Compositions and methods for utilizing co 2

Abstract

Provided herein are systems and methods for contacting particles of a composition comprising solid cementitious material and exogenous carbon dioxide while the particles are treated to reduce the size of the particles. Further, provided herein are cement composition comprises one or more carbonates produced by the disclosed systems and methods.

Description

COMPOSITIONS AND METHODS FOR UTILIZING CO2CROSS-REFERENCE

[0001] This application claims the benefit of U.S. Provisional Application No.63 / 550,577 filed February 6, 2024, which application is incorporated herein by reference.BACKGROUND

[0002] The process of producing hydraulic cement, such as Portland cement, involves production of clinker, which are relatively large particles of cementitious material, and treating the clinker, generally in the presence of other substances, to reduce its size to a desired range for use as hydraulic cement, e.g., Portland cement. The process provides opportunities for methods to modify the cement in one or more ways as it is ground, or immediately after.INCORPORATION BY REFERENCE

[0003] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.BRIEF DESCRIPTION OF THE DRAWINGS

[0004] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

[0005] Figure 1 shows temperature development during CO2 treatment in Ball mill - 5 min treatment.

[0006] Figure 2 shows temperature development during CO2 treatment in Ball mill - 10 min treatment.

[0007] Figure 3 shows temperature development during CO2 treatment in Ball mill (Preheated sample) - 2 min treatment.

[0008] Figure 4 shows temperature development during CO2 treatment in Ball mill (Preheated sample) - 5 min treatment.

[0009] Figure 5 shows temperature development during CO2 treatment in Ball mill (Preheated sample) - 5 min treatment.DETAILED DESCRIPTIONGeneral

[0010] Provided herein are systems and methods for contacting a composition comprising one or more solid cementitious materials, such as compositions comprising hydraulic cement clinker, e.g. Portland cement clinker, and / or supplementary cementitious material (SCM) or alternative supplementary cementitious materials (ASCM), with exogenous carbon dioxide. The contacting can occur 1) while the particles are being treated in an apparatus to reduce the size of the particles, for example by grinding the particles in a grinding system, thereby producing a population of reduced-size particles; 2) while reduced-size particles are transported to a cooling vessel; 3) while the particles are cooled in a cooling vessel, or any combination of 1), 2), and 3). As used herein, “exogenous carbon dioxide” includes any carbon dioxide that is in addition to any atmospheric air that may be present in the environment of methods or compositions, i.e., not atmospheric air itself; exogenous carbon dioxide includes, but is not limited to, carbon dioxide derived directly or indirectly from atmospheric air (e.g., carbon dioxide from direct air capture, biogenic carbon dioxide, and the like), produces in an industrial or other artificial process (e.g. cement production, power plants and other point sources, or produced or derived from any other suitable source. In certain embodiments, carbon dioxide is sourced from a biogas operation. Unless otherwise indicated, “carbon dioxide,” as used herein, refers to exogenous carbon dioxide. Also provided are compositions, e.g., compositions used or produced in one or more of the methods herein.

[0011] Pure Portland cement is made up of ground Portland cement clinker and gypsum, with a small amount (<1%) of mineral additives. Cement is mixed with water, sand, and gravel to form concrete. The gypsum is added to the cement to assist in controlling the set or hardening time of the resultant concrete. Portland cement clinker, manmade lava, is manufactured by fusing calcium oxide (lime) with other minerals, most notably silica, alumina, and iron at temperatures up to 1500 C. Lime is the main ingredient in Portland cement clinker. The lime (CaO) is produced in the manufacturing process by calcining limestone (CaCO3) at temperatures around 850 °C.CaCOs + Heat <=> CaO + CO2

[0012] The production of Portland cement clinker releases carbon dioxide through the calcination process (see above) and the combustion of the fuel required to achieve the high temperatures involved. Minerals that have cement like properties have been used as Portland cement additives to reduce the clinker content in “cement”. These minerals are collectively known as Supplemental Cementitious Materials (SCMs). Traditional SCMs include blast furnace slag, fly ash, and natural pozzolans. Two other mineral admixtures that have traditionally been used in small quantities in concrete are silica fume and metakaolin. Both of these latter products consist of very fine particles that enhance the strength and durability of concrete. The traditional SCM materials have been available in sufficient quantities in the past and have been used to substitute for Portland cement clinker in cement and concrete.

[0013] The desire to further reduce cement’s carbon footprint has led to an increase in the use of SCMs. Fly ash is the ash that is collected from coal combustion. The quantity of fly ash is diminishing as more and more coal fired power plants have shut down. Slag is a waste product from iron production and is limited in supply. Natural pozzolans mostly come from volcanic ash which is not widely available is all countries.

[0014] The scarcity of traditional SCMs has led to the development of additional materials that can be added to cement, ASCMs or alternative supplemental cementitious materials. There is a plethora of ASCMs which can include calcined clay, ground bottom ash, ground glass, and other ashes to name a few. Many companies are looking to manufacture their own proprietary ASCMs as well. The vast majority of ASCMs have a high silica and / or alumina content and provide some beneficial properties to the concrete.

[0015] Limestone has been approved as a cement additive in the US and Canada. Limestone is an inert material that does not add considerable strength to concrete. However, research has shown that adding very fine limestone particles to a blend of cementitious materials can enhance the performance of the resulting concrete. Today limestone is added to the clinker and other mineral additives in a cement grinding circuit. The limestone is softer than the Portland cement clinker and often forms the finer particles in the interground cementitious mix.

[0016] Injecting carbon dioxide into ground cementitious materials can form much smaller sized carbonate particles than the ground limestone itself. Without being bound by theory, it is thought that these finer sized particles act as nucleation sites to speed up the hydration of concrete providing a higher strength concrete. These very fine carbonate particles can also improve other cement and concrete properties such as durability.

[0017] The addition of carbon dioxide can be made at any place in the production and use chain of the ground cementitious products. This includes from the cement grinding circuit through to the final storage and proportioning of the cement into concrete.

[0018] The cementitious materials have to be fine enough to have a sufficient surface area to react. The normal process for grinding cement consists of intergrinding Portland cement clinker, and other cementitious materials in a cement grinding circuit. The ground materials are then sized to ensure that the final ground cementitious material meets the quality control standards. The sizing and grinding are performed in a cement grinding circuit that can comprise different pieces and arrangements of equipment.

[0019] The grinding operation has an optimum operating temperature range that ensures the drying and heating of all the cementitious materials. Ideally the temperature of grinding the cementitious materials is controlled between 100 and 110 °C. At these temperature a portion of the gypsum is dehydrated transforming it into hemihydrate which improves its performance in concrete. Meeting the desired temperatures could mean that additional heating or cooling of the materials is required. Water sprays can be used if necessary for material cooling. Cement is normally cooled after grinding to temperatures below 80 °C to prevent additional gypsum dehydration in the cement silos. The release of water from the gypsum in the cement silos creates lumps that negatively impact the load out of cement.

[0020] Often grinding circuits that have too much heat incorporate an indirect cooler, known in the cement industry as a “cement cooler”. The cement cooler is normally installed in the grinding circuit where it receives the finish ground product and cools it before transport to the storage silo.

[0021] Cement can be transported by several different means. One of the most common means is by pneumatic pump. The pneumatic pump uses compressed air to transport the dry, ground cementitious material to the storage area(s). The advantage of pneumatic pumps is that they can access several different storage locations via a pipeline and valve system. They are simple to operate but do consume a lot of power for the pump and compressor.

[0022] Mechanical transport systems usually consist of Airslides and bucket elevators. The Airslide is a device specifically designed to move fine powders. The Airslide is constructed in two sections, a gas side and a material side separated by a cloth fabric. A stream of low-pressure gas is forced upwards from the gas side through the cloth fabric which fluidizes the fine material above the cloth. The Airslide is installed on an angle that allows the fluidized material to flow by gravity at a high speed down the slope to the discharge point. Mechanical conveying systems can also use belt conveyors and screw conveyors. Ingeneral, mechanical conveying systems consume less power, but can be more complex when filling multiple storage locations.

[0023] Horizontal ball mills and Vertical Roller Mills (VRMs) are the most popular mills used for grinding cement. Roll presses and ring roller mills are also widely used. Separators are used to ensure the proper sizing of the cementitious product. The separator uses gravity and air flow to separate the material into fine and coarse fractions. The fine fraction is sent to the product cooling and transport. The coarse fraction is returned to the grinding circuit.

[0024] Separators are internal to the VRMs and are a separate piece of standalone equipment for the other mill types. Mill discharge material is normally conveyed by bucket elevator and Airslides to the external, standalone separators. Standalone separators are used in the ball mills, roll presses, and ring roller mills.

[0025] In certain embodiments disclosed herein, CO2 is fed into fine cementitious materials after they have been ground but before they are mixed into concrete. Carbonation reactions are impacted by temperature, pressure, CO2 concentration and contact time. The best location and process for the carbonation reaction will vary due to differences in cement grinding, transport, and storage circuits.

[0026] The CO2 would be expected to be mineralized, stored, and locked permanently in the ground cement. The mineralization of 1-2% CO2 (by weight of clinker) would form around 2-4% of CaCCh, considering a mineralization efficiency of 90%. The CaCCh formed in-situ can potentially offset a portion of the raw limestone used as feedstock. The newly formed CaCCh is generally considerably smaller in size than the interground limestone particles.

[0027] Compositions comprising solid cementitious materials can include compositions comprising hydraulic cement, such as Portland cement, e.g., Portland cement clinker, and / or other suitable cementitious materials, such as SCM and / or ASCM. SCM can include one or more of quarried limestone (e.g., when ground to finer particles), fly ash, slag, silica fume, natural pozzolons, calcined claim, biomass ashes, or any combination thereof. ASCM can include any suitable ASCM. In certain compositions, a composition comprising solid cementitious material may not include hydraulic cement, e.g., Portland cement, e.g, a composition may comprise SCM and / or ASCM but no hydraulic cement. The composition comprising cementitious material may include other materials, e.g., gypsum, grinding aids, and / or other suitable materials.

[0028] The layout and operation of a typical cement manufacturing plant is as follows:

[0029] 1) Extraction of Raw Materials: Limestone, clay, and other raw materials are extracted from quarries, mines, or natural deposits. Limestone is the primary raw material used for cement production and is normally quarried on site. The raw materials are hauled from their place of origin to the cement plant.

[0030] 2) Crushing and Pre-Blending: The extracted materials are crushed and then stored on site to provide a buffer stock. The materials can be stored separately or in a prehomogenization yard where one or more materials are mixed to enhance the consistency and quality of the raw material.

[0031] 3) Raw Material Preparation: The crushed materials are proportioned by weigh feeders to obtain the desired chemical composition. The combined raw materials are then ground together into a fine powder. The ground raw materials are then stored in regular and homogenization silos providing 1 - 2 days of buffer stock.

