CN117412937A

CN117412937A - Production of cement from non-limestone materials

Info

Publication number: CN117412937A
Application number: CN202280039015.1A
Authority: CN
Inventors: C·费恩克; M·J·德莱; V·卡夏普; E·T·卡伦布; N·哈维-科斯特洛; J·A·布雷松; M·J·凯勒; H·F·莱安德里
Original assignee: Sulfur Energy Co ltd
Current assignee: Sulfur Energy Co ltd
Priority date: 2021-04-12
Filing date: 2022-04-12
Publication date: 2024-01-16

Abstract

Methods and compositions for deriving cement and/or supplementing cement materials, such as pozzolans, from one or more non-limestone materials, such as one or more non-limestone rocks and/or minerals, are provided. The non-limestone material, such as non-limestone rock and/or minerals, is processed in a manner that produces a desired product, such as cement and/or supplemental cementitious material.

Description

Production of cement from non-limestone materials

The present application claims U.S. provisional patent application No. 63/173,703 filed on day 4, month 12 of 2021; U.S. provisional patent application No. 63/240,319 filed on 9/2 of 2021; and priority of U.S. provisional patent application No. 63/279,596 filed on 11/15 of 2021, which is incorporated herein by reference in its entirety.

Background

Cement and cement products are necessities of modern life, building essentially the entire human infrastructure. The most common type of cement is ordinary portland cement, which is used to produce concrete, mortar, stucco, non-specialty cement slurries, and many other products. Although cement is necessary for us, we need to deal with many drawbacks on a regular basis due to cement production. Portland cement is toxic; the exploitation, manufacture and transportation of raw materials requires a great deal of energy. In addition, the production of portland cement also releases a large amount of greenhouse gases, with portland cement production constituting 8% of world carbon dioxide emissions. Furthermore, by the International Energy Agency (IEA) it was expected that cement production would increase by 12-23% by 2050.

Thus, there is a need in the art of cement generation to create a new, useful and more environmentally friendly cement generation process.

Incorporated by reference

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 Drawings

Fig. 1 shows a flow chart representation of a first method.

Fig. 2 shows a flow chart representation of a second method.

Fig. 3 shows a method of producing a calcium-rich liquid fraction and a calcium-depleted solid fraction from a non-limestone material.

Fig. 4 shows a method of producing SCM from a calcium-depleted solids portion.

Fig. 5 shows three different methods of precipitating aluminum, iron and/or magnesium from a calcium-rich liquid fraction.

Fig. 6 shows a method of producing a dechlorinated solid comprising calcium from a solid comprising calcium chloride.

Fig. 7 shows a method of producing clinker from dechlorinated solids comprising calcium.

Fig. 8 shows an apparatus for producing clinker from a non-limestone starting material, the apparatus comprising a first processor and a second processor.

Fig. 9 shows an embodiment of the first processing machine of fig. 8.

Fig. 10 shows an embodiment of the second processing machine of fig. 8.

Fig. 11 shows a system and method for producing Supplemental Cement Material (SCM) and clinker (e.g., clinker for OPC) from non-limestone material (e.g., rock) using only an alkali precipitation unit/step.

Fig. 12 shows a system and method for producing Supplemental Cement Material (SCM) and clinker (e.g., clinker for OPC) from non-limestone material (e.g., rock) using at least one thermal hydrolysis precipitation unit/step and an alkali precipitation unit/step.

Fig. 13 shows an exemplary embodiment of a system for producing clinker, e.g., clinker for OPC.

Fig. 14 shows an optical micrograph of a clinker sample obtained in the procedure of example 4.

Fig. 15 shows the procedure of example 5.

Detailed Description

The following description of the embodiments of the invention is not intended to limit the invention to those embodiments, but to enable any person skilled in the art to make and use the invention.

1.Overview of the invention

Methods and apparatus for extracting cement precursors and minerals from non-limestone materials containing elemental calcium and silicon are presented. The method can comprise the following steps: using a leaching agent to dissolve and separate the non-limestone material into a calcium-rich portion and a calcium-depleted (calcium-depleted) portion (also referred to herein as a calcium-depleted) portion; converting the calcium-depleted fraction to pozzolans and/or other cement precursor compounds; extracting a calcium compound from the calcium-rich fraction; and regenerating the leaching agent. As used herein, a "calcium-rich fraction" includes a fraction that is typically liquid, resulting from, for example, dissolution of a non-limestone material with a leaching agent such as an acid (e.g., HCl); obviously, the portion may undergo one or more additional steps to, for example, remove certain materials; the resulting material typically has a relatively low amount of one or more particular materials, or is otherwise altered, and may still be referred to as a "calcium-rich portion". Typically, the "calcium-rich fraction" continues through the process until it is dehydrated to produce a solid, such as a solid comprising calcium chloride, for example in embodiments in which HCl is the leaching agent. Depending on the composition of the non-limestone material, the method may include extracting other minerals (e.g., by precipitation and/or thermal decomposition or thermal hydrolysis). The method is used as a versatile extraction and production process, wherein the method is capable of extracting cement precursor materials (e.g. SCM, lime, clinker, etc.) in addition to potentially valuable elements (e.g. aluminum, iron, magnesium, etc.). As used herein, the term "clinker" includes cement clinker, such as portland cement clinker, unless otherwise indicated. In addition, the method may be used to produce cement (e.g., ordinary portland cement). In these variations, the method may further comprise converting the calcium compound to cement (e.g., by a curing or sintering process).

The method is particularly useful in the fields of mineral extraction and concrete production. The method may be carried out during or after mineral extraction to produce/extract additional resources. By this method, cement precursor materials and cement can be extracted and produced. In one mineral extraction implementation, non-limestone rock may have been extracted and processed such that the mineral has been removed from the rock. The method can then be carried out to potentially extract other minerals and produce a cement product.

The method may also be particularly useful for general purposes of cement production. The production of cement from non-limestone rock may help the cement production become more environmentally friendly.

The method may provide a number of potential benefits. The method is not limited to always providing such benefits, and is presented only as an exemplary representation of how the method is used. The list of benefits is not exhaustive and other benefits may additionally or alternatively exist.

The method may provide the benefit of being able to produce cement in a more environmentally friendly manner. The most common method of producing cement is currently to heat limestone to produce lime and carbon dioxide. By producing cement without the use of limestone, carbon dioxide emissions can be substantially reduced.

The method may provide new resources for cement production. Because limestone is not required, cement production can be extended to more areas of the world.

In addition, the method may potentially provide the benefit of simplifying concrete production. The production of concrete typically requires Ordinary Portland Cement (OPC), supplementary Cement Materials (SCM) and aggregate. Currently, concrete producers need to use different sources to obtain OPC and SCM. The method may enable SCM extraction and OPC generation from the same source (e.g., starting material). In addition, the method may enable SCM extraction from the same source and production of OPC and aggregate. This can significantly simplify the concrete production process and potentially reduce the cost of concrete production. Accordingly, provided herein is a method of producing concrete from portland cement and SCM (e.g., pozzolan), wherein the portland cement and SCM (e.g., pozzolan) are derived from the same source, e.g., the same non-limestone material, e.g., non-limestone rock and/or minerals. In certain embodiments, provided herein is a method of producing concrete from portland cement, SCM (e.g., pozzolan), and aggregate, wherein the portland cement, SCM (e.g., pozzolan), and aggregate are derived from the same source, e.g., the same non-limestone material, e.g., non-limestone rock and/or mineral. In certain embodiments, a system for producing concrete is provided, wherein the concrete comprises portland cement and an SCM, such as a pozzolan, wherein the portland cement is produced from non-limestone materials (e.g., non-limestone rock and/or minerals) in a cement production facility (e.g., a facility described herein); and SCM is produced from non-limestone material (e.g., non-limestone rock and/or minerals) in an SCM production facility (e.g., the facility described herein); wherein the cement generating equipment, the SCM generating equipment, and the non-limestone material (e.g., non-limestone rock and/or mineral) are all located in a single location, such as where non-limestone rock and/or mineral is mined from a source. In certain embodiments, the cement generating device and the SCM generating device are the same device. The concrete may also contain aggregate and the system may further comprise aggregate generating equipment, such as equipment including crushers, grinders and sieves, for generating aggregate from non-limestone material, such as non-limestone rock and/or minerals, wherein the aggregate generating equipment is co-located with the cement generating equipment and the SCM generating equipment. The same location may be the following: for example, each device is within a 10, 5, 1, or 0.5 mile radius, such as within a 1 mile radius or even within a 0.5 mile radius; the source of non-limestone material, such as non-limestone rock and/or minerals to be mined, may also be within the radius, or may be further away, but in any event not more than 10, 5, 4, 3, 2 or 1 miles, such as not more than 2 miles, of the location.

