Compositions and manufacturing methods for auxiliary cement-based materials

Abstract

A method for producing an auxiliary cement-based material ("SCM"). This method comprises contacting an input flow with a mechanothermal activating agent, heat-treating the input flow to form a heat-treated input flow, and cooling the heat-treated input flow to obtain an auxiliary cement-based material. This method may further include carbonizing the heat-treated input flow. A composition comprising a calcium silicate hydrate bond, an auxiliary cement-based material, and a mechanothermal activating agent. This composition may further contain a carbonate.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the priority and benefit of the filing of U.S. Provisional Patent Application No. 63 / 456,636, filed on April 3, 2023, entitled "Compositions for Supplementary Cementitious Material and Methods of Making". The above application is hereby incorporated by reference in its entirety.

[0002] The present invention relates to a method for manufacturing a composition comprising a supplementary cementitious material ("SCM") and a composition comprising the same.

Background Art

[0003] Concrete has been an important construction material for thousands of years and continues to be widely used today. Cement, the binding component of concrete, enables it to harden in the composite material at ambient temperature. Many binder chemicals have been used to manufacture concrete, but Portland cement and its variants have been the main binders for nearly 200 years. Unfortunately, the production of Portland cement is a highly CO2 - intensive process, accounting for approximately 8% of the world's anthropogenic CO2 emissions. Cement demand is predicted to increase by 12% - 23% by 2050, but the need for complete decarbonization of the global economy is at odds with this increasing demand. Therefore, there is a need to reduce the specific CO2 emissions of cement production, especially since production volumes are increasing.

[0004] One approach to reducing CO2 emissions from cement is to develop blends with auxiliary cementitious materials that can replace Portland cement in concrete mixtures. These materials include granular blast furnace slag ("GGBFS") and combustion by-product ash such as coal fly ash, calcined clays such as metakaolin, and natural pozzolans such as volcanic ash. However, the supply of these materials is geographically and volcanically limited compared to the enormous demand for cement, and their suitability as cementitious reagents varies between manufacturing plants and over time.

[0005] Fly ash is a partially vitreous aluminosilicate by-product of coal combustion, frequently used in hydraulic cement mixtures to create pozzolanic reactions that improve fluidity and enhance concrete properties. However, only certain coals and combustion processes produce fly ash of acceptable quality for use in concrete. GGBFS, on the other hand, is a vitreous CaO-SiO2 by-product of iron production that possesses many advantageous properties when incorporated into concrete, but its supply is limited due to the small number of operating blast furnaces.

[0006] While natural pozzolanes can be an effective supply chain management (SCM), they require the extraction of non-renewable resources and often necessitate large-scale processing such as calcination to enhance reactivity. Therefore, there is a need for a designed cementitious reagent that can be ubiquitously produced from globally abundant input materials, has low or zero process CO2 emissions, is reactive in cementitious systems, and allows for the selection of its production location based on market needs. This would provide a cementitious reagent that can be reliably manufactured and supplied to meet global demand while reducing CO2 emissions in Portland cement production.

[0007] Scrap, construction waste, clay, landfill bottom ash, and mineral waste are all potential sources of raw materials for SCM (Structural Chemical Manufacturing). These waste streams often contain minerals such as silica, alumina, and iron, which are key components of conventional SCM such as fly ash and slag. By extracting these minerals from waste streams and processing them to meet the required specifications, they can be used as sustainable alternatives to conventional SCM. Furthermore, using waste as a raw material for SCM can offer environmental benefits such as reduced waste treatment, reduced energy consumption, and reduced greenhouse gas emissions. With the increasing demand for low-carbon building materials, utilizing waste as a resource for SCM production can help meet sustainability goals and reduce the environmental impact of the cement and concrete industry.

[0008] SCM can be pozzolanic or potentially hydraulic. Pozzolanic SCMs, such as fly ash, react with calcium hydroxide and water at high pH to form compounds containing CSH bonds. Fly ash is an amorphous glass that thereby reacts with calcium hydroxide and water to form CSH bonds. Pozzolanic SCMs, such as fly ash, silica fume, and pulverized blast furnace slag, react with calcium hydroxide via a pozzolanic reaction that occurs between pozzolanic and calcium hydroxide in the presence of water to form additional CSH gels.

[0009] Potentially hydraulic SCMs such as slag react with water to form CSH bonds, eliminating the need for calcium hydroxide. For example, Portland cement forms a CSH gel through a hydraulic reaction between the cement and water.

[0010] Highly crystallinity inert materials do not react with calcium hydroxide and water. Inert fillers such as mineral scrap do not react with calcium hydroxide and therefore do not exhibit cement activity. Therefore, SCM should be reactive when mixed with calcium hydroxide and water and participate in CSH bond formation. In some cases, SCM is inert but can still meet the ASTM C 618 strength activity requirements due to its filler effect. Therefore, inert materials such as mineral scrap and mineral waste need to be sufficiently activated so that they react with calcium hydroxide and / or water to form CSH bonds that impart hardening properties.