[0032] 4) Pre-Heating and Pre-Calcining: The raw mix is extracted from the blending silo and fed to the pyro-processing system. The feed material is pre-heated and then fed into a pre-calciner where fuel is burned at a high temperature (around 1650°F). This process removes carbon dioxide from the limestone converting it to lime which allows it to react with the other minerals in the feed material.

[0033] 5) Clinker Production: The pre-calcined raw mix is fed into the rotary kiln where additional fuel is burned to further heat the raw material to the reaction temperatures (around 2500 °F). At this temperature, the materials fuse to form small marble-sized balls known as clinker.

[0034] 6) Clinker Cooling: The clinker is then rapidly cooled by blowing ambient air through a moving grate system aka “clinker cooler”, which reduces the temperature of the clinker to a suitable level for grinding.

[0035] 7) Clinker Grinding: The cooled clinker is ground into a fine powder along with a small amount of gypsum to control the setting time and other mineral additives along with various grinding aids. The cement is passed through a cement separator which classifies the cement particles to the proper fineness. The coarser particles are sent back to the grinding mill for further processing and the finished cement is directed to a conveying system for transport to storage. Cement conveying can be either through mechanical means (belt conveyors and bucket elevators) or through a pneumatic pump which uses compressed air to transport the material.

[0036] 8) Packing and Dispatch: The final cement product is stored in silos and can then be shipped in bulk or packed into bags and palletized. Finished cement can be transported bytruck, rail, barge and / or ocean-going vessel. Cement terminals can provide intermediate storage between the cement manufacturing plant and the final customer. Cement is usually shipped by truck to the final use point.

[0037] 9) Cement is received at the use point which normally consists of a ready-mix concrete plant or concrete products plant. The ready-mix concrete plant combines the cement with the sand, aggregate, and water to produce concrete that is delivered by truck to work sites. The concrete product plants use concrete mixed on site to produce cured concrete items such as pipes, blocks, culverts, etc. Some cement can be delivered directly to large projects such as concrete roadways, airports, and dams, etc.

[0038] In certain embodiments disclosed herein, the process starting with the clinker / cement grinding mill is of interest. Grinding mills are operated to pulverize the clinker along with a small percentage of gypsum and other mineral additives. The clinker, gypsum, limestone and grinding aids are fed into the cement mill, where they are crushed and finely ground to produce cement. There are several different types of grinding mill in use today.

[0039] The apparatus to reduce size of particles is typically a grinding apparatus, also referred to as a grinding system or grinding mill herein. The grinding apparatus can be any suitable apparatus, such as a ball mill, a vertical roller mill, a horizontal roller mill, or a hybrid combination thereof. The grinding apparatus can be configured to run in batch or continuously. The grinding apparatus can be configured to introduce exogenous carbon dioxide to the particles at any stage of the grinding process, for example at feeding, in the grinding system, and / or at discharge.

[0040] Thus, particles of compositions, such as those disclosed herein may be ground in any suitable grinding apparatus, for example a vertical apparatus or a horizontal apparatus. Suitable grinding apparatuses include ball mills, vertical roller mills, roller press with ball mill, horizontal roller mills, or the like. In certain embodiments, a vertical roller mill (VRM) is used. In certain embodiments, a horizontal ball mill is used. In certain embodiments, a horizontal roller mill is used. Inside the grinding system, particles of the composition are ground to form a fine powder of a desired particle size. In certain embodiments, the system further comprises an apparatus configured to deliver spray water to the grinding apparatus.

[0041] Ball mills. In certain embodiments, a ball mill is used. Ball mills are cylindrical devices that rotate around a central axis comprising a grinding medium (such as steel balls or rods). As particles of compositions, such as those as disclosed herein, are added to the mill, the mill rotates resulting in the grinding media crushing the particles of the composition,resulting in a population of reduced-sized particles. Ball mills are versatile, simple to operate, and suitable for both wet and dry grinding operations.

[0042] Typical ball mills comprise a horizontal cylindrical shell comprising a feed end and a discharge end oriented along a central axis of the shell, grinding media within the shell, and a drive system configured to rotate the cylindrical shell. The cylindrical shell can comprise any suitable material. Typically, the material comprises steel. Inside the shell, the cylindrical section is partially filled with grinding material, typically steel balls. The size and composition of the grinding media may vary depending on the desired particle size. At both ends of the shell, there are openings for feeding the particles of the composition, such as those disclosed herein, into the cylindrical shell (feed end) and for discharging the resultant population of reduced-size particles (discharge end). Ball mills are typically powered by a motor coupled to a gear reducer, which drives the mill rotation. The motor and gear reducer are usually place on a stationary based, and the rotation motion is transmitted to the cylindrical shell via a pinion-gear arrangement. Material is fed into one end and travels through the mill to discharge out of the other end. The mill can be divided into different segments or compartments by installing grate systems in the mill. Most cement mills are divided into two compartments. The inlet compartment is filled with larger balls (50 to 100 mm) and performs the crushing action. The second compartment is filled with smaller balls (17 to 50 mm) and performs the fine grinding.

[0043] As the mill rotates, the grinding media cascade and tumble over one another, impacting and crushing the particles of the composition, such as those disclosed herein. This action results in the production of the population of reduced-sized particles. The grinding action in ball mills involves both impact and attrition forces. The grinding media collide with the particles of the composition, such as those disclosed herein, exerting impact forces, and also grind against each other, causing attrition. The grinding process may continue for any suitable time until the material reaches the desired fineness, typically measured by the product’s particle size distribution. The ground material is discharged from the mill and directed to an external separator. The separator can use air flow to carry the material into a separation zone where spinning blades allow only the finer material to pass. The coarse material drops out of the separator and is returned to the mill for additional grinding. Any moisture that is contained in the raw materials is quickly dried due to the heat from the hot clinker and the friction from the grinding action. It is common for mills to become too hot which impacts the gypsum quality. Water sprays are almost always used in ball mills for temperature control. The product can be discharged either directly from the separator and / orthe separator dust collector depending on the type of separator. Modem “3rdgeneration” separators take the entire separator gas flow to a dust collector where the product is collected and discharged.

[0044] Ball mills may operate in either batch or continuous modes. In batch operation, the mill is filled with particles of the composition, such as those disclosed herein, ground to produce the population of reduced-size particles, and then emptied for further processing by transferring the population of reduced-size particles to a suitable downstream operation. In continuous operation, particles of the composition, such as those disclosed herein, are continuously introduced into the mill and the resultant population of reduced-sized particles is continuously discharged and transferred to a suitable downstream operation. Typically, the mill product is then transported to an external separator where the coarse material is removed and returned to the mill.

[0045] Modem ball mills often incorporate one or more control systems to optimize the grinding process. Parameters such as mill speed, feed rate, and grinding media size can be adjusted to achieve the desired product quality and throughput.

[0046] Vertical roller mill. In certain embodiments, a vertical roller mill is used. The vertical roller mill utilizes pressurized grinding rollers to grind the material. The feed material is dropped onto the center of a rotating table. Centripetal force moves the material outwards from the center where it passes under the grinding rolls. The separator is internal to the mill so that the mill product is already properly sized, and the coarse material falls back onto the grinding table. VRMs are energy-efficient and provide excellent grinding ability for various types of cement. They offer lower operating temperatures and have a smaller footprint. These mills have become popular for cement grinding and are being installed in many new installations.

[0047] Vertical roller mills, for example ordinary vertical roller mills, Raymond mills, Ring roller mills, vertical shaft mills, and the like, comprise a vertical rotating table onto which grinding rollers are mounted. Particles of compositions, such as those as disclosed herein, are fed into the mill from above and ground between the rollers and the table. Vertical roller mills are energy efficient and able to handle high moisture content in feed materials. Populations of reduced-size particles may be generated with more precise control over particle size and distribution using vertical roller mills.

[0048] Typical vertical roller mills comprise a grinding table, grinding roller mounted on the grinding table, a separator at the top of the mill, and a drive system. The grinding table is typically mounted on a vertical shaft. The grinding table may comprise any suitable material,for example steel. Grinding rollers are mounted on the grinding table and are configured to enable them to exert pressure on fed particles of the composition, such as those disclosed herein, thereby crushing and grinding the particles against the table surface to produce a population of reduced-size particles. At the top of the mill, a separator may separate the population of reduced-size particles into fine and coarse fractions. The fine fraction of reduced-size particles is discharged, while the coarse fraction returns for further grinding. Vertical roller mills are typically driven by electric motors through a gearbox arrangement. The motor drives the grinding table to rotate, and the grinding rollers are drive by separated hydraulic or spring-loaded systems.

[0049] Particles of compositions, such as those disclosed herein, are fed into the mill through a central feed chute, The particles fall onto the grinding table and are ground and crushed by the grinding rollers. As the grinding table rotates, the particles are subjected to compressive and shearing forces between the rollers and the table resulting in efficient production of a population of reduced-size particles. In most of the mills, some water is added on the grinding table to control the bed stability and reduce mill vibration. The ground material may be entrained by airflow and conveyed to the separator, which separates the fine and coarse fractions as described above. For example, the ground material can be picked up by the high velocity, gas stream entering around the table periphery. The gas and material are pulled to the internal classifier positioned above the grinding table. Larger particles fall back to the grinding table and are reground. The fine material is carried through the separator to the external dust collector. Vertical roller mills may also incorporate drying, such as with gasses, to evaporate moisture from the feed material. As a part of the grinding process, the additives undergo simultaneous drying. The heat contained in the clinker plus the heat generated by the grinding action may be sufficient to dry the additives and evaporate the bed stabilization water spray. If more heat is required, it can be supplied by an external furnace. The finely ground product is carried from the mill by the gas stream to a dust collector. A cyclone may be used ahead of the dust collector to capture some of the fines. The collected fine material is then transported mechanically or pneumatically to the cement silos for eventual dispatch. A portion of the mill exhaust gas can be recirculated to save heat in the system.

[0050] Roller presses with ball mills. In certain embodiments, a roller press with ball mill is used. Roller presses with ball mills are hybrid grinding systems combining a roller press with a ball mill. The roller press pre-grinds particles of the composition, such as those disclosed herein, to generate a first population of reduced-size particles. The first populationof reduced-size particles are then fed into a ball mill and subjected to a second grinding step in a ball mill thus producing a second population of reduced-size particles. Roller presses with ball mills may increase throughput, save energy through pre-grinding, and produce populations of reduced-size particles with finer particle size distribution than either roller presses or ball mills alone.

[0051] Horizontal roller mills. In certain embodiments, a horizontal roller mill is used. Horizontal roller mills are similar to vertical roller mills but are oriented horizontally. They may comprise a horizontal shell with a rotating shaft and multiple grinding rollers. Particles of compositions, such as those as disclosed herein, are fed into the horizontal roller mill, where the material is crushed and ground between the rotating rollers and the shell.Horizontal roller mills are energy efficient and able to handle high moisture content in feed materials. Populations of reduced-size particles may be generated with more precise control over particle size and distribution using horizontal roller mills.

