concrete using relatively small, decentralized, in-flight micro-kilns is shown. The micro-kilns can be located at any suitable location and, due to their size and properties, are particularly well-suited for deployment at aggregate quarries, at concrete batch plants, between quarries and concrete batch plants, or at any other suitable location to minimize or at least reduce the transportation time and distance typically required to transport concrete batch plants that rely on Portland cement.

[0368] At 1602, aluminosilicate aggregate is provided, as described herein. The aggregate material can be any suitable aluminosilicate material and can be mined specifically for the intended purpose, or can be waste material, such as mine tailings, ground concrete, or some other type of aggregate. At block 1604, the aluminosilicate material is ground into a powder, as described herein.

[0369] At block 1606, the ground aluminosilicate material can be stored, transported, or provided to the feed port of a microfurnace as described herein. At block 1608, energy is added to the ground aluminosilicate aggregate, such as combustion of an air / fuel mixture, a flare, industrial heat, or some other form of energy to increase the temperature of the aggregate. In some embodiments, the aluminosilicate particles are optionally modified and blended (e.g., prior to thermochemical treatment in a vessel), for example, by adding a composition adjustment material to achieve a desired ratio relative to one or more of the elements Ca, Mg, Na, K, Al, Fe, and Si.

[0370] At block 1608 , the energy causes the aluminosilicate aggregates to melt, which in some cases occurs in flight, such as where the aggregates are entrained within air and / or an air / fuel column within a melting chamber.

[0371] After the aggregate is melted and quenched, the feedstock becomes glassy aluminosilicate particles at block 1612. In some cases, the particles are substantially spherical with a roundness R>0.8.

[0372] At block 1614, the pellets are mixed with other ingredients at a concrete batch mixing facility, which in some cases may be co-located with a micro-kiln. At block 1616, additives such as hardeners, environmental curing agents, admixtures, plasticizers, reinforcements, etc. may be added to the concrete. At block 1618, sand and coarse aggregate may be added to the cement, as is known in the art.

[0373] At block 1620, the final concrete mix is ​​formed and ready for use.

[0374] According to some embodiments, the cement production method reduces the distance cement has to be transported (and therefore the cost) compared to conventional methods. Some embodiments allow for the decentralized production of alternative cement materials (ACMs) near aluminosilicate aggregate quarries and concrete batch plants. The ACMs can be advantageously used as the primary agent in suitable alternative cement formulations that can be used to produce cost-effective and CO2-reduced concrete.

[0375] Alternatively, ACM can be used as an alternative supplementary cementitious material (ASCM) to replace a portion of the Portland cement in conventional concrete, thereby reducing the cost and environmental impact of the resulting concrete.

[0376] Figure 17 A typical Portland cement plant 1702 is shown, where cement may typically be transported long distances to reach a concrete batching plant 1704. Similarly, aggregate from a quarry 1706 may also be transported long distances to reach its destination at the concrete batching plant 1704. The time and energy required to transport these dense and bulky products significantly increases the costs associated with making concrete and contributes to the overall CO2 emissions associated with concrete production.

[0377] Figure 18Another configuration 1800 utilizing the ACM described herein is shown. In some cases, the ACM micro-kiln 1802 can be processed at the aggregate quarry 1706 site. Thus, aluminosilicate material mined at the aggregate quarry 1706 can be processed on-site at the ACM micro-kiln 1802, eliminating the need to transport the aggregate to a remote location. The ACM and sufficient aggregate can then be sent to a concrete batch plant 1704, which can be much closer.

[0378] Figure 19 Another configuration 1900 utilizing the ACM described herein is shown. In the illustrated embodiment, an ACM micro-kiln 1802 can be configured with a concrete batch plant 1704. Thus, aggregate from an aggregate quarry 1706 can be delivered to the concrete batch plant 1802, and the aggregate can be used by the ACM micro-kiln 1802 as described herein and can also be used as coarse aggregate in a concrete mix.