[0011] Despite the abundance of inert fillers, they lack the reactivity necessary to function as supply chain materials (SCMs). Therefore, to reduce overall greenhouse gas ("GHG") emissions from building material manufacturing, including cement production, and to mitigate the environmental impact of waste materials such as scrap, it is necessary to produce reactive SCMs from abundant input materials, such as scrap. Furthermore, the energy requirements for preparing SCMs must be reduced.

[0012] Crystalline minerals such as ore scrap, aggregates, dust, sand, and clay are not typically used as auxiliary cementitious materials (SCMs) in concrete because they do not exhibit pozzolanic or hydraulic properties. Crystalline materials do not react with calcium hydroxide in cement paste and do not form additional CSH gels. Consequently, they do not offer the same advantages as SCMs and are not typically used in concrete on their own.

[0013] One common approach to converting crystalline materials into SCMs is through thermal activation, which involves heating the material to high temperatures to induce chemical changes that produce a reactive phase. For example, firing kaolin clay can produce metakaolin, a pozzolanic material that can be used as an SCM in concrete. However, thermal activation is usually carried out at high temperatures, exceeding 700°C for clays and over 1000°C for silicates and / or aluminosilicates, in order to induce structural changes in the crystalline network that affect amorphousness.

[0014] While traditional SCMs such as fly ash and slag have been useful in improving the sustainability and performance of concrete, the need for more consistent, environmentally friendly, and cost-effective alternatives is driving the exploration of novel and innovative SCMs. Waste minerals such as mine scrap, construction waste, clay, bottom / landfill ash, and / or aggregate dust may offer viable solutions to address the significant challenges associated with the global availability of large quantities of SCM. This approach not only provides a substantial source of sustainable building materials but is also useful in mitigating the environmental impacts of both the mining and construction industries. [Overview of the project] [Problems that the invention aims to solve]

[0015] This invention discloses the production of sustainably sourced chemicals (SCM) from globally abundant input materials to reduce the environmental footprint of cement and mining. The invention also relates to the production of SCM at temperatures below 1000°C, reducing the energy requirements for SCM preparation. Furthermore, the invention relates to an additional carbonation step to capture CO2 and reduce the water demand for chemically produced SCM during the carbonation process. [Means for solving the problem]

[0016] Embodiments of the present invention relate to a method for producing an auxiliary cement-based material, comprising contacting an input flow with a mechanothermal activator, heat-treating the input flow to form a heat-treated input flow, and cooling the heat-treated input flow to obtain an auxiliary cement-based material. Another embodiment further comprises carbonizing the heat-treated input flow. Another embodiment includes carbonation by contacting the heat-treated input flow with CO2.

[0017] In another embodiment, the method further includes mixing the feed stream and a mechanothermal activator. In another embodiment, the method further includes milling the heat-treated feed stream. In another embodiment, the mechanothermal activator lowers the vitrification formation temperature. In another embodiment, the mechanothermal activator modifies the network structure. In another embodiment, the mechanothermal activator lowers the temperature required for dehydroxylation.

[0018] In another embodiment, the mechanothermal activator includes an alkaline mechanothermal activator. In another embodiment, the mechanothermal activator includes an aluminate. In another embodiment, the mechanothermal activator includes a borate. In another embodiment, the mechanothermal activator includes a fluoride. In another embodiment, the mechanothermal activator includes a phosphate.

[0019] In another embodiment, the heat treatment includes heating the input material and the mechanothermal activator to a temperature of less than about 1000°C. In another embodiment, the input material includes silica oxide. In another embodiment, the input material includes aluminosilicate. In another embodiment, the method further includes measuring the reactivity of the auxiliary cement-based material.

[0020] Another embodiment of the present invention also, The present invention also relates to compositions comprising calcium silicate hydrate binders, auxiliary cement-based materials, and mechanothermal activation aids. In another embodiment, the composition further comprises a carbonate. In yet another embodiment, the composition further comprises a CSH gel.

[0021] Further scope of the applicability of the present invention is partially described in the following detailed description in conjunction with the accompanying drawings and may become partially apparent to those skilled in the art by considering the following, or may be acquired through the practice of the present invention. The objects and advantages of the present invention may be realized and achieved by means and combinations particularly indicated in the accompanying claims. [Brief explanation of the drawing]

[0022] The accompanying drawings incorporated herein and forming part of herein illustrate one or more embodiments of the present invention and, together with the specification, help to illustrate the principles of the present invention. The drawings are for illustrative purposes only and should not be construed as limiting the present invention. [Figure 1] This is a process flow diagram illustrating the production of (non-carbonation) SCM from waste minerals containing silicates and / or aluminosilicates according to one embodiment of the present invention. [Figure 2] This table shows the reactivity of SCM generated from mineral scrap and aggregate fine powder to a control sample in one embodiment of the present invention. [Figure 3] This table shows the strength activity index of SCM (with and without carbonation) prepared from various sources after 20% cement replacement in a mortar mixture according to ASTM C618, according to one embodiment of the present invention. Detailed description of the invention