[0052] Typically, horizontal roller mills comprise a roller assembly, a feed system, and a drive system. The roller assembly may comprise one or more pairs of horizontally arranged rollers configured to rotate in opposite directions thereby exerting pressure on the particles of compositions, such as those disclosed herein, introduced from the feed system. The feed system typically comprises a hopper or chute configured to evenly distribute the fed particles across the width of the rollers. Horizontal roller mills are typically powered by electric motors through a gearbox arrangement. The rotational motion of the rollers is transmitted from the motor to the rollers via gears or belts.

[0053] Particles of compositions, such as those disclosed herein, are fed between the rollers either manually or through a feeding mechanism. The particles are then drawn into the gap between the rollers, when grinding takes place. As the rollers rotate, they exert pressure on the particles, crushing and grinding them against the opposing roller and / or stationary surface. This action results in production of a population of reduced-size particles. Horizontal roller mills may further comprise a separation system to separate the ground materials into fine and coarse fractions.Temperature Control:

[0054] The temperature of cement in finish grinding is important for the proper quality control of the cement. Typically, gypsum is added to the clinker to assist in controlling the set time. Too little gypsum and the clinker will set too quickly and cannot be properly finished. Gypsum can be dehydrated at temperatures above 80 °C. The gypsum crystal is composed of a calcium sulfate molecule with two attached water molecules (CaSO4-2H2O).

[0055] Heating gypsum at temperatures up to -100 °C will drive off one water molecule, creating what is known as hemihydrate (CaSO4-H2O). Hemihydrate is water soluble and more reactive than gypsum and a portion of hemihydrate is preferable. If the cement is heated past 100 °C the second water molecule can be driven off the gypsum creating anhydrite or pure calcium sulfate (CaSCh). For this reason, it is preferred that the cement temperature be less than 110 °C in the grinding process.

[0056] The gypsum will continue to dehydrate in the storage system if the temperature is above 80 °C. For this reason, many ball mill circuits utilize cement coolers to reduce the temperature of cement in storage. The cement cooler is an indirect cooler that uses a high- volume flow of water over the outer shell of a steel cylinder. Hot cement is transported in a counter flow direction inside the steel shell.

[0057] Ball mills tend to generate too much heat and require water spray for cement temperature control and cement coolers to prevent further gypsum dehydration in the silos. Vertical and the other mill types tend to produce too little heat to form the desired hemihydrate.Transport: Pneumatic Pump

[0058] In certain embodiments of the invention, a transport system, also referred to herein as a transport apparatus and the like, is used to transport reduced-size particles from one area to another, e.g., to or from a grinding apparatus to or from a classifier, from a grinding apparatus or classifier to a vessel to contain the reduced-size particles, e.g., a storage vessel, a cooling vessel, or the like. Unless otherwise indicated herein, a “transport system” and the like does not include systems to transport large quantities of reduced-size particles in bulk, e.g., trucks, rail cars, and the like. Transport systems can be of any suitable type. In certain embodiments, a transport system comprises a pneumatic transport system, such as a pneumatic pump. In certain embodiments, a transport system comprises a mechanical transport system, such as an airslide.

[0059] Pneumatic transport is widely used for conveying cement. The advantages of pneumatic transport are easy arrangement of equipment as the material is transported in pipes, small footprint and low installed costs. This is offset by a higher power consumption. The material to be transported is forced into a compressed air stream that carries the material to the destination(s). The pneumatic pump is the most popular equipment for transporting cement.

[0060] The pneumatic pump uses a rotating screw to push material through an airlock flap into the compressed air stream in the pump’s “wind box”. The compressed air is suppliedby a low-pressure compressor or blower and enters the wind box through nozzles. The wind box is connected to the pneumatic transport line. The exact volume and pressure of the compressed air depends on the quantity of cement to be transported and the transport distance with an allowance for the piping design.Transport: Airslide

[0061] Airslides are widely used in cement grinding and transport systems. Airslides are low energy, high capacity, dust free conveying equipment. An air slide comprises a rectangular sheet metal tube that is divided into two parts separated by a cloth fabric. The lower part contains the fluidizing gas, and the upper part contains the material. Airslides can be straight or curved and are usually mounted on a 6-10 degree slope depending on the material to be conveyed.

[0062] Low pressure air / gas is delivered by a fan or blower into the air chamber at the bottom of the air slide. The gas passes through the fabric and fluidizes the material above the fabric. The fluidized material then flows by gravity down the slope of the Airslides. The gas is typically cleaned in a bag filter and can then be vented or recirculated if desired.Cement Storage & Blending

[0063] Cement is usually stored in large concrete silos at the cement plant. These silos can range from 1,000 to 10,000 tons or more per silo. It was more common to have many small silos in older cement plants while newer cement plants have fewer larger silos. Silos can be either flat bottomed or have a conical discharge. Almost all new cement silos have conical discharges.

[0064] The cement is delivered to the silos through mechanical or pneumatic conveying equipment. The pneumatic pump is the most common pneumatic conveying equipment in use in cement plants, however other pneumatic systems exist including but not limited to air lifts, blow tanks, and ejector type systems. Mechanical conveying systems usually consist of Airslides and bucket elevators, but also could utilize belt conveyors, screw conveyors and other mechanical conveying equipment.

[0065] Storage silos can have compressed air / gas injected either continuously or intermittently. Intermittent gas injection is used for fluidizing the cement to allow for quick and easy discharge from the silo. Continuous gas injection can be used for blending and to keep the cement fluidized for discharge. Gases are typically supplied by compressors.

[0066] The cone of the silo can also be used to blend the cement as it discharges from the silo. Some cement plants and terminals utilize standalone blenders to produce a blend ofdifferent fine materials, such as cement and fly ash and / or ground granulated blast furnace slag. These blenders can also be used for carbonation.Compositions and Methods

[0067] Compositions and methods disclosed herein relate to processes where CO2 is added to ground, fine cement either during or after the grinding process and / or up to the final use process. Sites of carbon dioxide can include one or more of: 1) grinding, 2) pumping (transporting), 3) storage, and / or 4) dispatch. The most likely addition point(s) can depend on mill circuit specifics and can include a grinding mill inlet or outlet, a separator, a cement transport system, a cement mixing (blending) system, cement storage, or any other location where mineralization could take place. The method of CO2 injection can vary depending on injection point.

[0068] Additionally or alternatively, carbon dioxide can be contacted with cement at a usage point. The cement is transferred in bulk to one of several use locations. The most common use location is the ready-mix concrete plant where the concrete is produced and shipped to customers. Other use locations include temporary batching plants set up at large project sites, concrete product producer sites, as well as independent bagging operations. The cement can be contacted with carbon dioxide at any one or more of these use locations. For example, the particle size of solid dry ice can be optimized for retention time in the ball mill circuit to ensure sufficient time of contact with the clinker / cement particles. Theoretically, CO2 dissolves in spray water to release carbonate and bicarbonate ions which can then chemically combine with calcium ions (possibly being made available from clinker) to precipitate calcium carbonate. The precipitated calcium carbonate can be very fine (typically < 5 pm size) and can be carried to the classifier and hence would not undergo further grinding. Alternatively or additionally, CO2 gas can be added into a humid compressed air stream used in a cement pneumatic transport system. The CO2 can be added at a compressed air source inlet or outlet or even in the pneumatic transport line. The water vapor can come from the natural humidity in the air and / or be augmented by water vapor injection in the compressed air line or pneumatic transport line.

[0069] In vertical mills the CO2 can be, for example, infused in water spray used to stabilize the material bed as it passes under the mill rollers.

[0070] Various amounts of CO2 can be mineralized in the cement (expecting higher amounts in the range of 1-2% by weight of clinker), contributing to the total calcium carbonate content in the cement. If there is 1-2% CO2 uptake and mineralization efficiency of 90%, then around 2-4% of CaCCh would form. Thus, in various embodiments, the totalamount of carbon dioxide added to the processes and sites described herein, e.g., grinding, transport, storage, and dispatch, can be at least 0.1, 0.2, 0.5, 0.7, 1.0, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 3.5, 4, 5, 7, or 10% and / or not more than 0.2, 0.5, 0.7, 1.0, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 3.5, 4, 5, 7, 10 or 15% by weight of clinker, such as 0.1-15%, preferably 0.5-10%, more preferably 0.5-5%, even more preferably 0.5-4%, e.g., 1.0-2.0%. The final cement, i.e., cement used in production of concrete, can comprise at least 0.2, 0.5, 0.7, 1.0, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 3.5, 4, 5, 7, or 10% and / or not more than 0.5, 0.7, 1.0, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 3.5, 4, 5, 7, 10 or 15% calcium carbonate formed in the carbonation processes, such as 0.2-15%, preferably 0.5-10%, more preferably 0.5-7%, even more preferably 0.5-5%. The calcium carbonate formed in the carbonation processes can be extremely fine, e.g., at least 10, 20, 30, 40, 50, 60, 70, 75, 80, 85, 90, or 95%, such as at least 50%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90% of calcium carbonate formed in carbonation processes is less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1, um in longest dimension (e.g., in the case of roughly spherical particles, in diameter). Thus, calcium carbonate can be added separately in the grinding circuit as limestone addition or mineralized in-situ as a CO2 addition. The finer calcium carbonate can - (1) increase the Blaine fineness of cement thereby saving energy consumption and (2) save the virgin limestone that is fed as raw material. (3) contribute to an optimized fineness distribution resulting in increased cement strengths and mechanical performance. (4) sequester significant amounts of CO2 thereby reducing the GWP (global warming potential) per ton of cement.

[0071] Any residual gaseous CO2 can also be used to pressurize the cement pump (~35 psi required) for pumping cement to silos. This will also reduce the energy consumption.

[0072] Another possible location for CO2 treatment is a cement cooler. The cooler is a closed container with the retention time being around 2 to 5 minutes. However, the cement would be almost dry with negligible moisture. While other factors associated with the cooler are favorable for CO2 mineralization, dryness of cement could be a limitation.

[0073] In embodiments in which carbon dioxide is introduced and contacted with particles of a composition comprising solid cementitious materials in a grinding apparatus, the carbon dioxide may be introduced into the grinding apparatus in any suitable manner. In certain embodiments, carbon dioxide from a container of liquid carbon dioxide is transported via one or more conduits to an orifice, where it is released to atmospheric or near- atmospheric pressure to form solid and gaseous carbon dioxide, which is then directed into the grinding apparatus, e.g., by means of another conduit. In certain embodiments, just gaseous carbon dioxide is introduced, in any suitable manner. Additionally or alternatively,solid carbon dioxide is introduced. In the latter embodiments, solid carbon dioxide may be mixed with a particulate composition comprising solid cementitious materials before and / or during introduction of the particles composition comprising solid cementitious materials into a grinding apparatus and / or during grinding and / or classification. The solid carbon dioxide can sublimate and enter into carbonation reactions such as described herein.

