CROSS-REFERENCE

[0001 | This application claims the benefit of U. S. Provisional Appl ication No.

61 /941 ,222, filed February 1 8, 2014, and of U. S. Provisional Application No. 62/096,01 8 tiled December 23, 201 4, both of which applications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

[0002] Building materials containing cementing material comprising calc ium or calc ium ions, e.g., hydraulic cement mixes, such as concrete mixes, are used in a multitude of compositions and procedures throughout the world. In addition, greenhouse gases such as carbon dioxide are a growing concern worldwide. There is a need for methods and compositions to contact building materials containing cementing materials comprising calcium or calc ium ions, e.g., hydraulic cement mixes with carbon dioxide and for hydraulic cement mixes containing incorporated carbon dioxide and carbonation products,

SUM MARY OF THE INVENTION

[0003] In one aspect the invention provides methods. In certain embodiments, the invention provides a method of carbonating concrete comprising i) pumping a wet concrete mix into a conduit at a pressure sufficient to move the concrete through the conduit at a desired rate; and, ii) introducing carbon dioxide into the condu it at a pressure at or above the pressure of i). In certain embodiments, the pressure is greater than 50 psi. In certain embodiments, the carbon dioxide is transported to the conduit in liquid form and released into the conduit under conditions whereby the carbon dioxide becomes gaseous and sol id in the conduit. In certain embodiments, the conduit provides a variable pressure down its length, for example, the variable pressure can be provided by the presence of at least one constricted section in the conduit, or the variable pressure can be provided by a plurality of constricted sections in the conduit which alternate with expanded sections, or the variable pressure can be provided by varying the rate of pumping of concrete into the conduit, or the variable pressure can be provided by pumping the concrete at a constant rate at the proximal end of the conduit and varying the size of an orifice at the distal end of the conduit. In certain embodiments, the method further comprises adding an admixture to the concrete to improve flowability, early strength, or both. In certain embodiments, the method further comprises determining one or more characteristics of the wet concrete mix, the conduit, or the area around the conduit, such temperature or carbon dioxide concentration. The rate of introduction of carbon dioxide can be adjusted based on the characteristic.

[0004| In another aspect, the invention provides compositions. In certain embodiments, the invention provides an apparatus for moving wet concrete m ix from a first area to a second area and adding carbon dioxide to the m ix comprising i) a container for holding mixed wet concrete in the first area; ii) a conduit operably connected to the container and extending to the second area; i ii) a system for providing pressure to the concrete to move it from the container, into the conduit at a proximal end of the conduit, and out of the conduit at a distal end into the second area; iv) a system for supplying carbon dioxide operably connected to the system of iii) or the conduit of ii) configured to introduce carbon dioxide under pressure to the mixed wet concrete so that the carbon dioxide mixes with the concrete passing through the conduit. In certain embodiments, the carbon dioxide is liquid carbon dioxide. In certain embodiments, the system for supplying carbon dioxide is configured to introduce the liquid carbon dioxide to the conduit in such a manner that the carbon dioxide becomes solid and gaseous carbon dioxide. In certain embod iments, the system for supplying carbon dioxide is configured to introduce the carbon dioxide at a pressure of at least 50 psi into the conduit. In certain embodiments, the conduit comprises at least one constricted area to decrease the pressure of the concrete/carbon dioxide mixture flowing through the constricted area. In certain embodiments, the conduit comprises a plural ity of constricted areas alternating with expanded areas to provide areas of alternating decreasing and increasing pressure to the concrete/carbon dioxide mixture flowing through the conduit. In certain embodiments, the system for providing pressure to the concrete is configured to provide variable pressure to the concrete as it is pumped through the conduit. In certain embodiments, the distal end of the conduit comprises an orifice or valve, wherein the orifice or valve is configured to provided a variable size so as to vary the pressure of the concrete/carbon dioxide mixture in the conduit. In certain embodiments, the apparatus further comprises a system for adding admixture to the wet concrete mix, wherein the system for adding adm ixture is operably connected to the container of i), the conduit of ii), or the system for provid ing pressure of i ii), or a combination thereof. In certain embodiments, the system for providing pressure comprises a boom pump, a line pump, or a skid or rai l pump. In certain embodiments, the apparatus further comprises a sensor for sensing a characteristic of the concrete mix, the conduit, or an area around the conduit, wherein the sensor is operably connected to the system for supplying carbon dioxide of iv), such as a sensor that detects carbon dioxide or temperature.

|0005] In certain embodiments the invention provides a conduit for transporting a wet concrete mixture from a first area to a second area, wherein the conduit comprises at least one constricted area so that the concrete flowing through the conduit experiences a reduced pressure as it flows through the restricted area. In certain embodiments, the conduit comprises a plural ity of restricted areas alternating with expanded areas so that the concrete flowing through the conduit experiences alternating reduced and increased pressures as it flows through the conduit.

[0006] In certain embodiments the invention provides a conduit for transporting a wet concrete mixture from a first area to a second area, wherein the conduit comprises a proximal end at the first area and a distal end at the second area, wherein the distal end of the conduit is configured to provide an orifice or valve for the exit of the concrete of variable size.