[0023] Embodiments of the present invention are methods for manufacturing SCMs, including contacting feedstock with a mechano-thermal activation aid, heat-treating the feedstock to activate the feedstock, and ball-milling the activated feedstock to form an auxiliary cementitious material. In some embodiments, after thermal activation, a dispersant can be added to permanently capture CO2 in the form of carbonate in the SCM after thermal activation, enabling carbonation of the SCM in a wet state. SCM carbonation can also reduce the water demand during SCM production. After carbonation, the produced SCM can be dried and ball-milled to form a final auxiliary cementitious material for use in a concrete mixture.

[0024] Embodiments of the present invention are methods for manufacturing cementitious reagents, including contacting feedstock with a mechano-thermal activation aid, heat-treating the feedstock to activate the feedstock, ball-milling the activated feedstock to form an auxiliary cementitious material, contacting the auxiliary cementitious material with calcium hydroxide and a base to form an auxiliary cementitious material mixture, curing the auxiliary cementitious material mixture, and contacting the auxiliary cementitious material mixture with a cement mixture. Curing of the auxiliary cementitious material mixture may be performed to test the reactivity of the auxiliary cementitious material mixture. Contacting the auxiliary cementitious material mixture with the cement mixture may include replacing the cement with the auxiliary cementitious material in a mortar mixture.

[0025] Embodiments of the present invention relate to a composition comprising an activated feedstock, a mechano-thermal activation aid, and a calcium silicate hydrate bond. The composition may further include carbonate derived from captured CO2.

[0026] Embodiments of the present invention relate, but are not limited to, methods for producing SCM from globally abundant and locally available input materials, including mineral waste flows, mine scrap, construction waste, clay, sand, or combinations thereof. The present invention also relates to a method for producing SCM by vitrification with a mechanothermal activator. SCM may be used to replace Portland cement in concrete mixtures. For example, up to 20% of Portland cement may be replaced with SCM in the concrete mixture, depending on the reactivity of the SCM.

[0027] As used herein, the term "ASTM C618" refers to the standard specification for coal fly ash and raw or calcined natural pozzolanes for use in concrete, in accordance with the ASTM International Standard.

[0028] The term "fine powder" is defined herein as a material that has been finely ground or powdered (such as ore).

[0029] The term “tailings” or “mineral tailings” is defined herein as the material remaining after the process of separating the valuable fraction from the uneconomical fraction of the material.

[0030] The terms “auxiliary cement-based materials” or “SCM” are defined herein as materials and / or compounds added to concrete to improve its performance and reduce its environmental impact. SCM reacts with calcium hydroxide or portranite present in the cement paste to form calcium silicate hydrate (CSH) gel, in addition to the calcium silicate hydrate (CSH) formed from the cement.

[0031] The term “mechanothermal activator” is defined herein as a material and / or compound that lowers the temperature at which a material vitrifies and / or acts as a network modifier in a Si-O matrix to modify the network structure. Mechanothermal activators can improve the reactivity of a material.

[0032] The term "vitrification" is defined herein as the conversion of a material into glass or a glassy substance by heat and fusion.

[0033] The term “Input Materials” is defined herein as materials and / or compounds from which SCM can be derived. Input Materials include, but are not limited to, natural pozzolans containing, but not limited to, zinc, lead, nickel, and copper scrap or combinations thereof; clays containing, but not limited to, aggregate powder, muscovite, illite, kaolinite clay, blue clay, or combinations thereof; concrete aggregates containing, but not limited to, recycled concrete aggregate, recycled concrete powder, or combinations thereof; sands containing, but not limited to, silica sand, bedding sand, or combinations thereof; mature fine tailings, shale ash, coal bottom ash, landfield ash, or combinations thereof; and natural pozzolans containing, but not limited to, zeolite, volcanic ash, or combinations thereof.

[0034] The term "heat treatment" is defined herein as applying heat to a material and / or compound.

[0035] As used herein, the term “source” may refer to a first compound from which a second compound is derived by a chemical reaction. For example, the source of sodium oxide may be sodium carbonate, which is approximately 58% sodium oxide. Sodium carbonate can be converted to sodium oxide by a chemical reaction.

[0036] As used herein, the term “environment” refers to physical and / or chemical conditions or combination of conditions that influence a reaction. For example, an oxidizing environment may be a reagent involved in a chemical reaction that assists or carries out an oxidation reaction.

[0037] This method can enhance the strength, durability, and other properties of concrete. It can also enable the production of concrete at a lower cost and with lower CO2 emissions.