In addition, the method may provide the potential benefit of increasing availability by adding materials to make concrete. That is, in addition to being able to perform concrete production, the method may also provide benefits over mineral extraction by concrete production (e.g., metals such as aluminum and iron may also be extracted for use or sale).

In addition, the method potentially provides the benefit of efficient mineral purification (e.g., purification of metals such as aluminum and iron) concurrent with cement material extraction for benefits other than mineral extraction for concrete production.

For certain variations, the methods may also provide the potential benefit of extracting high purity SCM (e.g., micro-or nano-silica or silicon powder). That is, in variants where the extracted silica is not reused for producing calcium base for, e.g., extracting metals (e.g., in variants where aluminum and iron are extracted by thermal decomposition), a large amount of the extracted silica may be retained in a purer form.

The method may provide a more energy efficient method for cement and other mineral extraction. In some variations, the process may incorporate the use of mechanical vapor recompression to recover latent heat of water evaporation or other electrical heating or to recombine heat from other reaction steps to reduce energy (especially non-electrical energy) consumption.

As shown in fig. 1, the method for extracting cement precursors and minerals from non-limestone starting materials comprises: obtaining a non-limestone material S110, wherein the non-limestone material comprises a material comprising elemental calcium and optionally silicon; producing a calcium-rich portion and a calcium-depleted portion from a non-limestone material S130, comprising dissolving at least calcium compounds, thereby producing a calcium-rich portion and a calcium-depleted portion of the non-limestone material, wherein dissolving the non-limestone material comprises adding at least one leaching agent S132; separating a calcium-depleted portion from a calcium-enriched portion S140, wherein the calcium-depleted portion may comprise a pozzolan; separating S150 the calcium-containing compound from the calcium-rich fraction (e.g., in the case of embodiments in which HCl is the leaching agent, producing a solid comprising calcium chloride); optionally decomposing a calcium compound (e.g., dechlorinating a solid comprising calcium chloride to produce a dechlorinated solid comprising calcium, and optionally curing the dechlorinated solid comprising calcium) S160; and optionally regenerating the leachable agent S170.

The method is used to extract pozzolans (also known as Supplementary Cementitious Materials (SCMs)) and/or other cementitious precursor materials (e.g., clinker, lime, slaked lime, tricalcium silicate, dicalcium silicate and calcium carbonate), magnesium compounds, and metals from non-limestone materials. Depending on the implementation and the type of non-limestone material, the method may have a number of variations, where the method may be modified for the desired input (i.e., the type of non-limestone material) and/or output (i.e., cement material and metal). Thus, in addition to having additional/alternative steps, method steps may be skipped, repeated, or altered depending on implementation requirements. The method may be particularly useful for processing calcium silicate rock, but may be implemented with any non-limestone material containing silicon and/or calcium.

In a modified embodiment, the method may be used to produce cement. In this embodiment, as shown in fig. 2, the method for producing cement and producing cement precursors comprises: obtaining a non-limestone material S110, wherein the non-limestone material comprises a material comprising elemental calcium and optionally silicon; producing a calcium-rich portion and a calcium-depleted portion from a non-limestone material S130, comprising dissolving at least calcium compounds, thereby producing a calcium-rich portion and a calcium-depleted portion of the non-limestone material, wherein dissolving the non-limestone material comprises adding at least one leaching agent S132; separating a calcium-depleted portion from a calcium-enriched portion S140, wherein the calcium-depleted portion may comprise a pozzolan; separating S150 the calcium-containing compound from the calcium-rich fraction (e.g., in the case of embodiments in which HCl is the leaching agent, producing a solid comprising calcium chloride); optionally decomposing a calcium compound (e.g., dechlorinating a solid comprising calcium chloride to produce a dechlorinated solid comprising calcium, and optionally curing the dechlorinated solid comprising calcium) S160; optionally regenerating the leachable agent S170; and wherein the decomposition comprises a calcium compound product from which clinker or cement S180 is produced.

This method is used to extract Supplemental Cement Material (SCM) and/or other cement precursor materials (e.g., clinker, tricalcium silicate, dicalcium silicate, lime or slaked lime) and metals from non-limestone materials and optionally convert the cement precursor materials to cement. Depending on the implementation and the type of non-limestone material, the method may have a number of variations, where the method may be modified for the desired input (i.e., type of non-limestone material) and/or output (i.e., type of cement and metal). Thus, in addition to having additional/alternative steps, method steps may be skipped, repeated, or altered depending on implementation requirements. The method may be particularly useful for processing calcium silicate rock, but may be practiced with any non-limestone material containing silicon and calcium. The method may be particularly useful for producing clinker or cement, such as Ordinary Portland Cement (OPC), and may be practiced for producing various types of portland cement (e.g., type 1 portland cement, type 2 portland cement, type 3 portland cement, type 4 portland cement, or type 5 portland cement, or the like), or more generally, other types of cement and cementitious materials (e.g., lime, slaked lime, mortar, fly ash, slag, tricalcium silicate, dicalcium silicate, and silica fume). Additionally or alternatively, the method may enable the production of any compound comprising amorphous silica, calcium oxide (CaO) and/or magnesium oxide (MgO) as starting material.

In some variations, the method may include additional or alternative steps. Additional steps may involve treating materials, regenerating compounds, treating waste, and/or improving other reactions. Additional/alternative steps may be combined to achieve the desired implementation. Examples of additional/alternative steps include: electrolytic reagents/materials, thermal decomposition or thermal hydrolysis reagents/materials or solutions, precipitation of reagents/materials, application of contact processes, and synthesis of reagents/materials, electrolysis of water to produce acids and bases, or only acids or bases, for dissolution of the starting rock and/or separation of calcium species. In many variations, the method may include a calcium enrichment step. That is, the method may include: the non-limestone material S120 is enriched, resulting in a material having a higher concentration of calcium than the original material. In many variations, the method may also implement a carbon capture/sequestration step. That is, the method may further comprise: and (5) washing the flue gas.

Starting materials

Block S110 includes obtaining a non-limestone material for obtaining starting material for the process. Obtaining the non-limestone material S110 may include any general process for obtaining non-limestone material, such as mining, purchasing, searching, receiving, etc., the non-limestone material.

In general, any suitable starting material may be used as long as it contains a sufficient amount of calcium to provide the desired end product, e.g. clinker or cement, such as final portland cement. If a method is used that also produces a Supplemental Cementitious Material (SCM), the starting material will also contain one or more compounds that can provide a final material that contains amorphous (non-crystalline) compounds that can be used as SCM. These may include amorphous silica, in which case the starting material will also comprise silicon. However, other materials may provide amorphous compounds that act as SCMs, such as amorphous iron and alumina compounds, as known in the art; in these cases, the starting material includes the necessary starting elements. In certain embodiments that produce both clinker or cement (e.g., portland cement) and SCM, the starting material includes non-limestone rock and/or minerals that include calcium and silicon, such as rock and/or minerals that include calcium silicate. Any suitable rock and/or mineral may be used, such as one or more of basalt, gabbro, pyroxene, clinohte, sika, amphibole, or combinations thereof.