INCORPORATION BY REFERENCE

|0007] 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 individual ly indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] 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:

[0009] Figure 1 depicts an embodiment of a Venturi system for creating areas of alternating high and low pressure in a conduit carrying concrete and carbon dioxide. |0010] Figure 2 depicts an embodiment of a fluctuating flowrate system for creating differential high and low pressure in a conduit carrying concrete and carbon dioxide. |001 1 ] Figure 3 depicts an embodiment of a fluctuating orifice/valve system for creating di fferential high and low pressure in a conduit carrying concrete and carbon dioxide.

DETAILED DESCRIPTION OF THE INVENTION

[0012] The invention provides melhods and compositions for adding carbon dioxide under pressure to a cement mix before the mix sets. For convenience, the invention is described in terms of concrete, but it will be understood that the description applies to any mix comprising a cementing material comprising calcium or calcium ions, to which carbon dioxide may be added to produce calcium carbonate.

[0013] Wet concrete, which is a m ixture that includes hydraulic cement, water, and aggregate, is often pumped from one location to another, greatly simplifying and increasing the efficiency of, e.g., a concrete pour. The concrete is provided in mixed form, generally via one or more ready mix trucks which typically deposit wet concrete m ix into a hopper, and pumped from the hopper via a conduit from one area to a second area; typically the first area is fixed for at least part of the pour and the second area can be varied as the conduit is moved to provide an even pour at a particular job site. Typical pumps include boom pumps, line pumps, and skid or rail pumps. The concrete is pumped into a conduit, e.g., a flexible hose, at its proximal end under pressure sufficient to move it to the distal end of the conduit at the desired rate, where it is discharged.

[0014| The invention provides methods and compositions for introducing carbon dioxide under pressure into a closed system comprising concrete, such as into the concrete that moves through the conduit so that the carbon dioxide mixes and reacts with the moving concrete mix to produce carbonated concrete, which is then discharged from the conduit. In some cases the invention provides methods and compositions for increasing COT uptake efficiency and/or manipulating precipitation products in carbonated hydraulic cement mixes in a closed system via modified pressure environments. The concrete can be considered to have a residence time in the conduit dictated by how long a distinct mass of concrete takes to travel from the pump to the exit of the conduit. The carbon dioxide reacts with the cement to form stable carbonate reaction products (e.g., reacting with the Ca ² ' ions from the anhydrous cement to form CaC(¾). The increased pressure in the conduit that faci litates pumping allows for increased solubility of carbon dioxide in the mix water and greater formation of CaC0 ₃ than would occur at atmospheric pressure carbonation. The carbonation under increased pressure promotes greater and/or faster conversion to CaCO,. It will be appreciated that many or all of the factors that apply to addition of carbon dioxide to the concrete in the conduit also apply to add ition of carbon dioxide under pressure at other points in the process, e.g., at the mixer, and in certain embodiments the invention includes the addition of carbon dioxide under pressure greater than atmospheric pressure into concrete in a concrete mixer, e.g., at a pressure of at least 5, 1 0, 20, 30, 50, 1 00, 1 50, or 200 psi or greater.

[0015| The term "hydraulic cement," as used herein, includes a composition which sets and hardens after combining with water or a solution where the solvent is water, e.g., an adm ixture solution. After hardening, the compositions retain strength and stability even under water. An important characteristic is that the hydrates formed from the cement constituents upon reaction with water are essentially insoluble in water. A hydraul ic cement used in the invention may be any hydraulic cement capable of forming reaction products with carbon dioxide. The hydraulic cement most commonly used is based upon Portland cement. Portland cement is made primarily from limestone, certain c lay minerals, and gypsum, in a high temperature process that drives off carbon dioxide and chemically combines the primary ingredients into new compounds. In certain embodiments, the hydraulic cement in the hydraulic cement mix is partially or completely composed of Portland cement.

[0016] A ^"" hydraulic cement m ix," as that term is used herein, includes a mix that contains at least a hydraulic cement and water. Additional components may be present, such as aggregates, admixtures, and the like. In certain embodiments the hydraul ic cement mix is a concrete mix, i.e., a mixture of hydraulic cement, such as Portland cement, water, and aggregate, optionally also including an admixture.

|0017| Carbonating in a closed system such as a conduit offers at least four benefits.

[0018| 1 ) ixing carbon dioxide into concrete contained in a vessel open to the atmosphere allows carbon dioxide to escape regardless of its delivery phase (liquid, gas or solid) thereby limiting the overall efficiency of capturing carbon dioxide as stable reaction products. If the process takes place in a conduit (e.g., pipe) then there is physical containment for the carbon dioxide and no possibility of carbon dioxide escaping. In addition, the flow within the pipe can promote mixing between the carbon dioxide and concrete. [0019] 2) Introducing carbon dioxide in a pipe allows the system to be pressurized. This allows the carbon dioxide phase to be managed, which offers the possibility of using liquid, gaseous, or supercritical carbon dioxide to mix with the concrete. Advantages of these systems are described in U.S. Patent No. 5,51 8,540, incorporated herein by reference in its entirety .

|0020] 3) The solubility of carbon dioxide is directly dependent on pressure. Increasing the pressure of the system increases the amount of carbon dioxide in solution. A change in pressure can change the equilibrium of the system. If the COi injection starts at a given pressure that is then decreased then there is a corresponding decrease in the solubi lity of the CO ₂ and the formation of CaCOs results.