[0038] Referring here to the drawings, Figure 1 shows a general schematic process for producing SCM from an input stream containing silicates and / or aluminosilicates. All SCMs exhibit a heat release of more than 100 joules / g ("J / g"), which clearly indicates that the material is inherently pozzolanic. In the case of the control samples, the heat release is very low, indicating that the material is inert. As shown in process 5, the input material 7 and mechanothermal activator 9 are mixed and / or pulverized 11, heat treated 13, followed by cooling 15 and milling 17 to form SCM 19. Optionally, the cooled, thermally activated input stream may also undergo a carbonation step 21.

[0039] Figure 2 shows the reactivity of SCM produced from zinc and lead scraps, nickel and copper scraps, and aggregate powder to control samples in terms of heat release.

[0040] Figure 3 shows the strength activity index of SCM prepared from various sources after 20% cement replacement in mortar mixtures according to ASTM C618.

[0041] Mechanothermal activators can lower the vitrification and / or glass phase formation temperature of input materials, including, but not limited to, inert materials, mine scrap, crystalline aluminosilicate, silicate, construction waste, aggregate, aggregate dust, silica sand, or combinations thereof. By contacting the input material with a mechanothermal activator during vitrification and / or glass phase formation, the thermal activation temperature of the input material can be lowered, and a chemical change can be induced that generates a reactive phase and forms a reactive material. Once activated, the reactive material can react with calcium hydroxide to form a CSH gel via a pozzolanic reaction, and may form SCM. Mechanothermal activators can also act as network modifiers in Si-O matrices to modify the network structure and improve the reactivity of the material.

[0042] This method may use mechanothermal activation aids to lower the temperature required for dehydroxylation, modify the Si and O network structure, improve process efficiency, and accelerate the removal of hydroxyl groups from clay mineral layers. Clay minerals may be sourced from waste, kaolin deposits, illite, smectite clay, mixed-layer clay, muscovite, or combinations thereof. Some sources of waste clay include, but are not limited to, oil sands waste, coal waste, or combinations thereof.

[0043] SCM can be prepared from input materials by thermally activating them. Activation may occur at lower temperatures by contacting the input materials with a mechanothermal activation aid. The temperature may be below about 1000°C, about 1000°C to about 400°C, about 950°C to about 550°C, about 900°C to about 600°C, about 850°C to about 650°C, about 800°C to about 700°C, or about 400°C. Thermal activation of the input materials may be carried out in an oxidizing environment. However, thermal activation may also be carried out by reducing or creating an oxygen-free environment by purging with an inert gas, including but not limited to CO2, H2, CO, nitrogen, and argon, helium, neon, krypton, xenon, and radon. Reduction or creation of an oxygen-free environment may lower the temperature required for vitrification. Reducing conditions may be generated by contacting and / or mixing reducing agents, including but not limited to thiourea, ascorbic acid, sodium sulfite, oxalic acid, tannic acid, citric acid, or combinations thereof, with an inert gas. The inert gas and / or reducing agent may be mixed in a kiln or other container in the presence of the input material to reduce the input material.

[0044] Input materials containing silica and / or aluminosilicate oxides can be sources of SCM. These silica and / or aluminosilicate oxides include, but are not limited to, waste mine scrap, construction waste, sand, or combinations thereof. While silica and / or aluminosilicate oxides may be rich in silicon or aluminum oxides, they can be highly crystalline in nature. However, crystalline materials do not exhibit pozzolanic or hydraulic properties and therefore do not react with calcium hydroxide in the cement paste to form additional CSH gels. Consequently, they do not offer the same advantages as SCM and must be converted to SCM according to the method of this invention.

[0045] Silicate minerals can be difficult to vitrify because they have high melting points and tend to crystallize at high temperatures. For example, pure silica sand vitrifies at approximately 1700°C, while silicate minerals such as feldspar have a vitrification temperature of approximately 1100-1200°C. Generally, silicate minerals vitrify above 1000°C. This method may involve using a mechanothermal activator to lower the temperature required for vitrification, modify the network structure, and / or prevent crystal growth while cooling. The mechanothermal activator can lower the melting point of the silicate mineral by forming a eutectic mixture with it. This mixture may have a lower melting point than the individual components, which can allow the material to melt and vitrify at lower temperatures. Vitrification in the presence of a mechanothermal activator can enable the production of SCM using globally abundant input materials, providing the superior performance characteristics needed to meet the demands of the construction industry while reducing the overall carbon footprint associated with cement production.

[0046] Clay minerals are naturally occurring minerals containing layers of metal-oxygen (e.g., aluminum-oxygen) octahedral sheets and silicon-oxygen tetrahedral sheets. These sheets can be held together by weak van der Waals forces and hydrogen bonds. Clay minerals can contain hydroxyl groups (-OH) located at the edges of the layers, which are responsible for the clay's ability to adsorb water and other polar molecules. Dehydroxylation is the process of removing hydroxyl groups from the edges of clay mineral layers. This process can be carried out by heat treatment, which involves heating the clay mineral to high temperatures (e.g., over 600°C in the case of kaolinite clay). During the heat treatment process, hydroxyl groups can decompose into water (H2O) and hydroxyl radicals (OH), which then react with adjacent hydroxyl groups, resulting in their removal. Hydroxylated clay minerals can be amorphous and can act as a source of SCM (Sulfur-Cellulose Mycelium).