In certain embodiments, non-limestone materials are used. As used herein, "non-limestone material" includes materials that contain small amounts of calcium carbonate (e.g., limestone), such as less than 10% calcium carbonate; generally, lower amounts of calcium carbonate are preferred to avoid carbon dioxide production in the various steps; however, many materials, such as non-limestone rock and/or minerals, may contain some amount of calcium carbonate and are suitable for use in the methods and apparatus described herein. The non-limestone material may be rock and/or minerals, or industrial waste, or a combination thereof. The non-limestone material contains calcium and typically contains silicon. Preferred starting non-limestone starting materials comprise at least 10% calcium, more preferably at least 15% calcium, even more preferably at least 25% calcium. Preferred starting materials comprise less than 30%, 25%, 20%, 15%, 10%, 5%, 2% or 1%, for example less than 10% or less than 5% calcium carbonate.

In some variations, the non-limestone material comprises silicate rock, but may generally comprise any one or more non-limestone materials, wherein the materials together contain calcium and optionally silicon. Non-limestone materials may be found/selected to additionally include any group of desired compounds (and/or unknown compounds). In addition to calcium and optionally silicon, the non-limestone material may also include other minerals and/or compounds. Examples include calcium compounds (e.g., calcium oxide), magnesium compounds (e.g., magnesium oxide), aluminum compounds (e.g., aluminum oxide), iron compounds (e.g., iron (II) oxide, iron (III) oxide), silicates (e.g., silica), and carbon compounds (e.g., carbon dioxide). Examples of silicate rock may include: clinoptilolite, sika, gabbro, pyroxene, olivine kalioplast, basalt, cupronite, tungsten-silicide-kate, fly ash, slag, old cement, concrete, quarry rock and tailings. Examples of other rocks may include: mafic rock and super mafic rock. More generally, suitable non-limestone rocks and/or minerals include basalt, igneous apatite, silica fume, anorthite, montmorillonite, bentonite, anorthite, diopside, pyroxene, ma Fudan (mafuhte), ka Ma Fudan (kamafuhte), monoclinic pyroxene, colemanite, plain pyroxene, volatile pyroxene, pearl mica, serpentine calcium, garnet, scheelite, skarnite, limestone, natural gypsum, apatite, fluorapatite, or any combination of these. Other suitable rocks and/or minerals will be apparent to those skilled in the art. The non-limestone material may also contain one or more industrial products, such as one or more industrial wastes.

In some variations, obtaining the non-limestone material S110 may include obtaining a processed, partially processed material. That is, the non-limestone material may initially be obtained and processed for some other reason and then transferred to this process (e.g., for salt extraction). In variations involving processed or partially processed non-limestone material, method steps may be added or skipped depending on the non-limestone material content. For example, in one example where some metals have been extracted, the separation step (e.g., precipitation) and the decomposition (e.g., thermal decomposition) step may be modified or skipped. In another example, an enrichment step (e.g., enrichment of non-limestone material S120) may be added to use a fairly depleted non-limestone material.

In some variations, the method may include block S120, enriching for non-limestone material. The effect of enriching the non-limestone material is to increase the calcium concentration of the non-limestone material. This is particularly useful for previously processed rock where minerals or compounds have been extracted. For example, flotation, magnetic separation, and other physical and chemical separation methods can be used to remove the calcium-depleted portion of the rock.

Non-limestone materials, such as rock and/or minerals, may be processed to provide particles in a desired size range. Any suitable method may be used, such as crushing, grinding and/or milling, sieving, and the like. Suitable size ranges include 1-500u, 5-300u, 10-200u, 20-130u, 45-90u, or combinations thereof. In a preferred embodiment, the size range is 20-130u. In a more preferred embodiment, the size range is 45-90u.

Producing calcium-rich and calcium-depleted fractions

Block S130 includes generating calcium-rich and calcium-depleted portions from the non-limestone material that function to decompose the non-limestone material to separate calcium compounds from non-calcium compounds (e.g., SCM). Block S130 may include dissolving the non-limestone material, including at least dissolving calcium compounds within the non-limestone material, thereby producing a calcium-rich portion and a calcium-depleted portion. In this way, the dissolved non-limestone material S130 may partially dissolve the non-limestone material such that the silica and silica compounds remain in a solid state, with other compounds (e.g., attached to the calcium) being dissolved.

Dissolving the non-limestone material S130 may include adding a leaching agent S132. The leaching agent may comprise a single compound, multiple compounds, and/or a series of compounds. In certain embodiments, the leaching agent comprises a single compound, such as HCl. The leaching agent may act to at least partially dissolve the non-limestone material. The leaching agent may be water, a metal salt, an acid and/or an oxidizing agent. In general, the leachables may have the following limitations: wherein the leachable agent dissolves calcium compounds in the non-limestone material. In some variations, the leachable agent comprises a replenishable compound.

In one example, the leaching agent is an acid, i.e., a first acid. In certain embodiments, only one acid is used, e.g., only HCl. The first acid is used to dissolve calcium compounds within the non-limestone material. In addition, the first acid may dissolve non-silicate compounds (e.g., metals and salts) in the material, thereby producing a calcium-depleted solid fraction, such as a silicate-based solid fraction and a mineral-based liquid fraction (calcium-enriched liquid fraction). Alternatively, the first acid may dissolve the silicate material. The first acid is preferably a strong acid, but may also comprise weak acids or protons generated at the anode, including protons generated by water splitting. In one variation, the first acid comprises hydrochloric acid (HCl). In one variation, the first acid consists essentially of HCl. In another variation, the first acid comprises hydroiodic acid (HI). Examples of other first acids may include: hydrobromic acid, nitric acid and hydronium ions generated by electrolysis of water. In one variation, HCl may dissolve metals in the non-limestone material, producing a metal-rich liquid fraction (calcium-rich liquid fraction).

In certain embodiments, a non-limestone material, such as rock and/or mineral material, is contacted with a strong acid to form a slurry comprising acid and rock and/or mineral. Any suitable strong acid may be used, for example HCl, HBr, HI, H ₂ SO ₄ Or HNO (HNO) ₃ . In certain embodiments, the strong acid comprises HCl; HCl may be the only strong acid used in the procedure. It will be appreciated that in general in such embodiments, other acids may be used for non-essential functions, such as cleaning equipment and the like, but the acid used to dissolve the non-limestone material is HCl. HCl is particularly useful because it produces chlorides, such as calcium chloride, which is a useful starting material for additional steps in the process. HCl is also suitable for relatively simple regeneration at one or more points in the process. For convenience, the remainder of the process will be described in terms of HCl; as will be apparent to those skilled in the art, if in addition to HClAnother acid is used or as an alternative to HCl, then appropriate adjustments may be made to accommodate the additional/alternative acid.

Non-limestone materials, such as rock and/or minerals, such as silicate rock materials, are dissolved in hydrochloric acid (HCl). In certain embodiments, the proportion of the strong acid comprising HCl is at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99% of the strong acid. In certain embodiments, 100% of the strong acid is HCl. Any suitable concentration of HCl may be used, such as 5-40%, 10-37%, 10-30%, 15-35%, 17-23%, 20-30%, or about or exactly 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, such as about or exactly 20%. In a preferred embodiment, the HCl is 10-37%. In a more preferred embodiment, the HCl is 15-35%. The ratio of starting material (e.g. solid rock and/or minerals) to leaching agent (e.g. liquid, e.g. acid) in the initial pulp may be any suitable ratio; it will be appreciated that some solid rock and/or minerals will immediately begin to dissolve in the acid and that these ratios will change as the solids dissolve into solution. Suitable initial ratios may be within the following ranges: 5% solids/95% liquid to 40% solids/60% liquid, e.g., 10% solids/90% liquid to 30% solids/70% liquid; in a preferred embodiment, 15% solids/85% liquid to 25% solids/75% liquid, e.g., 20% solids/80% liquid.