[0379] Figure 20 Another configuration 2000 utilizing the ACM described herein is shown. In the illustrated embodiment, an ACM micro-kiln 1802 is located between an aggregate quarry 1706 and a concrete batch plant 1704. In this arrangement, aggregate can be delivered to the ACM micro-kiln, which uses the aggregate to formulate the ACM described herein, and the ACM and additional aggregate can be transported to the concrete batch plant.

[0380] The mini-kiln architecture allows for a distributed system that takes advantage of the smaller, even portable nature of the ACM mini-kiln. Rather than relying on a single centralized Portland cement plant that must ship cement long distances, many ACM micro-kilns can replace a Portland cement plant and significantly reduce shipping time and costs. Figure 17-20 The illustrated embodiment provides a structure that is flexible, efficient, and reduces waste by locating the ACM micro-kiln near the aggregate quarry, concrete batch plant, or both.

[0381] Suitable raw material compositions and methods for converting the raw materials into microspherical glassy particles are disclosed in the applicant's co-pending applications Serial No. 62 / 867,480, filed on June 27, 2019, and Serial No. 63 / 004,673, filed on April 3, 2020, the entire disclosures of which are incorporated herein by reference in their entirety. Suitable raw materials are generally rocks and minerals containing certain proportions of aluminum and silicon oxides. Common building aggregate materials used in concrete are suitable, economical, and conveniently positioned to serve as ideal cement raw materials. Previously, it was not possible to prepare cement materials from such common crystalline aluminosilicate materials.

[0382] A particular advantage of using aluminosilicate aggregates as the raw material for ACM is that this material is inexpensive and abundant.

[0383] Another particular advantage is that aluminosilicate aggregate quarries are widely available and generally in most markets there is no need to allow new quarries to be opened for the production of ACM by the method of the present invention.

[0384] Another particular advantage of using aluminosilicate aggregate as the raw material for ACM is that micro-kilns (e.g., as described in Applicant's co-pending application No. 63,004,673), or concrete batch plants, or both, can be deployed at or very near the aggregate quarry, thereby minimizing cement transportation costs. Since cement from large centralized kilns moves an average of 5-10 times more than aggregate (the supply of aggregate is decentralized), the availability of aggregate is widespread, the price of aggregate is low, and the cost of transporting aggregate is high.

[0385] Another particular advantage of using aluminosilicate aggregate as an ACM feedstock is that quarries often have large quantities of by-product material available that is "off-spec," meaning that there is no general use for that particular gradation, even though this material has generally the same composition as the main quarry product. This by-product material is available very cheaply at crushed stone aggregate quarries as well as sand and gravel quarries.

[0386] Another particular advantage of decentralized ACM micro-kilns is that the capital cost per unit of production is expected to be similar to that of conventional rotary cement kilns, although the absolute scale of capital requirements is 1 / 10 that of Portland cement production. th of magnitude.

[0387] Another particular advantage of decentralized ACM micro-kilns is that the operating expenditure per unit of production is expected to be no more than the corresponding expenditure in Portland cement manufacturing. Therefore, ACM production is cost-competitive with Portland cement at a smaller scale, but requires 5-10 times less transportation costs.

[0388] This disclosure includes the following numbered clauses.

[0389] Item 1, solid microspherical glassy particles, wherein the particles comprise one or more of the following properties: average roundness (R) > 0.8; and less than about 40% of the particles have (R < 0.7) angular morphology.

[0390] Item 2. The particle according to Item 1, wherein the particle has an average roundness (R) of at least 0.9.

[0391] Item 3, the particles of Item 1 or 2, wherein less than about 30% of the particles, or less than about 25% of the particles, or less than about 20% of the particles, or less than about 15% of the particles, or less than about 10% of the particles have an angular morphology (R<0.7).

[0392] Item 4. The particle according to any one of Items 1 to 3, wherein the particle comprises an average oxide represented by Formula 1: (CaO, MgO) a (Na2O, K2O) b (Al2O3,Fe2O3) c (SiO2) d [Formula 1], wherein a is from about 0 to about 4; b is from about 0.1 to about 1; c is 1; and d is from about 1 to about 20.