[0047] This method may include contacting the input material with a mechanothermal activator. Contacting the mechanothermal activator with the input material may promote the vitrification of crystalline silicates and / or aluminosilicates. The mechanothermal activator may be an alkaline mechanothermal activator containing, but is not limited to, sodium oxide, potassium oxide, lithium oxide, barium oxide and their respective sources, or combinations thereof. Mechanothermal activation aids include, but are not limited to, sodium oxide and its sources including, but not limited to, sodium carbonate, sodium hydroxide, sodium chloride, sodium silicate, sodium nitrate, or combinations thereof; potassium oxide and its sources including, but not limited to, potassium carbonate, potassium hydroxide, potassium chloride, potassium silicate, potassium nitrate, or combinations thereof; lithium oxide and its sources including, but not limited to, lithium carbonate, lithium hydroxide, lithium chloride, lithium silicate, or combinations thereof; barium oxide and its sources including, but not limited to, barium carbonate, barium hydroxide, barium nitrate, or combinations thereof; calcium oxide and its sources including, but not limited to, limestone, dolomite, gypsum, calcium chloride, calcium hydroxide, or combinations thereof; Magnesium, and its sources including, but not limited to, magnesite, brucite, magnesium sulfate, or combinations thereof; aluminates including, but not limited to, aluminum oxide, aluminum hydroxide, sodium aluminate, or combinations thereof; borates including, but not limited to, boric acid, boron oxide, borax, colemanite or urexite ore, or combinations thereof; fluorides and fluoroborates including, but not limited to, potassium fluoride, sodium fluoride, calcium fluoride, or combinations thereof; phosphates including, but not limited to, P2O5-based phosphates, calcium diphosphate, sodium hexametaphosphate, or combinations thereof; iron oxides including, but not limited to, hematite, magnetite, or combinations thereof; or combinations thereof.

[0048] A mechanothermal activator may be brought into contact with the input material in the presence of heat and / or high temperature. The input material and temperature may be selected based on the composition of the input material. For example, in the case of kaolinite-rich clay minerals, an alkali flux containing sodium carbonate, but not limited to this, may be used at a temperature below 600°C. In the case of illite, muscovite, mixed clays, and smectite clays, the alkali mechanothermal activator may be used in combination with and / or simultaneously with borate and / or aluminate to improve the vitrification process. For example, alkali flux is usually combined with borate to lower the vitrification temperature and produce SCM from silicate and / or aluminosilicate-rich minerals.

[0049] SCM may be pozzolanic and may react with calcium hydroxide (Ca(OH)2) in the presence of water to form cementitious compounds. These cementitious compounds may be reactive amorphous aluminosilicate materials that can be used for geopolymerization to form geopolymers. Geopolymers are inorganic materials that can be formed from the reaction of an aluminosilicate precursor with an alkaline solution, typically a sodium or potassium hydroxide or silicate solution. Cement produced from geopolymers may be formed at lower temperatures than conventional Portland cement and may have lower carbon emissions. The reaction between the aluminosilicate precursor and the alkaline solution can form a three-dimensional network of tetrahedral units linked by covalent bonds, resulting in a stable and durable material. Geopolymers may have properties similar to conventional cement, including, but not limited to, high compressive strength, low permeability, good fire resistance, or a combination thereof, and may be more environmentally friendly and chemically resistant than conventional cement.

[0050] The reactivity of SCM can be measured by contacting SCM with an alkaline solution of Ca(OH)2 and 0.5 M KOH. The resulting mixture can be cured at temperatures of at least about 45°C, about 45°C to about 55°C, about 47°C to about 53°C, 49°C to about 51°C, or about 50°C. SCM is pozzolanic and, if SCM cures after 24 hours, is formed from a cement-like product containing calcium hydroxide.

[0051] SCM reactivity can be measured as the heat released in a model system containing calcium hydroxide, an alkaline solution of KOH, and SCM. The heat release of reactive SCM can be at least about 80 J / g, about 80 J / g to about 200 J / g, about 90 J / g to about 190 J / g, about 100 J / g to about 180 J / g, about 110 J / g to about 170 J / g, about 120 J / g to about 160 J / g, about 130 J / g to about 150 J / g, or about 200 J / g.

[0052] SCM can be used to replace cement in mortar mixtures. The replacement may be carried out as outlined in ASTM C618. The amount replaced may be at least about 10%, about 10% to about 40%, about 15% to about 35%, about 20% to about 30%, or about 40% of the mortar mixture.

[0053] The compressive strength of the material may be measured and the strength activity index ("SAI") may be determined by comparing it to a 100% cement control. According to ASTM C618, materials exhibiting an SAI greater than 75% at a 20% substitution level are classified as SCM.