[0074] Additionally or alternatively carbon dioxide is contacted with reduced-size particles as they are transported from a grinding apparatus to a cooling vessel. Typically, the process is assisted by blowing air from below to fluidize the particles. Some or all of the air can be replaced by gaseous carbon dioxide, either as part of an air mix or separately; in certain embodiments, all the gas used to fluidize the reduced-size particles is carbon dioxide. Residual carbon dioxide from a grinding apparatus may contribute some or all of the carbon dioxide used.

[0075] Additionally or alternatively, carbon dioxide is contacted with reduced-size particles in a vessel, such as a storage vessel and / or a cooling vessel. The carbon dioxide can be gaseous carbon dioxide, introduced into the vessel in any suitable manner.

[0076] Exogenous carbon dioxide can be a gas, a solid, or a combination thereof. Carbon dioxide can be a gas. Carbon dioxide can be a solid, for example, pellets of dry ice. Carbon dioxide can be a mixture of solid and gaseous carbon dioxide, such as a mixture produced by releasing liquid carbon dioxide into atmospheric or near-atmospheric pressure, causing the liquid to convert to a mixture of solid and gaseous carbon dioxide. In embodiments in which solid carbon dioxide is used, either alone or as a component of a gas-solid mixture, it is thought that the solid carbon dioxide sublimates to gaseous carbon dioxides over time. Gaseous carbon dioxide, e.g. alone, as part of a gas-solid mixture, and / or sublimated from solid carbon dioxide, is thought to dissolve in water associated with the grinding process, transport, and / or cooling; in particular, in a typical grinding process, water is introduced during the process, and may also be introduced in a cooling vessel. Water that is introduced before, during, or after grinding may remain associated with the reduced-size particles as they are transported, as well. Some or, preferably, all of the water is water that would normally be used in the process, e.g., water added while reducing the size of the composition. The aqueous carbon dioxide and / or other aqueous carbon dioxide-derived species, such as bicarbonates and / or carbonates, can react with a suitable cation, such as a divalent cation, e.g., calcium, to produce solid carbonate products, e.g., calcium carbonate. These products, e.g., calcium carbonate, can be formed on outer surfaces of particles, and some or all of the carbonate products, e.g., calcium carbonate, can be ground off or otherwise removed from theparticles during one or more of the grinding, transport, or cooling processes. The resulting free carbonate products, e.g., calcium carbonate, can be very fine, in some cases finer than particles of carbonate, e.g., calcium carbonate, produced in the grinding process by reduction of size of larger particles of the carbonate, e.g., calcium carbonate, such as particles of quarried limestone that are interground with cementitious material, e.g., with Portland cement clinker. Carbonates, e.g., calcium carbonate, can alternatively or additionally be formed in a similar process as reduced-size particles are transported to a cooling vessel, and / or in the cooling vessel itself. In certain embodiments, at least 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 22, 25, 27, 30, 35, 40, 50, 60, 70, 80, or 90% and or not more than 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 22, 25, 27, 30, 35, 40, 50, 60, 70, 80, 90, 95, or 100% of free calcium carbonate particles in the final mix, preferably 0.5-50%, more preferably 0.5-40%, even more preferably 0.5 — 30%, still more preferably 0.5-25%, yet more preferably 0.5-20% have a diameter of less than 10 um, preferably less than 5 um, more preferably less than 3um, even more preferably less than 2 um, still more preferably less than 1 um, yet more preferably less than 0.5 um. Such a large proportion of calcium carbonate particles with such low diameters is not present in mixes where all calcium carbonate is produced by intergrinding with limestone. In certain embodiments, some or all of these finer calcium carbonate particles produced by methods herein may be separated from other components of the reduced-size particles.

[0077] Thus, typically, some amount of water is present in and / or around the particles of the composition to facilitate the reaction between the calcium and exogenous carbon dioxide. The water can be water that is normally added during one or more stages of the process, e.g., to aid grinding and the like. Additionally or alternatively, some additional amount of water, such as liquid water, can added during or after treatment to reduce size of particles. In certain embodiments, gaseous carbon dioxide is taken up by water that is contacted with the solid cementitious material to produce aqueous carbon dioxide and / or carbon dioxide derivatives, and the aqueous carbon dioxide and / or carbon dioxide derivatives contacts the particles of the compositions comprising solid cementitious material. The aqueous carbon dioxide and / or carbon dioxide derivatives can then react with one or more components of the particles of cementitious material to produce carbonated material, e.g., carbonate compounds. The carbonate compounds can include metal carbonates, such as calcium carbonates. The resulting calcium carbonates may replace at least a portion, such as at least 1, 2, 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 50, 60, 70, 80, or 90 % and / or not more than 2, 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 50, 60, 70, 80, 90, 95, or 100 % of calcium carbonateparticles derived from quarried limestone in the final ground and cooled cementitious product, preferably 1-100%, more preferably 1-50%, even more preferably 1-40%, yet more preferably 1-35%, still more preferably 1-30%, yet still more preferably 1-20%, and even yet still more preferably 1-5%. The methods can result in carbonation of cementitious materials, such as Portland cement and / or SCM and / or ASCM and / or other components in the composition comprising solid cementitious material whose size is reduced to reduced-size particles, of at a level of at least 0.001, 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4 or 5% and / or not more than 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7, 8, 9, or 10 % by weight of cementitious material, for example 0.001-10%, preferably 0.1-8%, more preferably 0.2-6%, even more preferably 0.2-5%, still more preferably 0.2-3%. In certain embodiments, the cementitious material is Portland cement clinker.

[0078] The systems and methods can further include one or more control systems comprising one or more sensors, one or more processors, and / or one or more actuators, the control system configured to monitor one or more characteristics of the method and adjust one or more variables of the system configured to treat the particles to reduce the size of the particles and / or transport system and / or cooling vessel, based on the one or more characteristics. In certain embodiments, the control system is configured to adjust the amount of carbon dioxide delivered to the grinding apparatus.

[0079] The resulting reduced-size particles will contain one or more carbonate products, such as calcium carbonate, for example calcium carbonate that is not produced by grinding limestone, that can be smaller than the majority of other particles in the reduced-size particles. Thus, included herein are compositions comprising ground cementitious material, such as ground Portland cement, and particles of carbonate products, e.g., calcium carbonate, that is not produced by grinding limestone (e.g., produced by methods as described herein), for example particles of calcium carbonate that have diameters less than the diameters of some or all of the other particles in the mix, e.g., in amounts and diameters as described elsewhere herein.

[0080] In addition, compositions can comprise particles of solid cementitious material mixed with solid carbon dioxide; the particles of solid cementitious material may be, e.g., clinker before, during, or immediately after its introduction into a grinding apparatus and / or reduced-size particles produced during the grinding process. Further compositions include particles of solid cementitious material that comprise one or more carbonate products, e.g., calcium carbonate, on the outer surface of the particles.

[0081] The reduced-size particles comprising one or more carbonate products, such as those produced herein, can be used in any suitable manner, e.g., to produce concrete. Additional carbon dioxide may be introduced to the mixing wet concrete, as part of mix water (e.g., as carbonated wash water), as part of some or all of carbonated RCA, or any combination thereof.

[0082] It will be appreciated that the systems and methods disclosed herein sequester carbon dioxide; thus, in certain embodiments provided is a method of sequestering carbon dioxide using any one of the methods described herein for contacting cementitious materials, such as reduced size cementitious particles, with carbon dioxide to produce carbonation products that result in the sequestration of carbon dioxide. The carbon dioxide can be from any suitable source, e.g., as described herein, such as biogas, or direct air capture.Methods

[0083] In certain embodiments, provided herein are methods comprising: contacting particles of a composition comprising solid cementitious material with exogenous carbon dioxide 1) while the particles are treated in an apparatus to reduce the size of the particles to produce reduced-sized particles; 2) during classification of the reduced-sized particles; 3) while the reduced-sized particles are transported , e.g., to a cooling vessel, a storage vessel, a transport apparatus (system) and / or other areas where reduce-size particles are transported as described herein; 4) in a vessel containing reduced-size particles, e.g., a storage vessel or a cooling vessel.

[0084] In certain embodiments, an apparatus to reduce the size of the particles comprises a grinding apparatus and particles of the composition are treated in one or more components of a grinding apparatus. Any suitable grinding apparatus can be used, e.g., a grinding apparatus as described herein, such as a vertical grinding apparatus, for example a vertical roller mill or a vertical shaft mill, or a horizontal grinding apparatus, such as a horizontal ball mill or a horizontal roller mill. This is not intended to be a limited list and one of skill in the art would be capable of selecting an appropriate alternative. The grinding apparatus can be configured to run in batch or continuously. The grinding apparatus can be configured to introduce exogenous carbon dioxide to the particles at any suitable stage of the grinding process, for example at feeding, in the grinding apparatus, and / or at discharge. Exemplary grinding apparatus are disclosed herein.

[0085] The reduced-size particles can be transported from the grinding apparatus e.g., to a cooling vessel and / or a storage vessel, and, additionally or alternatively to contactingmaterials in the grinding apparatus, reduced size particles can be contacted with exogenous carbon dioxide while the particles are transported to a grinding vessel. Such contact may be the result of using carbon dioxide as part or all of a gas used to fluidize the reduced-sizer particles, as described herein.

[0086] Compositions comprising solid cementitious material can be any suitable composition, as described herein. In certain embodiments, a composition comprising solid cementitious material comprises Portland cement, e.g., Portland cement clinker. Additionally or alternatively, solid cementitious material can comprise one or more non-Portland cement components, such as those disclosed herein, such as one or more additional cementitious materials, one or more supplementary cementitious materials (SCM), and / or one more alternative supplementary cementitious materials (ASCM), for example limestone, silica fume, natural pozzolans, calcined clay, biomass ashes, fly ash, and / or slag. The composition comprising cementitious material can further comprises one or more additional substances, such as gypsum, one or more grinding aids, and any other suitable material. In certain embodiments, the composition comprises gypsum.

[0087] Exogenous carbon dioxide (CO2) contacted with a composition comprising cementitious material and / or reduced size particles of the composition in any suitable form. Forms of carbon dioxide are described further herein. In certain embodiments, the carbon dioxide comprises solid carbon dioxide, gaseous carbon dioxide, or combinations thereof. In certain embodiments the carbon dioxide comprises solid carbon dioxide. In certain embodiments, the carbon dioxide comprises gaseous carbon dioxide. In certain embodiments, the carbon dioxide comprises gaseous and solid carbon dioxide. Any suitable source of carbon dioxide can be used, such as a source as disclosed herein, for example carbon dioxide derived from calcining limestone and / or carbon dioxide captured directly from air, e.g., direct air capture (DAC) or carbon dioxide produced in biogenic processes. In certain embodiments, the method further comprises introducing exogenous carbon dioxide into a grinding apparatus, during transport of reduced-size particles to a cooling vessel, and / or into the cooling vessel.