[0393] Clause 5, particles of any one of items 1 to 4, wherein the particles comprise one or more of the following properties: (i) an X-ray amorphous solids content of 45% to 100%, and preferably 90% to 100%; and (ii) having (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 The molar composition ratio

[0394] Item 6. The particle of any one of items 1 to 5, wherein the particle is 40-100% X-ray amorphous, more preferably about 80-100% X-ray amorphous, even more preferably 100% non-crystalline.

[0395] Clause 7. The particle of any one of Clauses 1 to 6, wherein the particle comprises less than about 10 wt% CaO.

[0396] Clause 8. The particle of any one of Clauses 1 to 6, wherein the particle comprises greater than about 30 wt% CaO.

[0397] Item 9. The particle of any one of items 1 to 6, wherein the particle comprises a high calcium content, Si / (Al,Fe 3+ ) has a molar composition of 1-20 and a CaO content of about 10-50 wt%, preferably about 20-45 wt%.

[0398] Item 10. The particle of any one of items 1 to 6, wherein the particle comprises an intermediate calcium content, Si / (Al,Fe 3+ ) has a molar composition of 1-20 and a CaO content of about 10-20% by weight.

[0399] Item 11. A cementitious agent comprising a mixture of microspheroidal glassy particles as defined in any one of Items 1 to 10.

[0400] Item 12. A cementitious agent comprising a mixture of microspherical glassy particles, wherein the particles comprise one or more of the following properties: (i) an average roundness (R) > 0.8; (ii) less than about 20% of particles having an angular morphology (R < 0.7); (iii) an oxide of Formula 1 as defined in Item 4; (iv) an X-ray amorphous solid content of 45% to 100%, preferably 90% to 100%; and (v) (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 and (vi) a low calcium content of less than about 10wt% CaO, or an intermediate calcium content of about 10-20wt% CaO, or a high calcium content of greater than 30wt% CaO.

[0401] Item 13. The cementitious agent of Item 12, wherein the cementitious agent is in the form of a non-crystalline solid.

[0402] Item 14, the cement agent of Item 12 or 13, wherein the cement agent is in powder form.

[0403] Item 15. The cement reagent of any one of items 12 to 14, wherein the cement reagent D[3,2] has a particle size distribution of about 20 μm or less, more preferably 10 μm or less, or most preferably 5 μm or less.

[0404] Item 16. The cementitious agent of any one of Items 12 to 15, wherein the particle mixture comprises an oxide of Formula 1 (CaO, MgO) a (Na2O, K2O) b (Al2O3,Fe2O3) c (SiO2) d [Formula 1], wherein a is about 0 to about 4, b is about 0.1 to about 1, c is 1, and d is about 1 to about 20.

[0405] Clause 17. The cementitious agent of any one of Clauses 12 to 16, wherein the cementitious agent comprises less than about 10% by weight CaO.

[0406] Clause 18. The cementitious agent of any one of clauses 12 to 16, wherein the cementitious agent comprises greater than about 30% by weight CaO.

[0407] Item 19. The cement reagent of any one of items 12 to 16, wherein the cement reagent is Si / (Al,Fe 3+ ) is a high calcium cement agent having a molar composition of 1-20 and a CaO content of about 10 to about 50% by weight, preferably about 20 to 45% by weight.

[0408] Item 20. The cementitious agent of any one of items 12 to 16, wherein the cementitious agent is Si / (Al,Fe 3+ ) An intermediate calcium-containing cementitious agent having a molar composition of 1-20 and a CaO content of about 10-20% by weight.

[0409] Item 21. The cementitious agent of any one of items 12 to 20, wherein the cementitious agent is about 40-100%, preferably about 80-100% X-ray amorphous, even more preferably 100% amorphous.

[0410] Clause 22. A geopolymer binder comprising a cementitious agent as defined in any one of clauses 11 to 21.

[0411] Clause 23. A supplementary cementitious material (SCM) comprising the cementitious agent according to any one of clauses 11 to 21.