(0021 ] This solubility change can be repeated along the length of the conduit through a pulsing action and a continual supply of CO ₂ to maintain the gas phase during pressure increases. There are a number of ways to create the pulsation described. Examples are described more fully below and shown in Figure 1 (Vcnturi method), Figure 2 (varying flowrate) and Figure 3 (varying orifice/valve).

[0022] 4) It is wel l known that crystal morphology of CaCC is dependent on temperature, pressure and ion content in which it is created. Modifying the pressure of a system allows manipulation of the precipitation products. Forcing rapid precipitation of reaction products via the described method offers the ability to favor formation of a given polymorph, or formation of crystals of a desired size, with benefits to the properties of carbonated concrete such as strength and rheology. Pressure modifications can determ ine crystal size (faster reactions for smaller crystals) and reaction velocity (faster reactions for more aragon ite). Other factors that influence polymorphs include chemical factors, e.g., presence of Sr ² ' , Ba ^2† , Mg ² ' , S04 ^" , temperatures above 30°C, reaction veloc ity, or pi 1.

[0023] The point of introduction of the carbon dioxide may be any suitable point, so long as at the point of introduction the system is sufficiently closed so as to allow no, or minimal, leakage of the carbon dioxide. In certain embodiments, the carbon dioxide is introduced into a c losed mixer in which concrete is mixed. In certain embodiments, the carbon dioxide is introduced at the pump. In certain embodiments, the carbon dioxide is introduced at the conduit, for example, in a line joining the conduit at or near the proximal end of the conduit, to allow maximum distance/time for the carbon dioxide to mix and react with the concrete, however, carbon dioxide may also be introduced further down the length of the conduit if there is sufficient distance/time for mixing and reaction. More than one point of introduction of carbon dioxide may be used, for example, at the pump and at the conduit, or at various points along the conduit, or a combination thereof.

|0024j The carbon dioxide is supplied to the concrete in the closed pressurized container, such as m ixer, pump, or conduit at a pressure that allows its entrance into the pressurized concrete in the pressurized container, e.g., conduit, thus at or above the pressures in the container, e.g., at which the concrete is pumped. The pressure at which the carbon dioxide is introduced may be at least 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1 000 psi. In certain embodiments, the pressure is at least 50 psi. In certain embodiments, the pressure is at least 1 00 psi. In certain embodiments, the pressure is at least 300 psi. In certain embodiments, the pressure is at least 500 psi. In certain embodiments, the pressure is at least 600 psi. In certain embodiments, the pressure is 100-3000, 1 00-2000, 100- 1 500, 200-3000, 200-2000, 200- 1 500, 300-3000, 300-2000, 300- 1 800, 300- 1600, 300-1 500, 300- 1400, 300- 1300, 300- 1 200, 400-3000, 400-2000, 400- 1 800, 400- 1600, 400- 1 500, 400- 1400, 400- 1300, 400- 1 200 psi, 500-3000, 500-2000, 500- 1 800, 500- 1600, 500- 1 500, 500- 1400, 500- 1 300, 500- 1 200, 600-3000, 600-2000, 600- 1 800, 600- 1700, 600- 1600, 600- 1 500, 600- 1400, 600- 1300, or 600- 1200 psi. In certain embodiment, the pressure is 200 to 1500 psi. In certain embodiments, the pressure is 400 to 1 500 psi. In certain embodiment, the pressure is 500 to 1500 psi. In certain embodiments, the pressure is 600 to 1 500 psi. The pressure of the carbon dioxide may additionally or alternatively be expressed as a pressure that is a certain amount above the pressure of the concrete in the c losed pressurized container, e.g., conduit, such as at least 1 , 2, 5, 10, 20, 50, 100, 200, or 500 psi above the pressure of the concrete in the container, e.g., conduit, or 1 - 1000, 1 -500, 1 - 1 00, or 1 -50 psi above the pressure of the concrete in the container, e.g., conduit, or 5- 1000, 5-500, 5- 1 00, or 5-50 psi above the pressure of the concrete in the container, e.g., conduit, or 1 0- 1 000, 10-500, 10- 1 00, or 10-50 psi above the pressure of the concrete in the container, e.g., conduit. The concrete may be suppl ied in any suitable form, such as a gas, liquid, supercritical, solid, or any combination thereof, so long as it is in a form that can enter and mix with the concrete in the conduit; the pressure and temperature will dictate which form or forms are suitable. In certain embodiments the carbon dioxide is supplied in liquid form. In certain embodiments, the carbon dioxide is in supercritical form. The carbon dioxide may be mixed with other gases or it may be pure or substantially pure; in certain embodiments the carbon dioxide is at least 90, 95, 99, or 99.5% pure. In certain embodiments the carbon dioxide is used alone, i.e., not mixed with water, surfactant, or any other substance other than impurities normally present in the carbon dioxide as supplied. It is important to note that the concrete is propelled through the conduit by the pressure of the pump, and that the carbon dioxide as added in the invention is added as a source of carbonalion and not as a propellent, as in the case of a sholcrete (concrete spray) appl ication. Thus, for example, in certain embodiments the methods and apparatus of the invention are not shotcrete methods and apparatus.