[0054] This method may include contacting SCM with calcium hydroxide. This method may also include contacting SCM with a base. The base may include, but is not limited to, KOH, NaOH, LiOH, CsOH, other strong bases, other ionic bases, or combinations thereof. This method may further include contacting SCM with calcium hydroxide and a base to form an activated SCM mixture. The SCM mixture may be cured at temperatures of at least about 40°C, about 40°C to about 60°C, about 42°C to about 58°C, about 44°C to about 56°C, about 46°C to about 54°C, about 48°C to about 52°C, or about 60°C. The SCM mixture may be cured for at least about 12 hours, about 12 hours to about 48 hours, about 16 hours to about 44 hours, about 20 hours to about 40 hours, or about 24 hours to about 36 hours, about 28 hours to about 32 hours, or about 48 hours.

[0055] Embodiments of the present invention provide a technology-based solution that overcomes existing problems of current state-of-the-art technologies, addressing existing problems for reducing CO2 emissions during cement production. Embodiments of the present invention achieve significant advantages beyond the current state of technology, such as reduced emissions in cement production using readily available source materials and the production of cement-based materials at temperatures below 1000°C. Some of the unconventional steps of embodiments of the present invention include the addition of a mechanothermal activator to induce vitrification of the supply material for producing SMC. Industrial applicability:

[0056] The present invention can be further illustrated by the following non-limiting examples. Example 1

[0057] SCM was prepared from zinc and lead scrap. The zinc and lead scraps were pulverized using 3% by weight solid sodium carbonate and 5% by weight solid boron oxide, and then heat-treated at 700°C for 1 hour. The heat-activated materials were then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and exhibited cement-like activity. Zinc scrap heat-treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is insufficient to induce vitrification of the scrap samples. Example 2

[0058] SCM was prepared from zinc and lead scrap. The zinc and lead scrap was pulverized with 2% by weight solid sodium carbonate and 3% by weight solid boron oxide, and then heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and exhibited cementitious activity. Example 3

[0059] SCM was prepared from nickel and copper scrap. Nickel and copper scrap was pulverized using 3 wt% solid sodium carbonate and 5 wt% solid boron oxide, and then heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Nickel and copper scrap heat-treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of the scrap samples. Example 4

[0060] SCM was prepared from nickel and copper scrap. Nickel and copper scrap was pulverized with 2% by weight solid sodium carbonate and 3% by weight solid boron oxide, and then heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and exhibited cementitious activity. Example 5

[0061] SCM was prepared from nickel and copper scrap. Nickel and copper scrap was pulverized with 7% by weight solid sodium carbonate and 3% by weight solid boric acid, and then heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and exhibited cementitious activity. Example 6

[0062] SCM was prepared from copper scrap. The copper scrap was pulverized using 3 wt% solid sodium carbonate and 5 wt% solid boron oxide, and then heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Copper scrap heat-treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of the scrap sample. Example 7

[0063] SCM was prepared from aggregate powder. The aggregate powder was pulverized using 3% by weight solid sodium carbonate and 5% by weight solid boron oxide, and then heat-treated at 700°C for 1 hour. Next, the heat-activated material was ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Aggregate powder heat-treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of aggregate powder. Example 8

[0064] SCM was prepared from muscovite and / or illite. Muscovite and / or illite-rich clay was pulverized using 2% by weight solid sodium carbonate and 3% by weight solid boron oxide, and heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Clay heat-treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of illite and / or muscovite clay. Example 9

[0065] SCM was prepared from muscovite and / or illite. Muscovite and / or illite-rich clay was pulverized with 2% by weight of solid sodium carbonate and 3% by weight of solid borax, and heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Clay heat-treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of illite and / or muscovite clay. Example 10

[0066] SCM was prepared from muscovite and / or illite. Muscovite and / or illite-rich clay was pulverized with 5% by weight of solid sodium carbonate and heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Clay heat-treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of illite and / or muscovite clay. Example 11

[0067] SCM was prepared from recycled cement paste. The recycled cement paste was pulverized with 2% by weight solid sodium carbonate and 3% by weight solid boron oxide, and heat-treated at 600°C for 1 hour. The heat-activated materials were then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Recycled cement paste treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of recycled cement paste. Example 12

[0068] SCM was prepared from recycled cement paste. The recycled cement paste was pulverized with 2% by weight solid sodium carbonate and 3% by weight solid borax, and heat-treated at 700°C for 1 hour. The heat-activated materials were then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Recycled cement paste treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of recycled cement paste. Example 13

[0069] SCM was prepared from recycled cement paste. The recycled cement paste was pulverized with 2% by weight solid sodium carbonate and 2% by weight solid aluminum hydroxide, and heat-treated at 700°C for 1 hour. The heat-activated materials were then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Recycled cement paste treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of recycled cement paste. Example 14