[0412] Clause 24. The SCM of Clause 23, comprising at least 20 wt% of the cementitious agent.

[0413] Clause 25. A solid concrete comprising a cementitious agent as defined in any one of clauses 11 to 20.

[0414] Item 26. Use of the microspheroidal glassy particles according to any one of Items 1 to 10 and / or the cementitious agent according to any one of Items 11 to 20 for the manufacture of geopolymer binders or cements, hydraulic cements, supplementary cementitious materials (SCMs) and / or solid concrete.

[0415] Item 27. A method for producing a cement reagent from an aluminosilicate material, comprising the following steps: i) providing a solid aluminosilicate material; (ii) melting / quenching the solid aluminosilicate material on the fly to melt the material into a liquid, and then quenching the liquid to obtain a melted / quenched powder containing solid microspherical glassy particles; thereby obtaining a cement reagent having a powder of the microspherical glassy particles.

[0416] Item 28. The method according to Item 27, further comprising step (iii): grinding the powder of the microspherical glassy particles into a finer powder.

[0417] Item 29. The method of Item 27 or 28, wherein the powder has a particle size distribution with D[3,2] of about 20 μm or less, more preferably 10 μm or less, or most preferably 5 μm or less.

[0418] Item 30. The method of any one of Items 27 to 29, wherein the particles comprise one or more of the following properties: an average roundness (R) of at least 0.7; less than about 20% angular particles; an oxide of Formula 1 as defined in Item 4; an X-ray amorphous solid content of 45% to 100%, preferably 90% to 100%; (Ca, Mg) 0-12 (Na,K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-2 and a calcium content of less than about 10 wt % CaO.

[0419] Clause 31, the method of any of clauses 27-30, wherein the cementitious agent comprises one or more of the following properties: being reactive in the cement system and / or the geopolymer system; providing a workable geopolymer cement mixture with a low yield stress of less than 25 Pa when the cement slurry has an oxide molar ratio of H2O / (Na2O,KO) < 20; requiring the water content in the cement slurry to be such that the oxide molar ratio H2O / (Na2O,KO) < 20; and providing a cement slurry having a higher workability than an equivalent slurry having a substantially angular morphology at the same water content.

[0420] Item 32. A method according to any one of Items 27 to 31, further comprising the step of adjusting the composition of the non-ideal solid aluminosilicate material to a desired content of the elements Ca, Mg, Na, K, Al, Fe and Si.

[0421] Item 33. A method according to Item 32, wherein the adjusting comprises blending the non-ideal aluminosilicate material with a composition adjusting material to achieve a desired ratio relative to one or more of the elements Ca, Mg, Na, K, Al, Fe, and Si.

[0422] Item 34. The method according to any one of Items 27 to 33, further comprising the step of sorting the solid aluminosilicate material to obtain aluminosilicate particle powder of a desired size.

[0423] Clause 35. A method according to any one of Clauses 27 to 34, further comprising the step of discarding unwanted waste from the solid aluminosilicate material.

[0424] Clause 36. A method according to any one of clauses 27 to 35, wherein the on-the-fly melting comprises heating at a temperature above the liquidus temperature to obtain a liquid.

[0425] Clause 37. The method of Clause 36, wherein the temperature is about 1000-1600°C, or about 1300-1550°C.

[0426] Item 38. A method according to any one of items 27 to 37, further comprising the step of adding a flux material to the solid aluminosilicate material to lower its melting point and / or induce greater enthalpy, volume or deagglomeration of the liquid.

[0427] Clause 39. The method of clause 38, wherein a flux material is mixed with the solid aluminosilicate material before or during the melting.

[0428] Clause 40. The method of any one of clauses 27 to 39, wherein the on-the-fly melting / quenching comprises reducing the temperature of the liquid to below the glass transition temperature to obtain a solid.

[0429] Clause 41. The method of Clause 40, wherein the on-the-fly melting / quenching comprises reducing the temperature of the liquid to below about 500°C, or preferably below about 200°C or less.