[0025] Typica l ly the carbon dioxide will be pumped from a storage container to the conduit via its own conduit and introduced into the concrete conduit at any suitable location as described herein. Carbon dioxide may be introduced at one point, e.g., at or near the proximal (pump) end of the conduit, or at multiple points, such as at 2, 3, 4, 5, 6, 7, 8, or more points in the conduit. As it is generally advantageous for the carbon dioxide to be in contact with the concrete mix as long as possible, a preferred site of entry is at the pump or at or near the proximal end of the concrete conduit. The positioning of the site or sites of entry also affects the length of time that the concrete is form ing carbonates before be ing discharged from the conduit, as well as the length of time that the concrete is in contact with water after mixing and before contact with carbon dioxide— an earlier point of entry, such as in the mixer, or pump, or at the proximal end of the conduit, means a longer time for the carbon dioxide to be in contact with the concrete and forming carbonalion products and a shorter time between beginning of concrete mixing with water and addition of the carbon d ioxide. In certain cases, it is desirable that the time of contact with carbon dioxide and carbonation before discharge be relatively short and/or the time from start of mixing be relatively long; in such cases, carbon dioxide may be introduced further toward the distal end of the conduit. In other cases, it is desirable that a longer time of contact with carbon dioxide and carbonation before discharge and time from mixing relatively shorter be used; in such cases, carbon dioxide may be introduced in a pressurized mixer, or in a pump, or further toward the proximal end of the conduit. Any combination of entry points may be used to achieve the desired timing of contact. I n certain embodiments, multiple entry points are used so that the concrete is exposed to additional doses of carbon dioxide beyond the first dose, and after the first dose has had a chance to start reacting with the concrete components. The pump, the conduit, an opening of the conduit, or any combination thereof, may be configured so as to provide a variable pressure to the concrete/carbon dioxide mixture as it moves through the conduit. [0026] CO2 injection may take place by as simple a mechanism as a conduit joining the main pumping conduit, where the CO? is supplied to the side of the concrete stream. Alternatively, or in addition, CO2 may be supplied in such a manner as to be injected into the body of the stream. For example, in certain embodiments, the CO2 injection takes place from within the concrete stream via an injecting member that resides in or is optionally inserted into the concrete. Such a member may have a single outlet or may be, e.g., a finger with multiple perforations, optionally directed in line with the flowing concrete. Several discrete point injections in the stream may be preferable than a single injection at the side of the stream. The injector can be inseitabie and/or removable, e.g., to allow for cleaning or installation only when needed. Additionally, an inline injector may have a geometry that facilitates mixing. Exemplary embodiments include a grid comprising hollow members with multiple gas injection outlets directed into the concrete, preferably down the stream of the flow. However, any suitable arrangement that fac ilitates mixing may be used.

[0027| In certain embodiments, the carbon dioxide is introduced into the wet concrete m ix in the conduit and not further manipulation takes place; as the concrete mix and carbon dioxide travel down the conduit carbonation reactions take place and the concrete is carbonated to the desired degree. In other embodiments, the pressure and/or other aspects of the concrete mix in the conduit are manipulated so as to promote carbonation and/or to promote formation of a desired crystal form of calcium carbonate. In either case, when the concrete exits the conduit, most or all of the carbon dioxide that was introduced into the concrete mix, e.g., at least 60, 70, 80, 90. 95, 97, 98, 99, 99.5, or 99.9%, is within the mix, either as carbonation products, or as dissolved carbon dioxide that is continuing to undergo carbonation reactions, as described below.

[0028| W ithout being bound by theory, it is thought that the following reactions take place: when carbon dioxide is introduced into a wet concrete mix, the reaction of carbon dioxide gas and hydrating cement takes place in solution between C(¾ ^3" and Ca ^{- t} ions, ultimately producing calcium carbonate. A simple set of equilibriums can explain the different parameters that impact solubility and thus calcium carbonate formation.

[0029] First, carbon dioxide reacts with water to produce carbonic acid, reaction 1 :

C0 ₂ (g) + H ₂ 0 (I) H2CO3 (aq) [ 1 ] |0030] The carbonic acid dissoc iates further creating new deprotonated species of carbonic acid, bicarbonate and carbonate, reactions 2 and 3.