[0070] SCM was prepared from recycled cement paste. The recycled cement paste was pulverized with 5% by weight of barium carbonate and heat-treated at 700°C for 1 hour. Then, the heat-activated material was ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Recycled cement paste treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of recycled cement paste. Example 15

[0071] SCM was prepared from recycled cement paste. The recycled cement paste was pulverized with 5% by weight of sodium carbonate and heat-treated at 700°C for 1 hour. Then, the heat-activated material was ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cement-like activity. Recycled cement paste treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of recycled cement paste. Example 16

[0072] SCM was prepared from recycled concrete aggregate. The recycled concrete aggregate was crushed using 3% by weight solid sodium carbonate and 5% by weight solid aluminum hydroxide, and then heat-treated at 700°C for 1 hour. Next, the heat-activated materials were ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Recycled concrete aggregate treated at 800°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of recycled concrete aggregate. Example 17

[0073] SCM was prepared from recycled concrete aggregate. The recycled concrete aggregate was crushed using 3% by weight solid sodium carbonate and 5% by weight solid boron oxide, and then heat-treated at 800°C for 1 hour. Next, the heat-activated materials were ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Recycled concrete aggregate treated at 800°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone is not sufficient to induce vitrification of recycled concrete aggregate. Example 18

[0074] SCM was prepared from recycled concrete aggregate. The recycled concrete aggregate was crushed using 5% by weight solid sodium carbonate and 5% by weight solid boric acid, and then heat-treated at 800°C for 1 hour. Next, the heat-activated material was ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Recycled concrete aggregate treated at 800°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of recycled concrete aggregate. Example 19

[0075] SCM was prepared from recycled concrete aggregate. The recycled concrete aggregate was crushed using 10% by weight solid calcium oxide and 3% by weight solid boric acid, and then heat-treated at 800°C for 1 hour. Next, the heat-activated material was ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Recycled concrete aggregate treated at 800°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of recycled concrete aggregate. Example 20

[0076] SCM was prepared from recycled concrete aggregate. The recycled concrete aggregate was crushed using 10% by weight solid sodium carbonate and heat-treated at 700°C for 1 hour. Then, the heat-activated material was ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Recycled concrete aggregate treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of recycled concrete. Example 21

[0077] SCM was prepared from recycled concrete aggregate. The recycled concrete aggregate was crushed using 10% by weight solid sodium carbonate and heat-treated at 700°C for 1 hour. The material was then dispersed in water with 0.1% polyacrylate dispersant in a 3:2 (solid:liquid) ratio and carbonated by bubbling CO2 into the slurry for 1 hour. The carbonated slurry was then filtered and dried. The carbon dioxide uptake of the material, measured by TGA, was 6%. The carbonation step can also be used to regenerate sodium carbonate. Furthermore, the presence of sodium carbonate catalyzes the reaction rate of carbon capture. The carbonated, heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture cured after 1 day and showed cementitious activity. Recycled concrete aggregate treated at 700°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot cause vitrification of recycled concrete. Example 22

[0078] SCM was prepared from silica sand. Silica sand was crushed using 3 wt% solid sodium carbonate and 5 wt% solid boron oxide, and then heat-treated at 700°C and 800°C for 1 hour. The heat-activated materials were then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Silica sand treated at 800°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of recycled concrete aggregate. Example 23

[0079] SCM was prepared from kaolinite clays. Kaolinite clays from Georgia, Spain, and Turkey were pulverized using 2% by weight of solid potassium difluoride and heat-treated at 450°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. All samples hardened strongly after 3 hours and showed cementitious activity. Kaolinite clays without the mechanothermal activator at 450°C showed some hardness after 1 day but did not show strong bonding. This indicates that the use of the mechanothermal activator improves the degree of dehydroxylation. Example 24

[0080] SCM was prepared from kaolinite-rich clay. The kaolinite-rich clay was pulverized using 3% by weight of solid sodium silicate and 0.25% ascorbic acid as a reducing agent, and then heat-treated at 500°C for 1 hour in a CO2 environment. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. All samples hardened strongly after 3 hours and showed cement-like activity. Kaolinite clay without the mechanothermal activator at 500°C showed some hardness after 1 day but did not exhibit strong bonding. This indicates that the use of the mechanothermal activator improves the degree of dehydroxylation. Example 25

[0081] SCM was prepared from mature fine tailings. Mature fine tailings from oil sands were pulverized with 3 wt% solid sodium carbonate and heat-treated at 450°C, 500°C, and 550°C for 1 hour, respectively. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solutions as described above and cured at 50°C for 1 day. All samples cured after 1 day and showed cement-like activity. Oil sand clay without mechanothermal activator at 550°C showed some hardness after 1 day but did not show strong bonding. This indicates that the use of mechanothermal activator improves the degree of dehydroxylation. Example 26