The pulp is treated to dissolve at least a sufficient amount of calcium compounds in non-limestone materials (e.g. rock and/or minerals) into solution to provide a satisfactory end product, for example conversion to clinker or cement, for example portland cement. In certain embodiments, at least 50%, 60%, 70%, 80%, 90%, 95% or 100%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90% of the calcium in the starting material goes into solution. The treatment may be performed during an open or at least non-pressurized process to the atmosphere. The treatment may include heating and/or maintaining the slurry at a temperature or temperature range for a period of time. In general, the duration and/or temperature of the treatment may be used to provide the desired dissolution. Maintaining the pulp at a suitable temperature range including 60-115 ℃, 80-115 ℃, 90-115 ℃, 100-115 ℃, 60-112 ℃, 80-112 ℃, 90-112 ℃, 100-112 ℃, 60-110 ℃, 80-110 ℃, 90-110 ℃ or 100-110 ℃; it will be appreciated that the boiling temperature of the HCL solution may be above 100 ℃ due to the high concentration of HCL present and when the material is dissolved in the liquid phase. Thus, in certain embodiments, the temperature is at least 95, 96, 97, 98, 99, or 100 ℃; in a preferred embodiment, the temperature is at least 90 ℃; in a more preferred embodiment, the range temperature is at least 95 ℃; in a more preferred embodiment, the temperature is at least 98 ℃; and in an even more preferred embodiment, the temperature is at least 100 ℃. In certain embodiments, the maximum temperature is 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, or 115 ℃; in a preferred embodiment, the maximum temperature is 105 ℃; in a more preferred embodiment, the maximum temperature is 108 ℃; in another more preferred embodiment, the maximum temperature is 110 ℃. In certain embodiments, the temperature is reached and/or maintained at 100-115 ℃. In certain embodiments, the temperature is reached and/or maintained at 100-110 ℃. In certain embodiments, the temperature is reached and/or maintained at 100-115 ℃. Any suitable duration of treatment may be used. This may depend to some extent on the calcium content of the starting material, e.g. non-limestone rock and/or minerals; materials with lower calcium content may take longer to treat to obtain the desired amount of calcium salt in solution. Thus, the duration of the treatment may be at least 1, 2, 3, 4, 5, 6, 7, 8 or 10 hours and/or no more than 2, 3, 4, 5, 6, 7, 8, 10, 12, 15, 20, 24, 30, 36, 40, 48, 60 or 72 hours. In certain embodiments, the duration may be 2-24 hours, such as 4-18 hours or even 4-12 hours or less. In certain embodiments, the duration may be from 6 to 72 hours, such as from 4 to 48 hours, or from 4 to 36 hours, or from 4 to 24 hours. The slurry may be agitated during the treatment, such as stirring, for example, at 10-1000RPM, 20-800RPM, 50-500RPM, 50-400RPM, or 100-300 RPM. In a preferred embodiment, the slurry is stirred at 50 to 400RPM, more preferably 100 to 300 RPM. Other agitation methods known in the art may be used. A calcium-depleted fraction (solids) and a calcium-enriched fraction (liquids) are produced from the pulp. Some acids, such as HCl, may be converted to a gas or vapor phase during the process and may be recaptured and returned for use as a leaching agent.

In some variations, adding the first acid may include adding an organic acid or a biological acid (e.g., oxalic acid). The addition of the organic first acid can selectively leach out non-limestone material, thereby enabling selective extraction of metals. Examples of organic acids that may be incorporated include: propionic acid, butyric acid, citric acid, succinic acid, malic acid, tartaric acid and oxalic acid. In one example, the first organic acid may selectively leach all minerals from the non-limestone material (e.g., by thermal decomposition). In another example, the organic first acid may selectively leach all minerals except calcium from the non-limestone material.

In some variations, microorganisms may be used to produce the first organic acid. Microorganisms can be engineered to utilize CO ₂ Organic acid is produced as a carbon source, and thus, CO produced by decomposing the organic acid in a subsequent step ₂ By combining this CO ₂ Is fed to the microorganism to be recycled or reduced.

Separating the calcium-rich fraction from the calcium-depleted fraction

Block S140 includes separating the calcium-depleted portion from the calcium-enriched portion, which functions to separate the solid portion and the liquid portion produced from the non-limestone material. In many variations, the calcium-depleted portion comprises a pozzolan. In some variations where a first acid leaching agent (e.g., HCl first acid) is added, this will include separating the solid portion silicate rock (calcium-depleted portion) from the dissolved liquid portion (calcium-enriched portion), thereby extracting SCM from the metals in the non-limestone material. Any suitable separation method may be implemented. In some variations, block S130 may also include drying the separated solid portion (e.g., drying SCM). Additional or alternative acids to HCl may include HBr, HI, HNO ₃ Or any acid that produces a soluble calcium salt.

In many variations, separating S140 the calcium-depleted portion from the calcium-enriched portion occurs after some and/or all portions of block S130. In some variations, separating the calcium-depleted portion from the calcium-enriched portion S140 may occur prior to or concurrent with dissolving the non-limestone material. This may occur by mechanical separation (e.g., separation by physical grinding of components, separation by density, etc.) and/or electrostatic separation of the calcium-enriched and calcium-depleted contents prior to dissolution of the non-limestone material.

In some variations, separating the calcium-depleted portion from the calcium-enriched portion is accomplished by filtering the non-limestone material S140. Filtration may be used to separate solid and liquid debris. In one implementation, vacuum filtration is used, wherein a pressure differential is used to cause fluid to flow through the filter. In another implementation, thermal filtration is used, wherein the solution is heated and then forced through the filter. In another implementation, cold filtration is used, wherein the solution is first cooled to crystallize additional components (e.g., SCM), and then filtered.

In some variations, a filter press is employed to separate the solid portion. The filter press can enable stacking of multiple filter elements and allow easy opening of the filter to remove filtered solids. The filter press may be implemented with any desired filtration process as described above.

Separating the calcium-depleted portion from the calcium-enriched portion S140 may significantly consume the volume of the liquid portion. Thus, before or once this occurs, additional solution may be added to the calcium-rich portion to replenish the volume. This may occur in any separation and/or precipitation step. Additional solutions may be added at any step to maintain the desired working volume.

Block S150 includes separating calcium compounds from the calcium-rich portion, for example, to form a solid comprising calcium chloride, which functions to separate calcium compounds from the non-limestone material. In addition, block S150 may include separating out other metal compounds, which may or may not be part of the calcium compound. Block S150 may be implementation specific and may vary depending on the desired metal extraction and/or mineral content of the non-limestone material. For example, in some variations, separating the calcium compound S150 from the calcium-rich portion includes precipitating the calcium compound from a liquid or liquid-like mixture. In addition, block S150 may depend on previous method steps. For example, the specific details of block S150 may be altered using HI as the first acid leachable agent as compared to HCl. In general, separating calcium compounds from the calcium-rich fraction S150 may include: changing thermodynamic conditions (e.g., increasing or decreasing temperature, increasing or decreasing pressure, increasing or decreasing compound concentration), adding an acid or base, and/or adding an oxidizing or reducing agent. In certain embodiments, for example, wherein HCl is an acid, separating the calcium compound comprises dehydrating the calcium-rich liquid portion (optionally after treating the calcium-rich liquid portion to remove one or more non-calcium compounds) to produce a solid comprising calcium chloride.

Treatment of calcium-rich fraction

Thus, the calcium-rich fraction is subjected to further treatment; in certain embodiments, the end result of the further treatment is the production of clinker or cement, such as portland cement, and typically regenerating the acid. In addition, depending on the treatment of the calcium-rich fraction, certain non-calcium species may be produced, such as species containing one or more of iron, aluminum and/or magnesium. Further processing may depend on the possible composition of the calcium-rich fraction, which in turn may depend at least in part on the starting material.