H ₂ C0 ₃ (aq) + H ₂ 0 (1) => H3O (aq) + HCO3 ^" (aq)

HCCV (aq) + H ₂ 0 (1) o Η ₃ θ" (aq) - C0 ₃ ^2" (aq) [3]

|0031 ] The solution will contain a mixture of the species H ₂ C0 ₃ , HC0 ₃ ^~ and C0 ₃ ~ ^~ . In the presence of calcium and carbonic acid, calcium carbonate wi ll precipitate out, reaction 4:

CO3 ² (aq) + Ca ²⁺ (aq) = CaC0 ₃ (s) [4]

|0032] Since the mix water of a hydrating cement system contains calcium ions, and carbonic acid is the result of the external supply of carbon dioxide, a simplified net reaction to form water soluble bicarbonate can be expressed as reaction 5:

Ca(HC0 ₃ ) ₂ (aq) = C0 ₂ (g) + H ₂ 0 (1) + CaC0 ₃ (s) [5]

|0033] Calcium and carbonic acid together in liquid form wi ll be in equilibrium with water, sol id calcium carbonate and CO ₂ gas.

|0034] Aspects of the calcium carbonate equilibrium can be predicted from Le Chatelier's equilibrium principle. This principle states that a chemical system at equilibrium will always adjust to counteract any imposed change in pressure, temperature, volume or composition. A change in any of these variables can thereby affect the equilibrium and the formation of calcium carbonate. The equil ibrium is affected by the parameters as fo llows. |0035] Pressure dependence: When pressure is decreased in a chemical system, the equil ibrium of reaction 5 will respond to increase the pressure. Because C0 ₂ is the only gaseous species, the only way to increase pressure is by shifting the equilibrium towards producing more C0 ₂ . This shift in equilibrium means that a decrease in pressure results in increased precipitation of calc ium carbonate.

[0036] Concentration dependence: If the concentration of calcium or carbonic acid is increased or the partial pressure of C0 ₂ is decreased, then there wou ld be an equilibrium shift of reactions 2 and 3 towards more prec ipitation of calc ium carbonate. Increasing the pH as per the hydration of cement would result in a neutralization of the H3O' complex. This will ield more carbonic acid. More carbonic acid will shift the equilibrium of reaction 5 towards the precipitation of more calcium carbonate.

|0037| Temperature dependence: The solubility of calcium carbonate decreases as the temperature increases. An increase in temperature will shift the equ i librium of equation 5 towards calcium carbonate formation.

[0038] The reaction between the carbon dioxide and the cement be promoted or manipulated by changing the pressure. A pressure drop promotes the formation of calc ium carbonate. Upon increasing the pressure the equilibrium would tend to re-form soluble bicarbonate at the expense of carbon dioxide gas, calcium carbonate, and water. W ithout being bound by theory, the calcium and carbon dioxide portions of the equilibrium are satisfied by more Ca ' ' having gone into solution form the hydrating cement (in response to consumption of Ca ions in the calcium carbonate formation) and the continued supply of carbon dioxide gas to the system. The calcium carbonate formed during the pressure drop remains stable upon pressure increase due to the fresh supply of the necessary ions.

[0039] Thus, in certain embodiments, the invention provides methods and compositions for vary ing the pressure in a closed conduit in which carbon dioxide is m ixed with a hydraulic cement m ix, e.g., a concrete mix, to promote carbonation and/or lo promote the formation of desired polymorphs of calcium carbonate. Any suitable method/apparatus may be used so long as it provides for variations in the pressure to which the concrete m ix is subjected in the conduit to promote the formation of CaCC>3, either in a single event, continuous down the length, or over more than one increase/decrease cycles. Three exemplary apparatus are il lustrated in Figures 1 -3. Figure 1 shows a Venturi system for alternating pressure decrease and increase, where a conduit is modified to provide for areas of constriction; as concrete flows through these areas, due to the Venturi effect, the pressure decreases, and as the concrete flows into expanded sections, the pressure increases. A single constriction may be used or, as illustrated in Figure 1 , a plurality of constrictions may be used. In certain embodiments, instead of a constriction, a grate may be utilized, which provides not only for a constricted flow but also for increased mixing. Figure 2 i llustrates a fluctuating flow rate system for provid ing pressure variation. In this sy stem, the flow rate of the concrete is varied by pumping at variable rates, thus changing the pressure in the system in a variable manner. Figure 3 illustrates a system in which a valve or orifice at the distal end of the conduit is varied in size, affecting pressure in the conduit; the smaller the orifice, the higher the pressure in the conduit.

[0040) Pressure and/or other variables manipu lation may also be used to manipulate the crystal form, i.e., polymorph, of calcium carbonate that is formed. Calcium carbonate exists as four polymorphs: from least stable to most stable (at atmospheric pressure, neutral pi I, and room temperature), these are amorphous calcium carbonate (ACC), vaterite, aragon ite, and calcite. However, changes in conditions, e.g., pressure, can affect stability of polymorphs; for example, at high pressures, aragonite is more stable than calcite. Thus the invention includes manipulating pressure and/or other variables in such a way as to favor the formation of one polymorph of calcium carbonate, such as to favor the formation of ACC, or to favor the formation of vaterite, or to favor the formation of aragonite, or to favor the formation of calcite. For example, the degree and speed of a pressure variation may be manipulated so as to favor the precipitation of a particular polymorph. In addition, crystal size may also be manipulated by manipu lating cond itions.

[0041 J In certain cases, one or more admixtures may be added to the concrete mix.