[0430] Clause 42. The method of clause 41, wherein lowering the temperature of the liquid comprises 2 ks -1 to about 10 6 ks -1 The rate is preferably >10 3.5 ks -1 quenching rate.

[0431] Clause 43, the method of clause 41, wherein the quench comprises cold air, steam, or water.

[0432] Item 44. The method of any one of Items 27 to 43, further comprising reducing the particle size of the powder of solid microspherical glassy particles.

[0433] Item 45. The method of Item 44, wherein reducing the particle size comprises crushing and / or pulverizing the powder in any one of a ball mill, a roller mill, and a vertical roller mill.

[0434] Clause 46. The method of any one of clauses 27 to 45, further comprising separating the quenched solid particles from the hot gas in a cyclone separator.

[0435] Item 47. An apparatus for producing microspheroidal glassy particles, comprising: a burner; a melting chamber; and a quenching chamber.

[0436] Clause 48. The apparatus of clause 47, wherein the melting chamber and the quenching chamber are first and second portions, respectively, of the same chamber.

[0437] Item 49. The apparatus of Item 47 or 48, wherein the apparatus is configured such that solid particles flow in suspension within the apparatus, melt in suspension, and then quench in suspension.

[0438] Clause 50. The apparatus of any one of clauses 47 to 49, wherein the burner provides a flame that heats the suspended solid particles to a heating temperature sufficient to substantially melt the solid particles into a liquid.

[0439] Clause 51. The apparatus of any one of clauses 47 to 50, wherein the burner comprises a flame fueled by a gas that carries the aluminosilicate feedstock particles into the melting / quenching chamber.

[0440] Clause 52. The apparatus of clause 51, wherein the gas comprises an oxidant gas and a combustible fuel.

[0441] Clause 53. The apparatus of any one of clauses 47 to 52, wherein the quench chamber comprises a cooling system for providing cold air within the quench chamber, the cold air quenching the molten particles into solid microspherical glassy particles.

[0442] Clause 54. The apparatus of clause 53, wherein the cooling system comprises a liquid cooling circuit located around the quench chamber.

[0443] Clause 55. The apparatus of any one of Clauses 47 to 54, wherein the apparatus further comprises a cyclone separator to collect the microspherical glassy particles.

[0444] Clause 56. The apparatus of any one of clauses 47 to 55, wherein the burner comprises at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a solar concentration furnace.

[0445] Item 57, a method for producing a cement reagent from an aluminosilicate material, comprising the following steps: (i) providing a solid aluminosilicate material; (ii) melting / quenching the solid aluminosilicate material on the fly to melt the material into a liquid, and then quenching the liquid to obtain a molten / quenched powder containing solid microspherical glassy particles; thereby obtaining a cement reagent having a powder of the microspherical glassy particles.

[0446] Item 58, a method for producing microspherical glassy particles, comprising the following steps: providing a flying melting / quenching device including a burner, a melting chamber and a quenching chamber; providing solid particles; causing the solid particles to flow in suspension in a gas burned by the burner; heating the solid particles in the melting chamber to a heating temperature higher than the liquid phase to obtain suspended liquid particles; and quenching the suspended liquid particles to a cooling temperature lower than the liquid phase to obtain a powder containing solid microspherical glassy particles.

[0447] Clause 59. The method of Clause 58, wherein the melting chamber and the quenching chamber are first and second portions, respectively, of the same chamber.

[0448] The method of clause 60, clause 58, or clause 59, wherein the heating temperature is about 1000-1600°C, or about 1300-1550°C.

[0449] Clause 61. The method of any one of clauses 58 to 60, wherein the cooling temperature is below 500°C, or below 200°C.

[0450] Clause 62. The method of any one of clauses 58 to 61, wherein the solid particles comprise an aluminosilicate material.

[0451] Clause 63. The method of any one of clauses 58 to 62, wherein the burner comprises a flame fueled by a gas that carries the particles into the melting chamber.

[0452] Clause 64. The method of clause 63, wherein the gas comprises an oxidant gas and a combustible fuel.