In general, the calcium-rich portion will contain a non-calcium salt, also referred to herein as a metal compound, in addition to the calcium salt (e.g., calcium chloride), and the subsequent procedure may depend on the ratio of the non-calcium salt (metal compound) to the calcium salt, or the desired ratio, which may be based at least in part on the starting material. If the proportion of the one or more non-calcium salts is above a certain threshold in the calcium-rich portion, the calcium-rich portion may be treated to remove at least a portion of the one or more non-calcium salts, e.g., to bring the level of calcium salts in the calcium-rich portion below the threshold. The threshold value may be determined by, for example, the desired composition of the end product, such as clinker or cement, such as portland cement. For example, certain non-calcium substances, such as derivatives of iron, aluminum and/or magnesium salts, may be allowed to be present in the clinker or cement (e.g. portland cement), but only below a certain level, typically depending on the type of cement (e.g. type 1, 2, 3, 4 or 5) and/or the criteria to be met, as the criteria may vary depending on the geographical location. The threshold may be based at least in part on the desired level of non-calcium salt derived materials (e.g., aluminum, iron, and/or magnesium species) in the final clinker or cement (e.g., the further processed portland cement product).

In certain embodiments, the calcium-rich fraction is not treated to remove non-calcium salts. This occurs if the calcium compound content of the starting material is particularly high; an exemplary such starting material is silica fume. In such cases, the calcium-rich portion treatment typically involves removal of water to produce a solid calcium salt, and further treatment to convert the calcium salt to a desired end product, such as clinker or cement, e.g., portland cement. Such processing is described further below.

In certain embodiments, the calcium-rich fraction is treated to remove one or more non-calcium salts. Any suitable treatment or combination of treatments may be used so long as a sufficient amount of the non-calcium salt is converted to a form that is separable from the calcium-rich fraction, such as to a solid form. The treatment or combination of treatments may also regenerate at least a portion of the original strong acid, such as HCl. It is not necessary to remove all non-calcium salts as long as the proportion remaining in the solution is below the threshold proportion. In certain embodiments, the calcium-rich portion is raised to and/or maintained at one or more temperatures or temperature ranges to cause formation of one or more insoluble non-calcium species from the one or more non-calcium salts. Additionally or alternatively, in certain embodiments, the calcium-rich fraction is treated with one or more substances (e.g., one or more bases), which causes the formation of one or more insoluble non-calcium substances from the one or more non-calcium salts.

Thus, the calcium-rich fraction may contain soluble non-calcium salts, such as salts of Al, fe and/or Mg, which may also be referred to as metal-containing compounds. Separating the calcium-containing compound from the calcium-rich fraction S150 includes precipitating the metal-containing compound. In certain embodiments, this includes a one-step thermal decomposition (thermal hydrolysis) process. In certain embodiments, this includes a multi-step thermal decomposition (thermal hydrolysis) process, such as a two-step thermal decomposition (thermal hydrolysis) process. In certain embodiments, this includes adding a base. In certain embodiments, one-step thermal decomposition (thermal hydrolysis) and addition of a base are used. In certain embodiments, two-step thermal decomposition (thermal hydrolysis) and addition of a base are used. In certain embodiments, only the addition of base is used. Generally, at least some of the strong acid, e.g., HCl, is also regenerated in the process.

In certain embodiments, the calcium-rich portion is raised to and/or maintained at a temperature or temperature range (one-step thermal decomposition or thermal hydrolysis) to form a set of insoluble non-calcium materials that can be removed from the calcium-rich portion. The temperature or temperature range may be a temperature at which one or more non-calcium salts (e.g., at least iron and aluminum salts) form insoluble materials (e.g., insoluble iron and aluminum materials). Other non-calcium salts that may form insoluble materials include boron salts, lithium salts, rubidium salts, cesium salts, strontium salts, barium salts, and/or radium salts. The temperature may be any suitable temperature or temperature range, for example at least 140, 145, 150, 155, 160, 165, 170, 175, or 180 ℃ and/or no more than 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, or 195 ℃; in certain embodiments, the calcium-rich fraction is heated to 140-195 ℃; in a preferred embodiment, the calcium-rich fraction is heated to 140-185 ℃; in a more preferred embodiment, the calcium-rich fraction is heated to 160-185 ℃, or even 175-185 ℃. In certain embodiments, the calcium-rich portion is heated to at least 1600 ℃, such as at least 170 ℃, such as at least 175 ℃, and in certain cases at least 180 ℃. Any suitable method of bringing the calcium-rich portion to and/or maintaining it at the desired temperature may be used; methods of heating and/or maintaining a solution at a temperature or temperature range are well known in the art. The calcium-rich solution may be maintained at or near the desired temperature for a suitable duration, such as at least 0, 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, or 10 hours, and/or no more than 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, 10, or 15 hours. In certain embodiments, the calcium-rich portion is maintained at or near the desired temperature for 10 minutes to 5 hours, such as 30 minutes to 4 hours, and in some cases 1 to 3 hours. HCl gas is driven off when the calcium-rich fraction is heated and/or maintained at a high temperature. Part or all of this gas can be captured and dissolved in water Regenerating HCl in the medium; in certain embodiments, HCl gas is captured and returned to an aqueous medium, such as HCl solution, which is used or will be used as a leaching agent for treating subsequent calcium-containing material. Insoluble material produced by increasing the temperature may be separated from the remaining calcium-rich fraction by any suitable means, such as centrifugation, filtration, and the like. The insoluble material may comprise one or more compounds of aluminium and/or iron, such as oxides, hydroxides, oxyhydroxides, silicates, silicate hydrates or complex phases containing Mg, al, fe, ca and any of Si, O and H, such as Al (OH) ₃ 、Al ₂ O ₃ 、AlO(OH)、Fe(OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc.

In certain embodiments, a two-step thermal decomposition (thermal hydrolysis) process is used. This is achieved by: firstly, performing two-step thermal decomposition; the mixture is first heated to a temperature or temperature range such that an aluminum salt, such as AlCl ₃ Formation of insoluble aluminium species, e.g. Al (OH) ₃ 、Al ₂ O ₃ AlO (OH) and the like, but iron salts, e.g. FeCl ₂ And/or FeCl ₃ Without formation of insoluble material, e.g. Fe (OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc., or substantially no insoluble material is formed. In certain embodiments, the first temperature is less than 150 ℃, preferably less than 145 ℃, even more preferably less than 140 ℃. In certain embodiments, the first temperature is 130-145 ℃, 131-144 ℃, 132-141 ℃, 133-139 ℃, or 135-137 ℃, such as about or exactly 136 ℃, or such as about 140 ℃. Any suitable method of bringing the calcium-rich portion to and/or maintaining it at the desired temperature may be used. The calcium-rich solution may be maintained at or near the desired temperature for a suitable duration, such as at least 0, 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, or 10 hours, and/or no more than 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, 10, or 15 hours. In certain embodiments, the calcium-rich portion is maintained at or near the desired temperature for 10 minutes to 5 hours For example 30 minutes to 4 hours, in some cases 1 to 3 hours. The process produces insoluble, e.g., oxidized, aluminum species, e.g., oxides, hydroxides, oxyhydroxides, silicates, silicate hydrates, or composite phases containing any of Al, ca and Si, O and H (e.g., forming Al (OH) ₃ 、Al ₂ O ₃ AlO (OH), etc.). HCl is also regenerated as described for the one-step thermal decomposition process. Insoluble aluminum (e.g., alumina) may then be separated from the calcium-rich partial solution; they may be further processed, for example dried. The remaining solution is then brought to a second temperature or temperature range at which one or more non-calcium salts, e.g., at least iron salts, form insoluble materials, e.g., oxides, hydroxides, oxyhydroxides, silicates, silicate hydrates, or complex phases containing any of Fe, ca and Si, O, and H, e.g., fe (OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc. The temperature may be any suitable temperature or temperature range, for example at least 140, 145, 150, 155, 160, 165, 170, 175, or 180 ℃ and/or no more than 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, or 195 ℃; in certain embodiments, the remaining solution is heated to 140-195 ℃; in a preferred embodiment, the remaining solution is heated to 145-190 ℃; in a more preferred embodiment, the remaining solution is heated to 145-185 ℃, in a preferred embodiment, 165-185 ℃, and in a more preferred embodiment, 175-185 ℃. In certain embodiments, the remaining solution is heated to at least 145 ℃, such as at least 150 ℃, in certain cases at least 155 ℃, such as a second heating step to about 180 ℃. Any suitable method of bringing the calcium-rich portion to and/or maintaining it at the desired temperature may be used. The calcium-rich solution may be maintained at or near the desired temperature for a suitable duration, such as at least 0, 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, or 10 hours, and/or no more than 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, 10, or 15 hours. In certain embodiments, the plant will be rich The calcium portion is maintained at or near the desired temperature for 10 minutes to 5 hours, for example 30 minutes to 4 hours, in some cases 1 to 3 hours. This temperature is used to form insoluble, e.g. oxidized, iron species (e.g. Fe (OH) forming) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc.) and simultaneously regenerating the HCl first acid as in the first heating step. Insoluble Fe may then be separated from the calcium-rich partial solution; it may then be further processed, for example dried.