Depending on the mix design and other conditions, carbonation of wet concrete mixes can lead to alterations certain characteristics, e.g., in flow characteristics, such as decreased flow abil ity, or early strength development, such as strength at 24 hours, or 7, 1 4, or 28 days. In some cases it may be desirable to add one or more admixtures to counteract such changes. The admixture may be added at any suitable point in the process, such as at the batching plant, in the ready mix truck, in the hopper, or at one or more points in the conduit, e.g., at one point, 2 separate points, 3 separate points, or 4, 5, 6, 7, 8, or more than 8 separate points, or any combination thereof, so long as sufficient mixing is provided to allow homogeneous incorporation of the admixture into the mixture. In certain embodiments, one or more admixtures is added at the hopper. In certain embodiments, one or more admixtures is added in the conduit, at one or more points in the conduit as described herein.. In some cases, one or more coarse grates, or similar devices, may be placed in the conduit to provide for thorough mixing of the admixture into the concrete mix. Any su itable admixture may be used to achieve the desired effect, such as improved flowability or improved early strength. Admixtures suitable for use in the invention are described in PCT Appl ication No. PCT/CA2014/05061 1 , and U .S. Patent Application Nos. 1 4/249,308, 61 /839,3 1 2, 61 /847,254, 6 1 /879,049, 61 /925, 1 00 and 6 1 /938,063, al l of which are incorporated herein by reference in their entirety. In certain embodiments, the admixture is a carbohydrate, i.e., saccharide, such as sugars, e.g., fructose, glucose, and sucrose, and sugar acids/bases, such as sodium gluconate and sodium glucoheptonate; phosphonates, such as nitrilotri(methyIphosphonic acid), 2-phosphonobutane- 1 ,2,4- tricarboxyl ic acid; and chelating agents, such as EDTA, Citric Acid, and nitrilotriacetic acid. Other saccharides and saccharide-containing adm ixes of use in the invention inc lude molasses and corn syrup. In certain embodiments, the adm ixture is sodium gluconate.

[0042] In certain cases, feedback from the operation may be used to modify the addition of carbon dioxide and/or other parameters, such as pump operation, addition of admixture, and the like. For example, increase in temperature of the concrete mix is indicative of extent of carbonation, and one or more temperature sensors on or in the conduit can provide feedback indicating whether the desired degree of carbonation is being achieved, allowing for adjustment of the rate of addition of carbon dioxide to the system. Other sensors include carbon dioxide sensors, which may be placed al the distal end of the conduit to indicate whether unreactcd carbon dioxide is exiling the conduit, indicating a need for reduction of carbon dioxide addition. Such sensors can also be used to ensure worker safety in any enclosed spaces in which the concrete is poured. Additional sensors and feedback mechanisms may be found in PCT Application No. PCT/CA2014/05061 1 , and U.S. Patent Appl ication Nos. 14/249,308, 61 /839,3 12, 61 /847,254, 61 /879,049, 61 /925.1 00 and 61 /938,063, all of wh ich are incorporated herein by reference in their entirely.

[0043] A control system can monitor pumping pressure and start injection once a desired pressure has been released. The pressure in the concrete builds from zero in an empty pipe to a maximum as the more concrete fi l ls the conduit, and the C0 ₂ injection can have a lower limit on pressure input given that the pressure drop from the liquid injection to the concrete can determ ine the gas/l iquid/solid balance of the injected COT.

Dose of carbon dioxide added to concrete

[0044] The dose of the carbon dioxide added to the concrete in embodiments of the invention may be any suitable dose.

[0045] Low doses of carbon dioxide, e.g.. less than 1 %, preferably less than or equal to 0.5% carbon dioxide by weight cement (bwc) are used in certain embodiments of the invention. Such low doses are advantageous in that the carbon dioxide is quickly and easily taken up by the concrete, generally does not appreciably alter the flowabil ity of the concrete, and can increase early strength development of the concrete. Thus, in certain embodiments, carbon dioxide is added to the pressurized concrete, for example, concrete in a conduit, at a dose of no more than 1 . 0.9. 0.8, 0.7, 0.6, 0.5, 0.4, 0.3. 0.2, 0. 1 , 0.05, or 0.0 1 % bwc. in certain cases also no less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0. 1 , 0.05, 0.01 , or 0.005%i bwc, such as a dose between 0.005 and 1 % bwc, or 0.05 and 1 % bwc, or 0.05 and 0.7% bwc, or 0.05 and 0.5% bwc, or 0.05 and 0.3% bvvc, or 0.05 and 0. 1 % bwc, or 0. 1 and 1 % bwc, or 0. 1 and 0.7% bwc. or 0. 1 and 0.5% bwc, or 0. 1 and 0.3% bwc. In certain embodiments, carbon dioxide is added at a dose of between 0.05 and 0.5% bwc.