[0088] Gaseous carbon dioxide is taken up by water to produce aqueous carbon dioxide and / or carbon dioxide derivatives (e.g., bicarbonate or carbonate), and contacted with the solid cementitious material and / or reduced-size particles, and reacts with one or more components of these to produce carbonated material, such as a carbonate, e.g., calcium carbonate. The fate of the carbonated material, e.g., calcium carbonate, is as described further herein; in certain embodiments, calcium carbonate produced by the method canreplace a portion of quarried limestone that would otherwise be used in the grinding process, in amounts / proportions as described herein. The level of carbonation, expressed as wt% of the solid cementitious material, e.g., as weight percent of Portland cement clinker, can be any level as described herein.

[0089] One or more characteristics of treatment of the composition comprising cementitious material in the apparatus to reduce size of the particles, transport of the reduced- size particles to e.g., a storage vessel and / or cooling apparatus, in the storage and / or cooling vessel, or any combination thereof, may be monitored, and the amount, rate of introduction, and / or form of the carbon dioxide adjusted based, at least in part, on the one or more characteristics. The one or more monitored characteristics can be measured using one or more sensors or manually entered by a used using a human machine interface (HMI). The one or more parameters include but are not limited to, feed rate of the particles, the amount of carbon dioxide delivered to the grinding apparatus, grinding rate, or the like. In certain embodiments, one or more sensors to monitor one or more characteristics send information to a processor, which processes the information and, based at least in part on the processed information, sends a signal to an actuator, such as a valve, to adjust flow of carbon dioxide.

[0090] In certain embodiments, provided herein is a method comprising treating a mixture of solid carbon dioxide and solid cementitious particles, e.g., a composition comprising solid cementitious parti, to reduce size of the particles. The solid carbon dioxide may be present in any suitable amount, e.g., at least 0.001, 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7, 8, or and / or not more than 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7 8, 9, orlO %by weight of particles of cementitious material, preferably 0.001- 10%, more preferably 0.01-5%, even more preferably 0.01-3%, still more preferably 0.2-3%, yet more preferably 0.2-2.5%. The composition comprising solid cementitious material may be any one of the compositions described herein; in certain embodiments, the composition comprises Portland cement, e.g., Portland cement clinker; i in certain embodiments, the composition does not comprise Portland cement, e.g., Portland cement clinker. The composition may comprise SCM and / or ASCM and / or other substances, as described herein. The method can be carried out in a container, e.g., a grinding apparatus. In certain embodiments the method includes introducing solid carbon dioxide into the container. Further aspects of methods for creating and treating mixtures of a composition comprising solid cementitious material and solid carbon dioxide are as described herein.

[0091] In certain embodiments, provided are methods to reduce an amount of quarried limestone used to produce a cement mix comprising (i) treating solid particles ofcementitious material comprising calcium to be used in the cement mix with exogenous carbon dioxide to produce calcium carbonate; and (ii) replacing at least a portion of the quarried limestone that would otherwise be used to produce the cement mix with the calcium carbonate. The treating of the solid particles of cementitious material comprising calcium with exogenous carbonation may be performed by any suitable method described herein. The calcium carbonate produced from the carbonation process may provide improved properties or other aspects of the cement mix, e.g., increasing the Blaine fineness of cement, which can, e.g., save energy consumption. Calcium carbonate produced in the method allows for less quarried limestone to be added for intergrinding, thus replacing at least a portion of the quarried limestone and reducing the amount used, compared to a process without carbonation. In certain embodiments, at least 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, or 90% and / or 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, 90, or 95% of quarried limestone in the cement mix is replaced with the calcium carbonate, preferably 0.1- 95%, more preferably 0.1-50%, even more preferably 0.1-40%, still more preferably 0.1- 30%, yet more preferably 0.1-25%, still yet more preferably 0.5-25%. Thus, also provided herein is a cement mix composition comprising calcium carbonate, wherein 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, or 90% and / or 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, 90, or 95% of the calcium carbonate comprises calcium carbonate produced by a method as disclosed herein.Compositions

[0092] In certain embodiments, provided herein are compositions,

[0093] In certain embodiments, provided is a composition comprising a plurality of particles of cementitious material mixed with intermixed with particles of solid carbon dioxide. In certain embodiments, the composition comprises at least 80, 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, or 98 and / or not more than 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 wt% particles of solid cementitious material and at least 0.1, 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, or 10.0, and / or not more than 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 12.0, or 15% wt% carbon dioxide. The particles of solid cementitious material can be any suitable size. In certain embodiments, the particles of solid cementitious material are 1 um to 25 mm mean diameter. The solid cementitious material can be any suitable cementitious material. In certain embodiments, thesolid cementitious material comprises one or more calcium compounds, for example a calcium oxide compound, a calcium silicate compound, such as tricalcium silicate (C3S), dicalcium silicate (C2S), tricalcium aluminate (C3A), tetracalcium aluminoferrite (C4AF), and combinations thereof. In certain embodiments, the cementitious material comprises Portland cement and / or Portland cement clinker. In certain embodiments, the particles of the composition comprising cementitious material comprise Portland cement clinker. Particles of the composition can comprise one or more additional components. Additional components, such as cementitious materials, supplementary cementitious materials (SCMs), and / or alternative supplementary materials (ASCMs) that can be present in particles of the composition include gypsum (e.g., calcium sulfate), limestone (e.g., calcium carbonate), fly ash, slag, silica fume, natural pozzolans, calcined clay, biomass ashes, or combinations thereof. This list is not intended to be limiting and, as such, the composition may comprise any suitable alternative. Gypsum may be present in the composition. Quarried limestone in an amount up to 15 wt% may be present. SCM, such as an SCM as described herein, may be present, e.g., one or more of fly ash in an amount up to 30 wt %, slag in an amount up to 70 wt%, and / or silica fume in an amount up to 10 wt%.

[0094] In certain embodiments, provided herein is a composition comprising a plurality of particles comprising solid cementitious material comprising hydraulic cement and one or more products of reaction of the hydraulic cement with carbon dioxide or aqueous derivatives of carbon dioxide. In certain embodiments, the products of reaction are present on an outer surface of the particles. The products of reaction may comprise one or more carbonate compounds, such as one or more bicarbonates and / or carbonates, for example a metal bicarbonate and / or metal carbonate, such as calcium carbonate.

[0095] In certain embodiments, provided is a composition comprising particles of one or more cementitious materials, e.g., a hydraulic cement, such as Portland cement, and / or other suitable cementitious material, such as SCM and / or ASCM, as described herein, wherein at least 50, 60, 70, 80, 90, or 95% of the particles have a mean diameter of 1 um-50 um, and calcium carbonate particles, wherein at least 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 22, 25, 27, 30, 35, 40, 50, 60, 70, 80, or 90% and or not more than 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 22, 25, 27, 30, 35, 40, 50, 60, 70, 80, 90, 95, or 100% of the calcium carbonate particles preferably 0.5-50%, more preferably 0.5-40%, even more preferably 0.5 — 30%, still more preferably 0.5-25%, yet more preferably 0.5-20% have a mean diameter of less than 10 um, preferably less than 5 um, more preferably less than 3um, even more preferably less than 2 um, still more preferably less than 1 um, yet more preferably less than 0.5 um. Theparticles of calcium carbonate with the recited mean diameters may be present in the composition in an amount of at least 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, or 20% and or not more than 0.2, 0.5, 0.7, 1, 1.2, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, or 25% by weight, preferably 0.1-25%, more preferably 0.1-15%, even more preferably 0.1-10%, yet more preferably 0.1-5%, still more preferably 0.1-3%. The calcium carbonate can be calcium carbonate produced by one or more of the methods provided herein. The calcium carbonate is not calcium carbonate produced from extreme grinding of limestone.Apparatus

[0096] In certain embodiments, provided herein is an apparatus comprising: (i) one or more of: 1) an apparatus configured to reduce size of particles of cementitious material to produce reduced-size particles of cementitious material; 2) a classifier to classify the one or more reduced-size particles (if not part of the apparatus configured to reduce size of particles of cementitious material); 3) one or more transport systems to transport the reduced-size particles, e.g., a pneumatic system or a mechanical system (e.g., airslide); 4) one or more vessels to contain the reduced-size particles, such as a storage vessel and / or a cooling vessel; and / or 5) a blending vessel to blend the reduced-size particles with other materials; and (ii) one or more delivery systems to deliver gaseous and / or solid carbon dioxide to the one or more apparatuses of (i). The apparatus can further comprise (iii) a carbon dioxide preparation system configured to produce the gaseous and / or solid carbon dioxide, such as a system to deliver solid carbon dioxide. The system can further comprise a container comprising carbon dioxide, such as a container comprising liquid carbon dioxide. In certain embodiments the carbon dioxide preparation system comprises a source of liquid carbon dioxide operably connected to an orifice which receives the liquid carbon dioxide and releases it to atmospheric or near-atmospheric pressure, to produce solid an gaseous carbon dioxide. The apparatus configured to reduce the size of the particles can be a grinding apparatus, such as a grinding apparatus as described herein. The apparatus can further comprise a controller, such as a controller comprising one or more sensors to monitor one or more characteristics of the apparatus or process occurring in the apparatus, which sends information to a processor, which processes the information and, based at least in part on the processing, sends a signal to one or more actuators to control delivery of carbon dioxide into the system.EXAMPLESExample 1

[0097] In this Example, CO2 treatment in a grinding mill was simulated using a small- scale ball mill connected to a gaseous CO2 line and a water addition port.

[0098] Anhydrous cement samples were treated using abundance of CO2 for fixed duration and moisture content. The steps were as follows.1. Add around 10 kg of anhydrous cement to the ball mill and seal the hatch.2. Hook the temperature and humidity logger inside of the drum3. Start rotating the drum.4. While the drum is rotating, add the required amount of water to the side port.5. Allow the water and cement to mix for 1 minute6. Inject CO2 to the drum through the connected CO2 line7. Mix for the determined duration of time8. Remove samples and the data logger from the drum.9. Dry samples in a nitrogen environment.10. Conduct tests on removed samples.

[0099] The untreated and treated samples were run through a carbon analyzer and thermogravimetric analyzer (TGA) to determine their CO2 uptake and prehydration levels.

[0100] The test matrix employed in Experiment 1 is shown in Table 1.TABLE 1 Example 1 Matrix

[0101] As shown in Figs. 1 and 2, the temperature change from Experiment 1 can be summarized as follows: Reference samples (no CO2 treatment) did not show any change intemperature, as expected. At 1 % moisture, the temperature change during the CO2 treatment was not significant for both the treatment duration of 5 minutes and 10 minutes. At 3% and 5% moisture, the temperature kept on increasing during both the treatment duration of 5 minutes and 10 minutes.