[0082] SCM was prepared from bedding sand. Bedding sand (a mixture of sand and clay) was crushed using 3% by weight solid sodium carbonate and 5% by weight solid boron oxide, and then heat-treated at 800°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Silica sand treated at 800°C without the use of a mechanothermal activator did not harden after 1 day. This indicates that heat treatment alone cannot induce vitrification of recycled concrete aggregate. Example 27

[0083] The prepared SCM was crushed and / or milled in a CO2 atmosphere to carbonize the minerals. Specifically, recycled concrete aggregate was crushed using 10 wt% solid calcium oxide and 3% boric acid and heat-treated at 800°C for 1 hour. Then, the thermally activated recycled concrete aggregate was ball-milled in a CO2 atmosphere (10 psi pressure) by purging to prepare SCM and capture CO2. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and showed cementitious activity. Example 28

[0084] SCM was prepared from nickel and copper scrap. Nickel and copper scrap was crushed using 10% by weight solid sodium carbonate and heat-treated at 700°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and exhibited cementitious activity. Example 29

[0085] SCM was prepared from oil shale ash. Oil shale ash was pulverized using 5% by weight solid barium carbonate and heat-treated at 500°C for 1 hour. The heat-activated material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture hardened after 1 day and exhibited cementitious activity. Example 30

[0086] SCM was prepared from bottom ash. Bottom ash was pulverized with 3 wt% solid sodium carbonate and heat-treated at 400°C for 1 hour. The heat-activated material was carbonated with 0.1% polyacrylate dispersant in a 7:3 solid / liquid ratio for 1 hour and dried. Furthermore, the presence of sodium carbonate catalyzes the carbon capture reaction rate. The dried material was then ball-milled to prepare SCM. The prepared SCM was mixed with calcium hydroxide and KOH solution as described above and cured at 50°C for 1 day. The mixture cured after 1 day and exhibited cement-like activity.

[0087] The above examples can be repeated and similarly successful by replacing those used in the above examples with the reactants and / or operating conditions described in general or specifically of the present invention.

[0088] In the specification and claims, “about” or “approximately” means within 20 percent (20%) of the cited figure. The terms “a,” “an,” “the,” and “said” mean “one or more” unless the context specifically indicates otherwise.

[0089] While the present invention has been described in detail with particular reference to these embodiments, other embodiments can achieve similar results. Variations and modifications of the present invention will be obvious to those skilled in the art, and all such modifications and equivalents are intended to be covered in the appended claims. All of the references, applications, patents and publications cited above are incorporated herein by reference.

Claims

1. A method for producing auxiliary cement-based materials, The steps include bringing the input flow into contact with the mechanothermal activation aid, The steps include: heat-treating the input flow in an oxidizing environment to form a heat-treated input flow; The steps include: cooling the heat-treated input flow to obtain an auxiliary cement-based material; Methods that include...

2. The method according to claim 1, further comprising the step of carbonating the heat-treated input stream.

3. Carbonation is performed by converting the heat-treated input flow into CO ２ The method according to claim 2, comprising bringing into contact with the following.

4. The method according to claim 1, further comprising the step of mixing the input flow and the mechanothermal activation aid.

5. The method according to claim 1, further comprising the step of milling the heat-treated feed stream.

6. The method according to claim 1, wherein the mechanothermal activating agent lowers the vitrification formation temperature.

7. The method according to claim 1, wherein the mechanothermal activation aid modifies the network structure.

8. The method according to claim 1, wherein the mechanothermal activation aid lowers the temperature required for dehydroxylation.

9. The method according to claim 1, wherein the mechanothermal activating agent comprises an alkaline mechanothermal activating agent.

10. The method according to claim 1, wherein the mechanothermal activation aid comprises aluminate.

11. The method according to claim 1, wherein the mechanothermal activating agent comprises borate.

12. The method according to claim 1, wherein the mechanothermal activating agent comprises fluoride.

13. The method according to claim 1, wherein the mechanothermal activation aid comprises a phosphate.

14. The method according to claim 1, wherein the heat treatment comprises heating the input material and the mechanothermal activator to a temperature of less than approximately 1000°C.

15. The method according to claim 1, wherein the input material includes silica oxide.

16. The method according to claim 1, wherein the input material includes aluminosilicate.

17. The method according to claim 1, further comprising the step of measuring the reactivity of the auxiliary cement-based material.

18. Calcium silicate hydrate bond, Auxiliary cement-based materials, Mechanothermetic activation aid and A composition containing the following:

19. The composition according to claim 18, further comprising a carbonate.

20. The composition according to claim 18, further comprising C-S-H gel.

21. A method for producing auxiliary cement-based materials, The steps include bringing the input flow into contact with the mechanothermal activation aid, In a reducing environment, the input flow is heat-treated to form a heat-treated input flow. The steps include: cooling the heat-treated input flow to obtain an auxiliary cement-based material; Methods that include...

22. The method according to claim 22, further comprising an inert environment.

Images