In certain embodiments, the calcium-rich fraction is treated with one or more bases to form a set of insoluble non-calcium materials that can be removed from the calcium-rich fraction. HCl may also be regenerated during the base addition. In certain embodiments, this is the only process used to cause the formation of insoluble non-calcium species (precipitated metal compounds). In certain embodiments, a one-step thermal decomposition process is used and a base is added. In certain embodiments, a two-step thermal decomposition process is used and a base is added. The base or bases may be any suitable base or bases, provided that the base or bases are strong and in an amount sufficient to precipitate the desired amount of the metal compound. In certain embodiments, the one or more bases comprise a calcium base, e.g., one or more calcium bases produced as a product in the process, e.g., caO, ca (OH) ₂ Or CaSi, such as dicalcium silicate and/or tricalcium silicate. In certain embodiments, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95% of the base comprises one or more products produced in the process, such as calcium base, e.g., caO, ca (OH) ₂ Or CaSi, such as dicalcium silicate or tricalcium silicate; in a preferred embodiment, at least 30%; in a more preferred embodiment, at least 80%; in another more preferred embodiment, at least 90%. In certain embodiments, 100% of the one or more bases comprise one or more products produced in the process, such as calcium bases, e.g., caO, ca (OH) ₂ Or CaSi, such as dicalcium silicate or tricalcium silicate. Some or all of the added base may be regenerated in other steps of the process, for example to produce CaO, dicalcium silicate and/or silicic acid, for exampleCalcium salt decomposition of tricalcium. In certain embodiments, a base is added to the calcium-rich fraction in a one-step process to precipitate all desired compounds, such as to precipitate Al, fe, and Mg compounds. In some processes, the base is added after some non-calcium salts (metal compounds) precipitate, for example by a one-or two-step thermal decomposition process; in such cases, sufficient base is added to precipitate the remaining metal compounds or a portion thereof (e.g., the remaining Fe and Mg compounds, or the remaining Mg compounds).

In certain embodiments, a base is added to precipitate Mg compounds. The precipitate may include one or more magnesium compounds, such as Mg (OH) ₂ Magnesium silicate hydrate, magnesium aluminum silicate and/or other magnesium compounds. The precipitate may be separated from the remaining calcium-rich fraction by any suitable method, such as the methods described herein. The precipitate may be further processed, for example by drying. The magnesium precipitate may be used to react with carbon dioxide, such as in a flue gas, for example, a flue gas produced as part of a process for powering the entire process (e.g., a flue gas from natural gas or coal combustion); and/or with atmospheric carbon dioxide and/or other carbon dioxide sources, such as bodies of water, e.g., oceans, to produce magnesium-carbon dioxide products, e.g., mgCO ₃ In some cases Mg (HCO) ₃ ) ₂ Thereby sequestering carbon dioxide. The amount of carbon dioxide sequestered thereby may reduce the total amount of carbon dioxide produced by the overall process, in some cases enough to render the overall process carbon neutral or even carbon negative. In addition, other substances in the flue gas, such as substances that need to be removed from the flue gas, such as SOx and/or NOx, may react with the Mg precipitates, in some cases reducing the content of one or more substances below what is required for the release of the flue gas into the atmosphere. Additionally or alternatively, the magnesium precipitate may sequester carbon dioxide from the atmosphere; any suitable arrangement may be used for this purpose. In certain embodiments, the magnesium precipitate optionally processed to increase surface area may simply be deposited in a pile, laid down in layers on the ground, or otherwise distributed in a suitable manner and allowed to sequester atmospheric carbon dioxide for a suitable period of time, which may be days, weeks, months, years or Over one year. In certain embodiments, the magnesium precipitate may be placed in an aqueous slurry/solution, where the magnesium precipitate is contacted with, for example, flue gas or the atmosphere. Additionally or alternatively, the magnesium precipitate may sequester carbon dioxide from a body of water, such as sea water; any suitable arrangement may be used for this purpose. In this case, soluble bicarbonate species can be formed, effectively doubling the carbon dioxide sequestration.

Decomposing calcium compounds

Block S160, which includes decomposing the calcium compound, serves to decompose the calcium compound (e.g., calcium chloride) into different calcium compounds, such as dechlorinated solids comprising calcium silicate, dicalcium silicate and/or tricalcium silicate, preferably into a usable form. Block S160 may additionally include decomposing other metal compounds. Examples include: magnesium compounds, aluminum compounds, and iron compounds. In some variations, decomposing includes performing thermal decomposition. For example, calcium carbonate is thermally decomposed into calcium oxide and carbon dioxide.

Additionally or alternatively, other types of decomposition (e.g., chemical decomposition, electrochemical decomposition) may be implemented. In some variations, block S160 includes electrochemically decomposing the calcium compound and the other metal compound by electrolysis. This can occur, for example, by electrolysis of sodium chloride using a chlor-alkali process.

In many variations, the resolved calcium compound S160 acts with the box S150. For example, in many variations, thermal decomposition is part of separating calcium compounds and/or other metal compounds. In these variations, block S160 may occur immediately before, concurrently with, or immediately after block S150.

For example, in some variations, block S160 may be incorporated to decompose and/or separate metal compounds (non-calcium compounds) from the calcium-rich portion S150 prior to separating the calcium compounds from the calcium-rich portion. In certain embodiments, one or more separate metals are used in the process, for example as a curing fluxing agent. This may serve to improve and/or simplify the separation of calcium compounds. In addition, this may enable a "purer" extraction of the extracted metal for reuse. In one example, the calcium-rich portionThermal decomposition or thermal hydrolysis is separately carried out to extract metals (e.g., aluminum and iron). Thermal decomposition or thermal hydrolysis may be implemented in any desired form, possibly depending on the system implemented (e.g., mechanical vapor recompression may be used to recombine heat generated from other parts of the reaction for thermal decomposition or water evaporation). In this example, the calcium-rich portion may be heated to 160-190 ℃, e.g., 175-180 ℃, e.g., about 180 ℃, to hydrolyze Al and Fe (e.g., to form Al (OH) ₃ 、Al2O ₃ 、AlO(OH)、Fe(OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc.). Additionally, thermal decomposition may aid in regenerating the leachable agent (e.g., regenerating HCl), as described below with respect to block S170. Hydrolysis of the metal effectively precipitates it from solution. Which may then be separated as another solid fraction from the calcium-rich fraction solution. The separated metal may also be sold as SCM with or without silica added. In certain embodiments, one or more separate metals are used in the process, for example as a curing fluxing agent.

In another exemplary implementation, block S160 may incorporate a two-step thermal decomposition prior to block S150. That is, the calcium-rich portion may be first heated to 125-145 ℃, such as 130-140 ℃, such as 135-140 ℃, and in some cases about 136 ℃, to hydrolyze the aluminum (e.g., form Al (OH)) ₃ 、Al ₂ O ₃ AlO (OH), etc.). The hydrolyzed aluminum solids may then be separated from the calcium-rich fraction. Once the aluminum is removed from the calcium-rich portion, the calcium may be heated a second time to 160-190 ℃, such as 175-185 ℃, such as about 180 ℃, to hydrolyze the iron (e.g., form Fe (OH)) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc.). In the same manner, the hydrolyzed iron solids may then be separated from the calcium-rich fraction. This two-step thermal decomposition allows the aluminum and iron to be separated more "clean" for potential reuse. In certain embodiments, one or more separate metals are used in the process, for example as a curing fluxing agent.