[0453] Clause 65. The method of any one of clauses 58 to 64, wherein the quenching comprises providing cool air within the quench chamber.

[0454] Clause 66. The method according to any one of Clauses 58 to 65, further comprising collecting the powder with a cyclone separator.

[0455] Item 67. Use of an apparatus comprising at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a solar concentrating furnace for producing microspherical glassy particles.

[0456] Item 68. Use of an apparatus comprising at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a solar concentration furnace for producing a cementitious agent from an aluminosilicate material.

[0457] Clause 69, all novel compounds, compositions, methods, devices, systems, methods and uses substantially as hereinbefore described with particular reference to the Examples and Figures.

[0458] This document includes headings for reference and to help locate certain sections. These headings are not intended to limit the scope of the concepts described herein, and these concepts may have applicability throughout other sections of the specification. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0459] The singular forms "a," "an," and "the" include the corresponding plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "solid microspherical glassy particles" includes one or more of such particles, and reference to "the method" includes reference to equivalent steps and methods known to those of ordinary skill in the art, which may be modified or substituted for the methods described herein.

[0460] Unless otherwise stated, all numerals representing the amount, reaction conditions, concentration, properties, etc. of the expression components used in the specification and claims should be understood to be modified by the term "about" in all cases. At least, each numerical parameter should at least be interpreted according to the numerical value of the reported significant figures and by applying common rounding techniques. Therefore, unless otherwise indicated, the numerical parameters set forth in this specification and the appended claims are approximate values, which can be changed according to the properties sought to be obtained. Although the numerical range and parameters of the wide range of embodiments are approximate values, the numerical value set forth in the specific examples is reported as accurately as possible. However, any numerical value inherently comprises some errors caused by the variation of experiments, test measurements, statistical analysis, etc.

[0461] It should be understood that the examples and embodiments described herein are for illustrative purposes only, and various modifications or variations thereof will be suggested to those skilled in the art and are included within the scope of the present invention and the appended claims. Those of ordinary skill in the art will recognize that any process or method disclosed herein can be modified in many ways. The process parameters and step sequences described and / or illustrated herein are given as examples only and can be changed as needed. For example, although the steps shown and / or described herein can be shown or discussed in a particular order, these steps do not necessarily need to be performed in the order shown or discussed.

[0462] The various exemplary methods described and / or shown herein may also omit one or more steps described or shown herein, or may include other steps in addition to the disclosed steps. In addition, the steps of any method disclosed herein may be combined with any one or more steps of any other method disclosed herein.

[0463] Unless otherwise indicated, the terms "connected to" and "coupled to" (and their derivatives) used in the specification and claims should be interpreted as allowing both direct and indirect (i.e., via other elements or components) connections. Furthermore, the terms "a" or "an" used in the specification and claims should be interpreted to mean "at least one." Finally, for ease of use, the terms "including" and "having" (and their derivatives) used in the specification and claims are interchangeable with the word "comprising" and should have the same meaning as the word "comprising."

[0464] The processors disclosed herein can be configured with instructions to perform any one or more steps of any of the methods disclosed herein.

[0465] As used herein, the term "or" is used inclusively, to mean optional and combinable items.

[0466] As used herein, characters such as numbers refer to like elements.

[0467] Embodiments of the present disclosure have been shown and described herein as examples only. Many modifications, changes, variations, and substitutions will be apparent to those of ordinary skill in the art without departing from the scope of the present disclosure. Several alternatives and combinations of the embodiments disclosed herein are possible without departing from the scope of the present disclosure and the invention disclosed herein. Accordingly, the scope of the presently disclosed invention should be limited only by the scope of the appended claims and their equivalents.