[0102] These results suggest that moisture content of cement / clinker should be more than 1% for the CO2 mineralization reaction to occur.

[0103] As shown in Table 2, the results from Carbon analysis and TGA can be summarized as follows: CO2 uptake of treated samples was calculated considering the CO2 level of reference samples as the baseline. CO2 uptake values determined by carbon analysis and TGA do not match, however, they show the same trend with increasing treatment duration and moisture content. At 1% moisture, although the temperature change was negligible, the measurements still showed around 1% CO2 uptake. For the same treatment duration (5 min and 10 min), CO2 uptake increased with increasing moisture content. For the same moisture content (1%, 3%, and 5%), increasing the treatment duration from 5 to 10 minutes also increased the CO2 uptake

[0104] Considering both the parameters (treatment duration and moisture content), the higher their values the higher was the CO2 uptake as well as the loss-on-ignition (LOI)

[0105] Increasing LOI suggest corresponding increments in the hydration of cement.TABLE 2CO2 uptake results from Example 1

[0106] Overall, the results from this experiment indicated a feasibility of CO2 mineralization in a grinding mill, given the moisture content is higher than 1%.Example 2

[0107] In Example 2, carbon dioxide uptake was assessed when the temperature of the cement sample is close to that in a cement grinding mill.

[0108] The ball mill of Example 1 was employed for this experiment; it was connected to a gaseous CO2 line and a water addition port.

[0109] Anhydrous cement samples were preheated in an oven before being treated using abundance of CO2 for fixed duration and moisture content. The steps were as follows.1. Preheat around 10 Kg of anhydrous cement in the oven at 110 °C2. Determine the actual sample temperature before adding to the mill3. Add the preheated anhydrous cement sample to the ball mill and seal the hatch.4. Hook the temperature and humidity logger inside of the drum5. Start rotating the drum.6. While the drum is rotating, add the required amount of water to the side port.7. Allow the water and cement to mix for 1 minute8. Inject CO2 to the drum through the connected CO2 line9. Mix for the determined duration of time10. Remove samples and the data logger from the drum.11. Dry samples in a nitrogen environment.12. Conduct tests on removed samples.

[0110] The untreated and treated samples were run through a carbon analyzer and thermogravimetric analyzer (TGA) to determine their CO2 uptake and prehydration levels.

[0111] The test matrix employed in Example 2 is shown in Table 3.Table 3.Example 2 (Preheated Sample) Matrix

[0112] As shown in Figs. 3 and 4, the temperature change from Experiment 2 can be summarized as follows: Reference samples (no CO2 treatment) did not show any significant change in temperature, as expected. At 0 % moisture (fully dried sample), the temperature change during the CO2 treatment was not significant for both the treatment duration of 2 minutes and 5 minutes. At 3% moisture, the temperature kept on increasing during both the treatment duration of 2 minutes and 5 minutes

[0113] These results suggest that CO2 mineralization cannot occur in a fully dried sample, however, with some moisture (3%) the reaction can occur even in samples at 100- 110 C.

[0114] The results from Carbon analysis and TGA (Table 3, below) can be summarized as follows: CO2 uptake of treated samples was calculated considering the CO2 level of reference samples as the baseline. CO2 uptake values determined by carbon analysis and TGA did not match for 0% moisture samples while they did show comparable values for 3% moisture samples. For the same moisture content (3%), increasing the treatment duration from 2 to 5 minutes also increased the CO2 uptake. Considering both the parameters (treatment duration and moisture content), the higher their values the higher was the CO2 uptake. As observed in Example 1, this experiment also showed increase in the loss-on- ignition (LOI) with increasing moisture content and treatment duration, suggesting higher prehydration levels.Table 4.CO2 uptake results from Example 2 (Preheated Sample)

[0115] Overall, the results from Example 2 indicated a feasibility of CO2 mineralization in a grinding mill even when the temperature of the clinker / cement is 100-110 C, given the moisture content is higher than 1%.Example 3

[0116] In this Example cement samples were preheated to 100-110 °C and the impact of treatment on chemical composition of cement was assessed.

[0117] Around 10 Kg of anhydrous cement samples was preheated in an oven to 110 °C. Thereafter, the same test procedure as employed in Example 2 was implemented. The samples were treated in the ball mill for fixed duration (5 minutes) and the moisture content was varied (3% and 5% by weight of cement sample). Conditions were as shown in Table 5:Table 5.

[0118] The untreated and treated samples were run through a carbon analyzer and thermogravimetric analyzer (TGA) to determine their CO2 uptake and prehydration levels.

[0119] Figure 5 shows the temperature change that occurred during the course of Example 3. The reference samples, which were not subjected to the CO2 treatment, demonstrated no significant temperature variations, as expected and seen in earlier Examples. When the sample had a 3% moisture content and was subjected to a 3-minute CO2 treatment, the temperature remained relatively stable, with the difference between the two curves being negligible compared to the reference sample. When the sample was subjected to a 5-minute CO2 treatment while all other conditions remained the same, the curve for the CO2 -treated sample showed a slow but noticeable increase compared to the reference sample.

[0120] The data implies that for the sample with a 3-minute CO2 exposure, temperature increase occurs at a barely negligible level, but when the exposure time is extended to 5 minutes under the same conditions, there is a distinguishable increase in temperature, as shown in Fig. 5.

[0121] As shown in Table 6, the results from Carbon analysis and TGA can be summarized as follows: As observed in Experiment 1 and 2, this experiment also showed an increase in the loss-on-ignition (LOI) with increasing moisture content, suggesting higherprehydration levels. For the same treatment duration (5 min), increasing the moisture content from 3 to 5% also increased the CO2 uptake.Table 6.CO2 uptake results from Experiment 3 (Preheated Sample)

[0122] An X-ray fluorescence (XRF) analysis was performed on the four samples to determine the impact of CO2 treatment on the chemical composition of cement. The results from the XRF analysis are shown in Table 7. These results indicate that the cement samples subjected to different moisture and CO2 treatment conditions do not have any significant impact on the major cement oxides such as SiCh, AI2O3, CaO, and SO3. This further suggests that the cement can be used as-is in various applications with the same performance even after CO2 addition.Table 7. Chemical composition of untreated and CO2 -added cementExample 4

[0123] In this Example, cement samples were preheated to 100-110 °C and the impact of CO2 addition on the compressive strength of mortar prepared using the cement was assessed.

[0124] Conditions were as shown in Table 8:Table 8.

[0125] Around 10 Kg of anhydrous cement samples was preheated in an oven to 110 °C. Thereafter, the same test procedure as employed in Example 2 was implemented. The samples were treated in the ball mill for fixed duration (5 minutes) and the moisture content was varied (0.5% and 1.0% by weight of cement sample).

[0126] All four cement samples (reference and treated) were then used to make mortar following ASTM Cl 09 standard procedure. The mortar mix proportion is shown in Table 9Table 9.

[0127] Mortar samples were tested for flowability following ASTM C230 standard test procedure and compressive strength was tested at 7 day and 28 day as per ASTM Cl 09 standard test procedure. As shown in Table 10, CO2 treatment at both moisture contents of 0.5% and 1.0% did not have any significant impact on the flowability as well as the compressive strength of mortar.TABLE 10.Effect of CO2 treatment on the flowability and compressive strength of cement mortarEmbodiments

[0128] In embodiment 1, provided is method comprising contacting particles of a composition comprising solid cementitious material with exogenous carbon dioxide (i) while the particles are treated in an apparatus to reduce the size of the particles to produce reduced- size particles; (ii) during classification of the reduced-sized particles; (iii) while the reducedsized particles are transported, e.g., by pneumatic pump or by airslide; (iv) in a vessel containing reduced-size particles, e.g., a storage vessel or a cooling vessel, or any combination thereof. In embodiment 2, provided is the method of embodiment 1 wherein the method comprises contacting the particles of a composition comprising solid cementitious material with exogenous carbon dioxide while the particles are treated to reduce the size of the particles to produce reduced-size particles. In embodiment 3, provided is the method of embodiment 1 or 2 wherein the method comprises contacting the reduced-size particles with carbon dioxide while the reduced-sized particles are transported. In embodiment 4, provided is the method of any one of embodiments 1 through 3 wherein the method comprises contacting the reduced-size particles with carbon dioxide while the reduced-sized particles are in a vessel comprising the reduced-size particles, such as a storage vessel or a cooling vessel. In embodiment 5 , provided is the method of any previous embodiment wherein the solid cementitious material comprises Portland cement. In embodiment 6 , provided is the method of embodiment 5 wherein the Portland cement comprises Portland cement clinker. In embodiment 7 , provided is the method of any previous embodiment wherein the solid cementitious material comprises supplementary cementitious material (SCM) and / or alternative supplementary cementitious material (ASCM). In embodiment 8 , provided is the method of embodiment 6 wherein the SCM comprises quarried limestone, fly ash, slag, silica fume, natural pozzolons, calcined clay, biomass ashes, or a combination thereof. In embodiment 9 , provided is the method of any previous embodiment wherein the composition comprising cementitious material further comprises gypsum. In embodiment 10 , provided isthe method of any previous embodiment wherein the carbon dioxide comprises gaseous carbon dioxide. In embodiment 11 , provided is the method of embodiment 10 wherein at least part of the gaseous carbon dioxide is produced from particles of solid carbon dioxide that sublimate to produce the gaseous carbon dioxide. In embodiment 12, provided is the method of any previous embodiment wherein the carbon dioxide comprises carbon dioxide derived from calcining limestone, from direct air capture (DAC), from biogenic sources such as biogas production, or a combination thereof. In embodiment 13, provided is the method of nay previous embodiment further comprising introducing the carbon dioxide into the apparatus to reduce the size of the particles to produce reduced-size particles. In embodiment14, provided is the method of any previous embodiment wherein the apparatus to reduce the size of the particles to produce reduced-size particles is a grinding apparatus. In embodiment15, provided is the method of embodiment 14 wherein the grinding apparatus is a vertical grinding apparatus. In embodiment 16, provided is the method of embodiment 15 wherein the vertical grinding apparatus is a vertical roller mill or vertical shaft mill. In embodiment 17, provided is the method of embodiment 14 wherein the apparatus is a horizontal grinding apparatus. In embodiment 18, provided is the method of embodiment 17 wherein the horizontal grinding apparatus is a horizontal ball mill or a horizontal roller mill. In embodiment 19, provided is the method of any previous embodiment wherein the gaseous carbon dioxide is taken up by water that is contacted with the solid cementitious material and / or reduced-size particles to produce aqueous carbon dioxide and / or carbon dioxide derivatives, and the aqueous carbon dioxide and / or carbon dioxide derivatives contacts the particles of solid cementitious material and / or reduced-size particles. In embodiment 20, provided is the method of embodiment 19 wherein the aqueous carbon dioxide and / or carbon dioxide derivatives react with one or more components of the particles of cementitious material and / or reduced size particles to produce carbonated material. In embodiment 21, provided is the method of embodiment 20 wherein the carbonated material comprises calcium carbonate. In embodiment 22, provided is the method of embodiment 20 or 21 wherein the carbonated material is separated from the particles. In embodiment 23, provided is the method of embodiment 21 or 22 wherein the calcium carbonate replaces at least a portion of quarried limestone in a cement mix produced from the reduced-size cementitious particles. In embodiment 24, provided is the method of embodiment 23 wherein at least 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, or 90% and / or 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, 90, or 95% of quarried limestone in the cement mix is replaced with the calciumcarbonate, preferably 0.1-95%, more preferably 0.1-50%, even more preferably 0.1-40%, still more preferably 0.1-30%, yet more preferably 0.1-25%, still yet more preferably 0.5-25%. In embodiment 25, provided is the method of any one of embodiments 20 through 24 wherein the carbonated material produced comprises at least 0.001, 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7, 8, or and / or not more than 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7 8, 9, orlO % by weight of particles of cementitious material, preferably 0.001- 10%, more preferably 0.01-5%, even more preferably 0.2-6%, still more preferably 0.5-5%, yet more preferably 0.5-4%. In embodiment 26, provided is the method of any previous embodiment further comprising monitoring one or more characteristics of the method and adjusting an amount of carbon dioxide delivered to the apparatus to produce reduced-size particles, the transport apparatus, and / or the cooling vesselbased on the one or more characteristics.