[0046] Higher doses of carbon dioxide, e.g., 0.5-5% bwc, preferably greater than or equal to 1 % bvvc, are used in certain embodiments of the invention. Higher doses can affect the flowabil ity of the concrete, generally decreasing flowabi lity. This can be useful in appl ications where it is desired that the concrete quickly becomes self-supporting, for example, in 3D concrete printing appl ications, or any other application in which rapid development of self-supporting concrete is desired. Thus, in certain embodiments, carbon dioxide is added to the pressurized concrete, for example, concrete in a conduit, at a dose of no less than 5, 4, 3. 2, 1 .5, 1 .2, 1 , 0.8, or 0.5% bwc, in certain cases also no more than 5 4, 3, 2, 1 .5, 1 .2, 1 . 0.8, or ().5% bwc, such as a dose between 0.5 and 5% bwc, or 0.8 and 5% bwc, or 1 and 5% bvvc, or 2 and 5% bwc, or 3 and 5% bwc, or 0.5 and 4% bwc, or 0.8 and 4% bwc, or 1 and 4%> bwc, or 2 and 4% bwc, or 0.5 and 3% bwc, or 0.8 and 3% bwc, or 1 and 3% bwc.

[0047| It will be appreciated that in embodiments in which the carbon dioxide is added to concrete flowing in a condu it, the flow rate of the carbon dioxide may be adj usted according to the flow rate of the concrete so as to achieve the desired dosage over the course of the pour; minor variations are acceptable so long as the overal l dosing is achieved.

Methods, Systems, Compositions, and Apparatus

[0048] The methods and compositions involve wet concrete pumped under pressure through a conduit in the presence of carbon dioxide, and apparatus and compositions for doing so.

[0049] In certain embodiments, the invention provides a method of carbonating concrete comprising i) pumping a wet concrete m ix into a conduit at a pressure sufficient to move the concrete through the conduit at a desired rate; ii) introducing carbon dioxide into the conduit at a pressure at or above the pressure of i). The carbon dioxide may be introduced at any suitable point, as described herein for example, at a pump that pumps the concrete into the conduit or at or near the distal end of the conduit, or elsewhere in the conduit, or any combination thereof. The pressure at which the carbon dioxide is introduced into the conduit may be any pressure as described herein, such as at least 50 psi, for example, at least 1 00 psi, or even at least 300 or at least 500 psi. Other suitable pressures are described elsewhere herein. The dosage of the carbon dioxide added to the concrete may be any suitable dosage as described herein, such as between 0.05 and 0.5% bwc, or between 0.5 and 5% bwc. The carbon dioxide can be transported to the conduit in any suitable form, such as in liquid form; in the later case, when the carbon dioxide is released into the conduit it may be released under conditions whereby the carbon dioxide becomes gaseous and solid in the conduit. In certain embodiments the carbon dioxide is in supercritical form. The initial state of the CO? in the line wi ll depend on the change in pressure of lhe CO? from the tank to the pump. At low pump pressures (< 20-30 bar depend ing on temperature) there is a phase change to vapor/solid and the temperature of the concrete will result in the sublimation of any solids quickly. At high pump pressures the CO? can enter and remain liquid (>300 psi or 2 1 bar). The pressure in the conduit depends on position and time of the pump cycle. The static pressure relates to how much concrete is above the position of interest and thus decreases w ith increasing height in the conduit. The pumping pressure occurs when the concrete moves. The pump cyc le moves the concrete according to its displacement (on the order of 1 -2 feet). The pressure at all locations increases while the concrete moves. Thus, as the concrete is pumped up the boom, the pressure drops causing the COT to go through a phase change to vapor/solid, then as it is discharged the pressure can drop to zero or negative. The concrete temperature wi ll sublimate the solid CO?, if any. If there is not enough time for the COT to be taken up during the pumping then it can go into the atmosphere or into the form as the concrete is discharged. The concrete may be manipulated so that it is under variable pressure down the length of the conduit. In certain cases, this may be done by having at least one constricted section in the conduit, or a plurality of constricted sections alternating with expanded sections; see, e.g., Figure 1 . Alternatively, or in addition, the variable pressure can be provided by varying the rate of pumping of concrete into the conduit; see, e.g., Figure 2. Alternatively, or in addition, the variable pressure can be provided by pumping the concrete at a constant rate at the proximal end of the conduit and varying the size of an orifice or valve at the distal end of the conduit. One or more adm ixtures may be added to the mix as descr ibed elsewhere herein. In addition, one or more feedback mechanisms as described elsewhere herein may be used to adjust, e.g., carbon dioxide addition according to one or more characteristics of the concrete mix or apparatus.

[0050] In certain embodiments the invention provides a method of modu lating the crystal structure and/or crystal size of calc ium carbonate formed in a wet hydraul ic cement mix comprising m ixing the wet hydraulic cement mix with carbon dioxide in an gastight container and varying the pressure of the mix, thereby modulating the crystal structure and/or crystal size of the calcium carbonate formed from the carbonation of the mix, compared to crystal structure and/or crystal size that would have been formed without modulation. The closed container may be a conduit as described herein, e.g., a conduit through which wet concrete mix is pumped, and the pressure modulation may be achieved as described herein.