Claims

1. A method for producing a cement reagent from an aluminosilicate material, characterized in that, The method comprises the following steps: providing a solid aluminosilicate material; grinding the solid aluminosilicate material to have a particle size distribution with D[3,2] less than 20 μm; melting the solid aluminosilicate material into a liquid in a furnace by on-the-fly melting, and then quenching the liquid by on-the-fly quenching to produce solid microspherical glassy particles; and grinding the solid microspherical glassy particles to a particle size distribution with D[3,2] of 20 μm or less, thereby obtaining a cement reagent having the solid microspherical glassy particles, wherein the solid microspherical glassy particles have an average roundness (R) of at least 0.8, and wherein the cementitious agent has (Ca, Mg) 0-12 (Na, K) 0.05-1 ·(Al,Fe 3+ )1·Si 1-20 The molar composition ratio of .

2. The method of claim 1, wherein the aluminosilicate material is selected from the group consisting of dredged sediments, demolished concrete, mine waste, glacial clay, glacial sediments, river sediments, rocks and mineral mixtures.

3. The method according to claim 1, characterized in that Also included is controlling the on-the-fly quenching profile to produce the solid microspherical glassy particles that are greater than 80% X-ray amorphous.

4. The method according to claim 1, wherein Also included is the step of locating the kiln at an aggregate quarry.

5. The method according to claim 1, wherein Also included is the step of locating the kiln at a concrete batching plant.

6. A cement reagent prepared by the method according to claim 1, characterized in that It contains particles of atoms of Si, Al, Fe, Ca, Mg, Na and K, wherein: Si / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0.295 to 0.605 Al / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0.190 to 0.340 Fe / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0 to 0.16 (Ca+Mg) / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0 to 0.215 as well as, (Na+K) / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0.04 to 0.24, wherein the particles have a spherical morphology with an average roundness (R) > 0.8; and wherein the particles are at least 80% X-ray amorphous, and the particles are prepared from an aluminosilicate material, wherein the particles are in the form of a powder comprising a particle size distribution with D[3,2] of 20 μm or less.

7. The cement reagent according to claim 6, characterized in that The aluminosilicate material is selected from the group consisting of dredged sediments, demolished concrete, mine waste, glacial clays, glacial sediments, river sediments, rocks and mineral mixtures.

8. The cement reagent according to claim 6, characterized in that wherein the particles are in the form of a non-crystalline solid.

9. The cement reagent according to claim 6, characterized in that The particles are solid microspherical glassy particles.

10. The cement reagent according to claim 6, characterized in that Less than 40% of the particles had an angular morphology with (R) < 0.

7.

11. The cement reagent according to claim 6, characterized in that The particles have an average roundness (R) of at least 0.

9.

12. The cement reagent according to claim 6, characterized in that It contains the average oxide shown in formula 1: [Formula 1](CaO, MgO) a ·(Na2O, K2O) b ·(Al2O3, Fe2O3) c ·(SiO2) d wherein a is 0 to 4; b is 0.1 to 1; c is 1; and d is 1 to 20.

13. The cement reagent according to claim 11, characterized in that wherein the particles comprise less than 10 wt% CaO.

14. The cement reagent according to claim 6, characterized in that wherein the particles have a size distribution D[3,2] of 20 μm or less.

15. The cement reagent according to claim 6, characterized in that wherein the particles have a size distribution D[3,2] of 10 μm or less.

16. The cement reagent according to claim 6, characterized in that wherein the particles are 100% amorphous.

17. Auxiliary cementitious material comprising a cementitious agent prepared by the method according to claim 1, characterized in that The cement reagent comprises non-fly ash microspherical glassy particles containing Si, Al, Fe, Ca, Mg, Na and K, wherein: Si / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0.295 to 0.605 Al / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0.190 to 0.340 Fe / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0 to 0.16 (Ca+Mg) / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0 to 0.215 as well as, (Na+K) / (Si+Al+Fe+(Ca+Mg)+(Na+K))=0.04 to 0.24, wherein the particles have a spherical morphology with an average roundness (R) > 0.8; and wherein the particles are at least 90% X-ray amorphous, and wherein the particles are in the form of a powder comprising a particle size distribution with D[3,2] of 20 μm or less.

18. The auxiliary cement material according to claim 17, characterized in that: wherein the cementitious agent comprises at least 20 wt % of the supplementary cementitious material.

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