[0129] In embodiment 27, provided is a method comprising treating a mixture of solid cementitious particles and solid carbon dioxide to reduce the size of the solid cementitious particles. In embodiment 28, provided is the method of embodiment 27 further comprising carbonating material of the solid cementitious particles to produce carbonated material. In embodiment 29, provided is the method of embodiment 27 or 28 wherein the solid carbon dioxide comprises at least 0.001, 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7, 8, or and / or not more than 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7 8, 9, orlO % by weight of particles of cementitious material, preferably 0.001- 10%, more preferably 0.01-5%, even more preferably 0.01-3%, still more preferably 0.2-3%, yet more preferably 0.2-2.5%. In embodiment 30, provided is the method of any one of embodiments 27 through 29 wherein the solid cementitious material comprises Portland cement. In embodiment 31, provided is the method of embodiment 30 wherein the Portland cement comprises Portland cement clinker. In embodiment 32, provided is the method of any one of embodiments 27 through 31 wherein the solid cementitious material comprises supplementary cementitious material (SCM) and / or alternative supplementary cementitious material (ASCM). In embodiment 33, provided is the method of embodiment 32 wherein the SCM comprises quarried limestone, fly ash, slag, silica fume, natural pozzolons, calcined clay, biomass ashes, or a combination thereof. In embodiment 34, provided is the method of any one of embodiments 27 through 33 wherein the composition comprising cementitious material further comprises gypsum. In embodiment 35, provided is the method of any one of embodiments 27 through 34 wherein the method is carried out in a container. In embodiment36, provided is the method of any one of embodiments 27 through 35 further comprising introducing the solid carbon dioxide into the container.

[0130] In embodiment 37, provided is a method to reduce an amount of quarried limestone used to produce a cement mix comprising(i) treating solid particles of cementitious material comprising calcium to be used in the cement mix with exogenous carbon dioxide to produce calcium carbonate; and (ii) replacing at least a portion of the quarried limestone that would otherwise be used to produce the cement mix with the calcium carbonate. In embodiment 38, provided is the method of embodiment 37 wherein at least 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, or 90% and / or 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, 90, or 95% of quarried limestone in the cement mix is replaced with the calcium carbonate, preferably 0.1-95%, more preferably 0.1-50%, even more preferably 0.1-40%, still more preferably 0.1-30%, yet more preferably 0.1-25%, still yet more preferably 0.5-25%.

[0131] In embodiment 39, provided is an apparatus comprising (i) an apparatus configured to reduce size of particles of cementitious material to produce reduced-size particles of cementitious material; and (ii) a delivery system to deliver gaseous and / or solid carbon dioxide into the apparatus configured to reduce size of particles of cementitious material. In embodiment 40, provided is the apparatus of embodiment 39 further comprising (iii) a carbon dioxide preparation system configured to produce the gaseous and / or solid carbon dioxide. In embodiment 41, provided is the apparatus of embodiment 39 or 40 wherein the delivery system delivers solid carbon dioxide into the apparatus. In embodiment 42, provided is the apparatus of embodiment 41 wherein the carbon dioxide preparation system comprises a source of liquid carbon dioxide operably connected to an orifice which receives the liquid carbon dioxide and releases it to atmospheric or near-atmospheric pressure, to produce solid and gaseous carbon dioxide. In embodiment 43, provided is the apparatus of any one of embodiments 39 through 42 wherein the apparatus configured to reduce size is a grinding mill. In embodiment 44, provided is the apparatus of embodiment 43 wherein the grinding mill is a vertical mill, e.g., a vertical roller mill. In embodiment 45, provided is the apparatus of embodiment 43 wherein the grinding mill is a horizontal mill, e.g. a horizontal ball mill. In embodiment 46, provided is the apparatus of any one of embodiments 39 through 45 further comprising a transport system to transport the reduced- size particles from the apparatus to produce the reduced-size particles to a cooling vessel and / or the cooling vessel. In embodiment 47, provided is the apparatus of embodiment 46 further comprising a system to deliver gaseous carbon dioxide to the transport system and / orthe cooling vessel. In embodiment 48, provided is the apparatus of any one of embodiments 39 through 47 further comprising a controller.

[0132] In embodiment 49, provided is an apparatus comprising (i) a transportation apparatus configured to transport reduced-size cementitious particles produced in an apparatus configured to reduce size of cementitious particles to produce reduced-size cementitious particles from one area to another area; and (ii) a delivery system to deliver carbon dioxide into the transportation apparatus to contact the reduced-size particles with carbon dioxide. In embodiment 50, provided is the apparatus of embodiment 49 wherein the carbon dioxide comprises gaseous carbon dioxide.

[0133] In embodiment 51, provided is an apparatus comprising (i) a cooling vessel configured to cool reduced-size cementitious particles produced in an apparatus configured to reduce size of cementitious particles to produce the reduced-size cementitious particles; and (ii) a delivery system to deliver carbon dioxide into the transportation apparatus to contact the reduced-size particles with carbon dioxide. In embodiment 52, provided is the apparatus of embodiment 52 wherein the carbon dioxide comprises gaseous carbon dioxide.

[0134] In embodiment 53, provided is a composition comprising a plurality of particles of solid cementitious material intermixed with particles of solid carbon dioxide . In embodiment 54, provided is the composition of embodiment 53 further comprising gaseous carbon dioxide. In embodiment 55, provided is the composition of embodiment 53 or 54 further comprising a clinker grinding aid. In embodiment 56, provided is the composition of any one of embodiments 53 through 55 further comprising solid gypsum. In embodiment 57, provided is the composition of any one of embodiments 53 through 56 further comprising limestone. In embodiment 58, provided is the composition of any one of embodiments 53 through 57 wherein the cementitious material comprises a hydraulic cement. In embodiment 59, provided is the composition of embodiment 58 wherein the cementitious material comprises Portland cement. In embodiment 60, provided is the composition of any one of embodiments 53 through 59 wherein the solid cementitious material comprises supplementary cementitious material (SCM) and / or alternative supplementary cementitious material (ASCM). In embodiment 61, provided is the composition of embodiment 60 wherein the SCM comprises quarried limestone, fly ash, slag, silica fume, natural pozzolons, calcined clay, biomass ashes, or a combination thereof. In embodiment 62, provided is the composition of any one of embodiments 53 through 61 comprising at least 80, 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, or 98 and / or not more than 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 wt% particles of solid cementitious material and at least 0.1, 0.2,0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, or 10.0, and / or not more than 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 12.0, or 15% wt% carbon dioxide. In embodiment 63, provided is the composition of any one of embodiments 53 through 62 wherein the particles of solid cementitious material are 1 um-25 mm mean diameter.

[0135] In embodiment 64, provided is a composition comprising a plurality of solid particles of hydraulic cement, wherein the particles comprise products of reaction of the hydraulic cement with carbon dioxide or aqueous derivatives of carbon dioxide. In embodiment 65, provided is the composition of embodiment 64 wherein the products of reaction are present in an outer layer of the particles In embodiment 66, provided is the composition of embodiment 64 or 65 wherein the particles are 1-25 um mean diameter. In embodiment 67, provided is the composition of any one of embodiments 64 through 66 wherein the reaction products comprise one or more bicarbonates and / or carbonates. In embodiment 68, provided is the composition of embodiment 67 wherein the carbonates comprise calcium carbonate.Equivalents

[0136] Throughout the description, where compositions are described as having, including, or comprising specific components, or where processes and methods are described as having, including, or comprising specific steps, it is contemplated that, additionally, there are compositions of the present invention that consist essentially of, or consist of, the recited components, and that there are processes and methods according to the present invention that consist essentially of, or consist of, the recited processing steps.

[0137] In the application, where an element or component is said to be included in and / or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components.

[0138] Further, it should be understood that elements and / or features of a composition or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present invention, whether explicit or implicit herein. For example, where reference is made to a particular compound, that compound can be used in various embodiments of compositions of the present invention and / or in methods of the present invention, unless otherwise understood from the context. In other words, within this application, embodiments have been described and depicted in a way that enables a clear andconcise application to be written and drawn, but it is intended and will be appreciated that embodiments may be variously combined or separated without parting from the present teachings and invention(s). For example, it will be appreciated that all features described and depicted herein can be applicable to all aspects of the invention(s) described and depicted herein.

[0139] The terms “a” and “an” and “the” and similar references in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. For example, the term “a cell” includes a plurality of cells, including mixtures thereof. Where the plural form is used for compounds, salts, or the like, this is taken to mean also a single compound, salt, or the like.

[0140] It should be understood that the expression “at least one of’ includes individually each of the recited objects after the expression and the various combinations of two or more of the recited objects unless otherwise understood from the context and use. The expression “and / or” in connection with three or more recited objects should be understood to have the same meaning unless otherwise understood from the context.

[0141] The use of the term “include,” “includes,” “including,” “have,” “has,” “having,” “contain,” “contains,” or “containing,” including grammatical equivalents thereof, should be understood generally as open-ended and non-limiting, for example, not excluding additional unrecited elements or steps, unless otherwise specifically stated or understood from the context.

[0142] Where the use of the term “about” is before a quantitative value, the present invention also includes the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term “about” refers to a ±10% variation from the nominal value unless otherwise indicated or inferred.

[0143] It should be understood that the order of steps or order for performing certain actions is immaterial so long as the present invention remain operable. Moreover, two or more steps or actions may be conducted simultaneously.

[0144] The use of any and all examples, or exemplary language herein, for example, “such as” or “including,” is intended merely to illustrate better the present invention and does not pose a limitation on the scope of the invention unless claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the present invention.