|0051 | In certain embodiments the invention provides an apparatus for moving wet concrete m ix from a first area to a second area and adding carbon dioxide to the mix comprising i) a container for holding mixed wet concrete in the first area; ii) a conduit operably connected to the container and extending to the second area; iii) a system for providing pressure to the concrete to move it from the container, into the conduit at a proximal end of the conduit, and out of the conduit at a distal end into the second area; iv) a system for supplying carbon dioxide operably connected to the system of iii) or the conduit of ii) configured to introduce carbon dioxide under pressure to the wet concrete mix so that the carbon dioxide mixes w ith the concrete passing through the conduit. The container may be, e.g., a hopper of a concrete pump system, and the system for provid ing pressure may be a concrete pump such as a boom pump, line pump, skid or rai l pump, or any other pump known or developed in the art. In certain embodiments the system for supplying pressure is a boom pump, a line pump, or a skid or rail pump. The carbon dioxide may be liquid, gaseous, solid, or supercritical carbon dioxide, or any combination thereof. In certain embodiments the carbon dioxide is liquid carbon dioxide; in such an embodiment, the system for supplying carbon dioxide may be configured to introduce the liquid carbon dioxide to the conduit in such a manner that the carbon dioxide becomes solid and gaseous carbon dioxide. The system for supplying carbon dioxide may be configured to introduce the carbon dioxide at any suitable pressure into the mix, such as into the conduit, as described herein, such as at pressure of at least 50 psi, for example, at least 1 00 psi. or even at least 300 or at least 500 psi. Other suitable pressures are described elsewhere herein. The conduit can comprise at least one constricted area to decrease the pressure of the concrete/carbon dioxide mixture flowing through the constricted area, or a plurality of such constricted areas alternating with expanded areas to provide areas of alternating decreasing and increasing pressure to the concrete/carbon dioxide m ixture flowing through the conduit. Alternatively, or additionally, the system for providing pressure to the concrete can be configured to provide variable pressure to the concrete as it is pumped through the conduit. Alternatively or additionally, the distal end of the conduit comprises an orifice or valve, wherein the orifice or valve is configured to provided a variable size so as to vary the pressure of the concrete/carbon dioxide m ixture in the conduit. The apparatus may further be provided with one or more sensors for sensing one or more of temperature of the concrete mix, carbon dioxide concentration, or other relevant characteristic, and providing feedback to the system of iii) to adjust the rate of addition of carbon dioxide according to the degree of carbonation of the wet concrete mix. The apparatus may be provided with one or more systems for adding admixture to the wet concrete mix, such as a system configured to add on or more admixtures to the m ix in the container for holding the mixed wet concrete, the system for providing pressure to the concrete, the conduit, or any combination thereof.

|0052] The invention also provides for retrofitting an existing apparatus to add carbon dioxide to the wet concrete m ix in the conduit, such as by adding to the apparatus a container for the carbon dioxide, a conduit for carrying the carbon dioxide to the concrete pump system, and the necessary fittings, regulators, valves and the like to allow the carbon dioxide to be added at the desired location, pressure, and flow rate.

[0053] In certain embodiments the invention provides a conduit for transporting a wet concrete mixture mixed with carbon dioxide from a first area to a second area, where the conduit comprises at least one constricted area so that the concrete flowing through the conduit experiences a reduced pressure as it flows through the restricted area and increased pressure as it flows beyond the constricted area. In certain embodiments, the constricted area constricts the cross sectional area of the conduit by at least 20, 30, 40. 50, 60, 70, 80, or 90%. The conduit may comprise a a plurality of restricted areas alternating with expanded areas so that the concrete flowing through the conduit experiences alternating reduced and increased pressures as it flows through the conduit, such as 2, 3, 4, 5, 6, 7, 8, 9, 1 0, or more than 1 0 constricted areas. [0054] In certain embodiments, the invention provides a conduit for transporting a wet concrete m ixture mixed with carbon dioxide from a first area to a second area, where the conduit comprises a proximal end at the first area and a distal end at the second area, and where the distal end of the conduit is configured to provide an orifice or valve for the exit of the concrete of variable size. The size of the orifice or valve may be varied by at least 1 0, 20, 30, 40, 50, 60, 70, 80. 90, or 95%. The orif ice or valve may further comprise a system for varying the size of the orifice or valve, such as in a predetermined manner, to provide an alternation of high and low pressure in the conduit.

[0055] In certain embodiments, the invention provides a condu it for transporting a wet concrete m ixture mixed with carbon dioxide from a first area to a second area and the carbonated wet concrete mix, where the wet concrete mix at the end of the conduit in the second area contains calcium carbonate that comprises at least 1 0, 20, 30, 40, 50, 60, 70, 80, or 90% aragonite. In certain embodiments, the invention provides a conduit for transporting a wet concrete mixture m ixed with carbon dioxide from a first area to a second area and the carbonated wet concrete mix, where the wet concrete mix at the end of the conduit in the second area contains calcium carbonate that comprises at least 10, 20, 30, 40, 50, 60, 70, 80, or 90% vaterite. In certain embodiments, the invention provides a conduit for transporting a wet concrete mixture mixed with carbon dioxide from a first area to a second area and the carbonated wet concrete mix, where the wet concrete m ix at the end of the conduit in the second area contains calcium carbonate that comprises at least 1 0, 20, 30, 40, 50, 60, 70, 80, or 90% amorphous calcium carbonate.

[0056] Wh ile preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will no occur to those sk illed in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.