In the same manner as the single-step and two-step thermal decomposition, a multi-step decomposition (e.g., thermal decomposition) may be incorporated, depending on the composition of the calcium-rich portion and the desired output. For example, multi-step thermal decomposition may be incorporated to hydrolyze other metal compounds from the calcium-rich fraction.

In general, calcium chloride (CaCl) is the calcium-rich fraction after removal of metal compounds ₂ ) The content is very high, for example at least 70%, at least 80%, at least 90%, in some cases at least 95%, or even at least 99% calcium chloride. The calcium-rich fraction is also typically highly concentrated, e.g. 40% CaCl ₂ 60% water to 70% CaCl ₂ 30% water, or 50%/50% to 60%/40%, or even 55%/45% to 60%/40%.

Whether produced by an acid dissolution step, a one-step thermal decomposition, a two-step thermal decomposition, an alkali addition, or any suitable combination thereof, the resulting calcium compound (e.g., including calcium chloride retained in the calcium-rich portion) may then be processed to produce one or more additional products, such as clinker, e.g., clinker for portland cement. This may include removing water (dewatering) from the remaining calcium-rich portion containing the calcium compounds to provide a composition comprising one or more calcium compounds (e.g. one or more calcium salts, for example CaCl ₂ ) And treating the solids, for example converting them to a dechlorinated calcium compound, which may or may not comprise lime (CaO), and/or after further treatment to clinker, for example clinker for portland cement, comprising dicalcium silicate and tricalcium silicate.

Dewatering

The water may be removed from the calcium-rich portion by any suitable method, such as heating to evaporate the water into steam; some or all of the generated steam may be used in further processes requiring steam, as described below. The resulting calcium compound solid comprises one or more calcium salts, e.g. CaCl ₂ (solids comprising calcium chloride) and may also comprise non-calcium salts, such as iron, aluminum and/or magnesium salts, and/or other salts, provided that they are present in amounts that do not render the end product unsuitable for its intended use, for example as clinker or cement, such as portland cement, and/or interfere with the process used to produce the clinker or cement, such as portland cement.

The calcium compound solids, such as solids comprising calcium chloride, may be processed to produce particles of a desired size for further processing, such as by tabletting, grinding, or other suitable methods. It may then be treated to decompose the calcium-containing compound, for example to dechlorinate a solid comprising calcium chloride to produce a dechlorinated solid comprising calcium, which may or may not comprise CaO, and regenerate HCl; to produce clinker or cement, such as portland cement, the clinker may be further heated (sintered) in the presence of fluxes, such as fluxes providing Si, fe and Al, to produce clinker, which may be further processed to produce cement, such as portland cement. It should be appreciated that one or more materials or processes of the overall process may be set, adjusted, or selected to produce a desired end product. For example, the starting materials, the Ca: si ratio of the dichlorination/curing, the composition and/or amount of the curing fluxing agent, and/or the curing conditions may be adjusted to produce a clinker or cement, such as portland cement, that contains a desired range of dicalcium silicate, tricalcium silicate, and, in some cases, other materials that are desirably present (or absent) in the product. Thus, one or more materials or processes may be set, adjusted or selected to produce a clinker comprising 40-70% w/w, in a preferred embodiment 50-65%, in a more preferred embodiment 52-63% tricalcium silicate (C3S); and/or comprises 10-35% w/w, in preferred embodiments 15-25%, in some embodiments less than 15% dicalcium silicate (C2S). In certain embodiments, mgO is less than a certain threshold, for example less than 1.0%, or less than 0.6%. In certain embodiments, no more than 15%, 12%, 10% or 8%, for example no more than 8%, tricalcium aluminate (C3A) is present. It will be appreciated that functional features may be desirable and operable as an alternative or in addition to compositional features, such as compressive strength of cement or mortar at one or more points in time.

Dechlorination of

In certain embodiments, the calcium compound solids, such as solids comprising calcium chloride, are heated in the presence of steam, silica, and optionally a fluxing agent. Typically, no fluxing agent is required in this step, but fluxing agents may be added to the mixtureFor example, for convenience, for example, containing aluminium (e.g. Al (OH) ₃ ) And/or iron (e.g. Fe (OH) _x ) Is a flux of (a) a flux of (b). In certain embodiments, some or all of the silica, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99% silica, or 100% silica is silica produced from non-limestone rock and/or minerals, e.g., in an earlier step of the process, e.g., in the production of SCM (volcanic ash) as described herein. In certain embodiments, some or all of the fluxing agent, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99% of the fluxing agent, or 100% of the fluxing agent is iron and aluminum oxides, hydroxides, and possibly other suitable compounds produced from non-limestone rock and/or minerals, e.g., precipitated as insoluble salts, e.g., from calcium-rich fractions, in an earlier step of the process, as described herein. It will be appreciated that a calcium compound solid, such as a solid comprising calcium chloride, may comprise one or more substances that may act as fluxing agents, but it is generally preferred to add an exogenous fluxing agent. The heating may be performed in one step at a sufficiently high temperature to decompose the calcium-containing solids, e.g. solids comprising calcium chloride, and curing/sintering the resulting compound with a fluxing agent. In the simplest case, a calcium compound solid, such as a solid comprising calcium chloride, is heated to a sufficiently high temperature in the presence of steam and silica to decompose the calcium compound, produce HCl and age/sinter with a fluxing agent. In a preferred embodiment, the heating may be performed in two or more steps with successively higher heat, and the fluxing agent (if used) is present in all or only part of the steps (curing/sintering).

As previously mentioned, the calcium compound solids may comprise calcium chloride; in certain embodiments, it comprises at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%, for example at least 90%, in some cases at least 95% calcium chloride. The decomposition process dechlorinates calcium chloride in the solid, e.g., at least 90%, 95%, 97%, 98%, 99%, 99.1%, 99.5%, 99.9%, 99.91%, 99.95%, or 99.99% of the calcium chloride in the solid. Surprisingly, it has been found that at least 99%, 99.5%, 99.9% or even 99.95% of the calcium chloride can be dechlorinated and that these dichloride levels are such that the chloride content of the final product is sufficiently low to meet the standards for portland cement, e.g. the chloride content is less than 1%, or less than 0.1%, without further treatment. In a preferred embodiment, at least 99% of the calcium chloride in the solids is dechlorinated; in a more preferred embodiment, at least 99.9% of the calcium chloride in the solids is dechlorinated; in a more preferred embodiment, at least 99.95% of the calcium chloride in the solids is dechlorinated.

In certain embodiments, a calcium compound solid (e.g., a solid comprising calcium chloride) is heated in the presence of steam and silica to one or more temperatures or temperature ranges, wherein the one or more temperatures or temperature ranges are sufficient to drive the expulsion of chlorine gas from the solid; the chlorine combines with protons in the steam to regenerate HCl, which may be recycled as described previously. At the same time, the calcium chloride is converted to a dechlorinated calcium compound, which may or may not contain calcium oxide; typically, the dechlorinated compound comprises one or more silicates, such as dicalcium silicate. The temperature may be insufficient to produce tricalcium silicate, or only a small amount of tricalcium silicate.