[0145] The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The foregoing embodiments are therefore to be considered in all respects illustrative rather than limiting on the invention described herein.Scope of the invention is thus indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.

Claims

CLAIMSWHAT IS CLAIMED IS:

1. A method comprising contacting particles of a composition comprising solid cementitious material with exogenous carbon dioxide(i) while the particles are treated in an apparatus to reduce the size of the particles to produce reduced-size particles;(ii) during classification of the reduced-sized particles;(iii) while the reduced-sized particles are transported, e.g., by pneumatic pump or by airslide;(iii) in a vessel containing reduced-size particles, e.g., a storage vessel or a cooling vessel, or any combination thereof.

2. The method of claim 1 wherein the method comprises contacting the particles of a composition comprising solid cementitious material with exogenous carbon dioxide while the particles are treated to reduce the size of the particles to produce reduced-size particles.

3. The method of claim 1 or 2 wherein the method comprises contacting the reduced-size particles with carbon dioxide while the reduced-sized particles are transported.

4. The method of any one of claims 1 through 3 wherein the method comprises contacting the reduced-size particles with carbon dioxide in a vessel containing reduced-size particles, e.g., a storage vessel or a cooling vessel.

5. The method of any previous claim wherein the solid cementitious material comprises Portland cement.

6. The method of claim 5 wherein the Portland cement comprises Portland cement clinker.

7. The method of any previous claim wherein the solid cementitious material comprises supplementary cementitious material (SCM) and / or alternative supplementary cementitious material (ASCM).

8. The method of claim 6 wherein the SCM comprises quarried limestone, fly ash, slag, silica fume, natural pozzolons, calcined clay, biomass ashes, or a combination thereof.

9. The method of any previous claim wherein the composition comprising cementitious material further comprises gypsum.

10. The method of any previous claim wherein the carbon dioxide comprises gaseous carbon dioxide.

11. The method of claim 10 wherein at least part of the gaseous carbon dioxide is produced from particles of solid carbon dioxide that sublimate to produce the gaseous carbon dioxide.

12. The method of any previous claim wherein the carbon dioxide comprises carbon dioxide derived from calcining limestone, from direct air capture (DAC), from biogenic sources such as biogas production, or a combination thereof.

13. The method of any previous claim further comprising introducing the carbon dioxide into the apparatus to reduce the size of the particles to produce reduced-size particles.

14. The method of any previous claim wherein the apparatus to reduce the size of the particles to produce reduced-size particles is a grinding apparatus.

15. The method of claim 14 wherein the grinding apparatus is a vertical grinding apparatus.

16. The method of claim 15 wherein the vertical grinding apparatus is a vertical roller mill or vertical shaft mill.

17. The method of claim 14 wherein the apparatus is a horizontal grinding apparatus.

18. The method of claim 17 wherein the horizontal grinding apparatus is a horizontal ball mill or a horizontal roller mill.

19. The method of any previous claim wherein the gaseous carbon dioxide is taken up by water that is contacted with the solid cementitious material and / or reduced-size particles to produce aqueous carbon dioxide and / or carbon dioxide derivatives, and the aqueous carbon dioxide and / or carbon dioxide derivatives contacts the particles of solid cementitious material and / or reduced-size particles.

20. The method of claim 19 wherein the aqueous carbon dioxide and / or carbon dioxide derivatives react with one or more components of the particles of cementitious material and / or reduced size particles to produce carbonated material.

21. The method of claim 20 wherein the carbonated material comprises calcium carbonate.

22. The method of claim 20 or 21 wherein the carbonated material is separated from the particles.

23. The method of claim 21 or 22 wherein the calcium carbonate replaces at least a portion of quarried limestone in a cement mix produced from the reduced-size cementitious particles.

24. The method of claim 23 wherein at least 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, or 90% and / or 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, 90, or 95% of quarried limestone in the cement mix is replaced with the calcium carbonate, preferably 0.1-95%, more preferably 0.1-50%, even more preferably 0.1-40%, still more preferably 0.1-30%, yet more preferably 0.1-25%, still yet more preferably 0.5-25%.

25. The method of any one of claims 20 through 24 wherein the carbonated material produced comprises at least 0.001, 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7, 8, or and / or not more than 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7 8, 9, orlO %by weight of particles of cementitious material, preferably 0.001- 10%, more preferably 0.01-5%, even more preferably 0.2-6%, still more preferably 0.5-5%, yet more preferably 0.5-4%.

26. The method of any previous claim further comprising monitoring one or more characteristics of the method and adjusting an amount of carbon dioxide delivered to the apparatus to produce reduced-size particles, the transport apparatus, and / or the cooling vesselbased on the one or more characteristics.

27. A method comprising treating a mixture of solid cementitious particles and solid carbon dioxide to reduce the size of the solid cementitious particles.

28. The method of claim 27 further comprising carbonating material of the solid cementitious particles to produce carbonated material.

29. The method of claim 27 or 28 wherein the solid carbon dioxide comprises at least 0.001, 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7, 8, or and / or not more than 0.01, 0.1, 0.2, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2.0, 2.2, 2.5, 2.7, 3, 4, 5, 6, 7 8, 9, orlO %by weight of particles of cementitious material, preferably 0.001- 10%, more preferably 0.01-5%, even more preferably 0.01-3%, still more preferably 0.2-3%, yet more preferably 0.2-2.5%.

30. The method of any one of claims 27 through 29 wherein the solid cementitious material comprises Portland cement.

31. The method of claim 30 wherein the Portland cement comprises Portland cement clinker.

32. The method of any one of claims 27 through 31 wherein the solid cementitious material comprises supplementary cementitious material (SCM) and / or alternative supplementary cementitious material (ASCM).

33. The method of claim 32 wherein the SCM comprises quarried limestone, fly ash, slag, silica fume, natural pozzolons, calcined clay, biomass ashes, or a combination thereof.

34. The method of any one of claims 27 through 33 wherein the composition comprising cementitious material further comprises gypsum.

35. The method of any one of claims 27 through 34 wherein the method is carried out in a container.

36. The method of any one of claims 27 through 35 further comprising introducing the solid carbon dioxide into the container.

37. A method to reduce an amount of quarried limestone used to produce a cement mix comprising(i) treating solid particles of cementitious material comprising calcium to be used in the cement mix with exogenous carbon dioxide to produce calcium carbonate; and(ii) replacing at least a portion of the quarried limestone that would otherwise be used to produce the cement mix with the calcium carbonate.

38. The method of claim 37 wherein at least 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, or 90% and / or 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 30, 32, 35, 40, 45, 50, 60, 70, 80, 90, or 95% of quarried limestone in the cement mix is replaced with the calcium carbonate, preferably 0.1-95%, more preferably 0.1-50%, even more preferably 0.1-40%, still more preferably 0.1-30%, yet more preferably 0.1-25%, still yet more preferably 0.5-25%.

39. An apparatus comprising(i) an apparatus configured to reduce size of particles of cementitious material to produce reduced-size particles of cementitious material; and(ii) a delivery system to deliver gaseous and / or solid carbon dioxide into the apparatus configured to reduce size of particles of cementitious material.

40. The apparatus of claim 39 further comprising(iii) a carbon dioxide preparation system configured to produce the gaseous and / or solid carbon dioxide.

41. The apparatus of claim 39 or 40 wherein the delivery system delivers solid carbon dioxide into the apparatus.

42. The apparatus of claim 41 wherein the carbon dioxide preparation system comprises a source of liquid carbon dioxide operably connected to an orifice which receives the liquid carbon dioxide and releases it to atmospheric or near-atmospheric pressure, to produce solid an gaseous carbon dioxide.

43. The apparatus of any one of claims 39 through 42 wherein the apparatus configured to reduce size is a grinding mill.

44. The apparatus of claim 43 wherein the grinding mill is a vertical mill, e.g., a vertical roller mill.

45. The apparatus of claim 43 wherein the grinding mill is a horizontal mill, e.g. a horizontal ball mill.

46. The apparatus of any one of claims 39 through 45 further comprising a transport system to transport the reduced-size particles.

47. The apparatus of claim 46 further comprising a system to deliver gaseous carbon dioxide to the transport system.

48. The apparatus of any one of claims 39 through 47 further comprising a controller.

49. An apparatus comprising(i) a transportation apparatus configured to transport reduced-size cementitious particles produced in an apparatus configured to reduce size of cementitious particles to produce reduced-size cementitious particles from one area to another area; and(ii) a delivery system to deliver carbon dioxide into the transportation apparatus to contact the reduced-size particles with carbon dioxide.

50. The apparatus of claim 49 wherein the carbon dioxide comprises gaseous carbon dioxide.

51. An apparatus comprising(i) a vessel configured to contain reduced-size cementitious particles produced in an apparatus configured to reduce size of cementitious particles to produce the reduced-size cementitious particles; and(ii) a delivery system to deliver carbon dioxide into the transportation apparatus to contact the reduced-size particles in the vessel with carbon dioxide.

52. The apparatus of claim 1 wherein the carbon dioxide comprises gaseous carbon dioxide.

53. A composition comprising a plurality of particles of solid cementitious material intermixed with particles of solid carbon dioxide.

54. The composition of claim 53 further comprising gaseous carbon dioxide.

55. The composition of claim 53 or 54 further comprising a clinker grinding aid.

56. The composition of any one of claims 53 through 55 further comprising solid gypsum.

57. The composition of any one of claims 53 through 56 further comprising limestone.

58. The composition of any one of claims 53 through 57 wherein the cementitious material comprises a hydraulic cement.

59. The composition of claim 58 wherein the cementitious material comprises Portland cement.

60. The composition of any one of claims 53 through 59 wherein the solid cementitious material comprises supplementary cementitious material (SCM) and / or alternative supplementary cementitious material (ASCM).

61. The composition of claim 60 wherein the SCM comprises quarried limestone, fly ash, slag, silica fume, natural pozzolons, calcined clay, biomass ashes, or a combination thereof.

62. The composition of any one of claims 53 through 61 comprising at least 80, 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, or 98 and / or not more than 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 wt% particles of solid cementitious material and at least 0.1, 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, or 10.0, and / or not more than 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 12.0, or 15% wt% carbon dioxide.

63. The composition of any one of claims 53 through 62 wherein the particles of solid cementitious material are 1 um-25 mm mean diameter.

64. A composition comprising a plurality of solid particles of hydraulic cement, wherein the particles comprise products of reaction of the hydraulic cement with carbon dioxide or aqueous derivatives of carbon dioxide.

65. The composition of claim 64 wherein the products of reaction are present in an outer layer of the particles66. The composition of claim 64 or 65 wherein the particles are 1-25 um mean diameter.

67. The composition of any one of claims 64 through 66 wherein the reaction products comprise one or more bicarbonates and / or carbonates.

68. The composition of claim 67 wherein the carbonates comprise calcium carbonate.

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