One general reaction may be

CaCl ₂ +H ₂ O→CaO+2HCl

More generally, however, the reaction can be expressed as:

CaCl ₂ +SiO2+H ₂ o→calcium silicate and other substances +2HCl

Although it is possible to carry out the decomposition and curing/sintering at one temperature, it is preferred to carry out the decomposition and curing (e.g. sintering) in a multi-step process at a continuously higher temperature, wherein the material may be maintained at a given temperature for a certain duration, e.g. 0.5-5 hours, or 0.75-4 hours, or 1-3 hours, e.g. 1, 2 or 3 hours, and/or the temperature may be continuously increased at one or more suitable rates. This increases the efficiency and yield of dechlorination and the process achieves surprisingly high levels of dechlorination, as discussed elsewhere. In particular, in certain embodiments, silica is present during heating, e.g., a molar ratio of Ca to Si of 2.5 to 3.25; the heating may also be maintained at a controlled rate, e.g., no more than 80, 70, 60, 50, 40, 30, 25, 20, 15, 10, 5, 2, or 1 ℃/min, e.g., no more than 20 ℃/min, or no more than 10 ℃/min, after a threshold temperature, e.g., 700-750 ℃, e.g., 700, 710, 720, 730, 740, or 750 ℃, is reached, and the rate is maintained until a second threshold, e.g., 800-1000 ℃, e.g., 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, or 1000 ℃, is reached. In some cases, the material may be held at one or more temperatures or temperature ranges for one or more durations before continuing. The exact rate and threshold may depend on the material and other conditions. Additionally or alternatively, the temperature may gradually increase from one temperature to the next. The heating may be performed in any suitable system, such as a fluidized bed or kiln; in a preferred embodiment, the heating is performed in a kiln, such as a rotary kiln.

Accordingly, provided herein is a process for dechlorinating calcium chloride, the process comprising heating calcium chloride to a first temperature in the presence of steam, silica, and optionally a fluxing agent comprising iron and/or aluminum compounds (e.g., one or more of these iron and/or aluminum compounds), followed by 1) maintaining the calcium chloride and other components at the first temperature for a first duration to produce a first set of one or more products comprising at least HCl, and optionally removing HCl; heating the remaining first set of one or more products to a second temperature in the presence of steam to a second higher temperature and maintaining the one or more products and steam at the second temperature to produce a second set of one or more products comprising HCl and optionally removing HCl; optionally, an additional step of heating to, for example, a third temperature, followed in certain embodiments even to a fourth temperature, and maintaining at each temperature for a duration to produce a set of products (one of which is HCl); temperature, aluminum and/or iron compounds (if used; as described above, typically not required at this stage), silica, and duration may be as described; or 2) gradually heating the calcium chloride and other components from a first temperature to a second, higher temperature, wherein the heating rate is slow enough to allow for a desired level (e.g., maximum) of HCl production and dechlorination; wherein the calcium chloride is at least 95% dechlorinated, in a preferred embodiment at least 99.9% dechlorinated, and in a more preferred embodiment at least 99.95% dechlorinated.

In certain embodiments, a method for dechlorinating a solid comprising calcium chloride is provided, the method comprising (i) combining a solid comprising calcium chloride with a solid comprising silica; (ii) The combined calcium chloride and silica is heated to a temperature of 750-1250 ℃ in the presence of steam to produce HCl gas and a decalcified product. In certain embodiments, the temperature is 900 to 1250 ℃. In certain embodiments, the temperature is 1000-1250 ℃. In certain embodiments, the temperature is 1100-1250 ℃. In certain embodiments, when the temperature reaches 700-750 ℃, such as 700 ℃, in some cases 720 ℃, in some cases 750 ℃, the heating is performed at a rate of no more than 60 ℃, 50 ℃, 40 ℃, 30 ℃, 10 ℃, or 5 ℃ per minute until the temperature reaches 800-850 ℃. Without being bound by theory, it is believed that maintaining the rate at or below a certain level of threshold temperature and rate is based on avoiding or reducing melting of calcium chloride and ensuring that dichloride and/or reaction with silica can occur. In certain embodiments, the solid comprising calcium chloride and the solid comprising silica are combined such that a Ca-Si molar ratio of 1 to 4, preferably 2.5 to 3.5, more preferably 2.5-3.25 is achieved. In certain embodiments, the solids comprising calcium chloride are present at 50-90wt% and the silica is present at 10-40 wt%. In certain embodiments, the solid comprising calcium chloride comprises at least 80%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% calcium chloride. In certain embodiments, the solids comprising silica comprise at least 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, for example at least 60%, preferably at least 75%, more preferably at least 80% silica. In certain embodiments, the solid comprising calcium chloride comprises at least 90% calcium chloride and the solid comprising silica comprises at least 80% silica. In certain embodiments, the steam is present at 5 to 100 vol%. In certain embodiments, the chloride content is reduced by at least 80%, 90%, 95%, 96%, 97%, 98% or 99%; this may be accomplished by using a ramp to heat, hold the material at one or more temperatures for one or more durations, and/or other operations, as described herein. In certain embodiments, the dechlorinated calcium product comprises at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80wt% dicalcium silicate, in some cases at least 30%, such as at least 50% dicalcium silicate, and less than 30, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1wt% CaO, in some cases less than 10%, such as less than 5% CaO. In certain embodiments, the dechlorinated calcium product comprises at least 30% dicalcium silicate and less than 10% calcium oxide. The decalcified product may also contain less than 5% Cl, in some cases less than 1% Cl.

In certain embodiments, solid compositions are provided that comprise 1) solids comprising at least 50%, 60%, 70%, 80%, 90% or 95% calcium chloride, for example at least 90%, in preferred embodiments at least 95% calcium chloride; 2) Silicon dioxide; and optionally 3) a fluxing agent comprising one or more iron compounds, such as Fe (OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ One or more of the above, and/or one or more aluminum compounds, such as Al (OH) ₃ 、Al ₂ O ₃ One or more of AlO (OH). The composition may have the following components in the following proportions (wt-%): 50-90% calcium chloride solids; 10-40% silica; 0-4% of an iron compound used as a fluxing agent; 0-4% of an aluminum compound used as a fluxing agent. In a preferred embodiment, the ratio is 60-85% calcium chloride solids; 15-30% silica; 1-3% of an iron compound used as a fluxing agent; 1-3% of an aluminum compound used as a fluxing agent. In a more preferred embodiment, the proportion is 70-80% calcium chloride solids; 15-25% silica; 1-2% of an iron compound used as a fluxing agent; 1-2% of an aluminum compound used as a fluxing agent. In certain embodiments, all components are derived from a single source, e.gSuch as a single source comprising non-limestone rock and/or minerals.

The calcium compound solid is preferably heated to and maintained at a first temperature in the presence of steam and typically silica and optionally a fluxing agent, for example, HCl may be treated according to methods known in the art. In certain embodiments, the solid is heated to no more than 1250 ℃, such as 800-1250 ℃, in some cases 850-1000 ℃, in the presence of steam, silica, and optionally aluminum and iron containing compounds to produce HCl and products containing dechlorinated calcium compounds (e.g., including CaO in some cases). The solids may be heated in any suitable manner and system; such as a fluidized bed or kiln. In this and other steps, the silica may be combined with a calcium compound, such as CaCl ₂ Is present in any suitable ratio; for example, a 100-105g sample may contain about 80g CaCl ₂ About 20g of silica and optionally about 1-3g of aluminum and iron compounds. This is merely exemplary and it will be appreciated that the ratio of the various components may vary depending on the standards of the clinker or cement type (e.g., portland cement to be produced), as will be apparent to one of ordinary skill in the art.

The product containing the dechlorinated calcium compound (e.g. including CaO in some cases) may then be heated to a second temperature, and optionally then to a third temperature, and in some cases also to a fourth temperature, typically also in the presence of steam, silica (some or all of which may have formed silicate), and a fluxing agent, such as an aluminum and/or iron compound used as a fluxing agent; at the highest temperature or temperatures, steam may not be present. Thus, products containing dechlorinated calcium compounds (e.g., including CaO in some cases) are cured in a process that may include sintering, such as in the presence of a fluxing agent (e.g., an aluminum and/or iron-containing fluxing agent) to produce clinker, such as portland cement clinker. The term "curing" as used herein includes the process of treating solid materials at elevated temperatures to produce cement clinker; "curing" and "sintering" are generally synonymously used herein; the methods described herein can include various amounts of sintering, in some cases, without sintering, so long as the desired product is produced. The fluxing agent may include materials produced in an earlier step of the process, such as aluminum and/or iron compounds removed from the calcium-rich portion, as described above. In certain embodiments, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the exogenous flux comprising aluminum and/or iron comprises one or more compounds removed from the calcium-rich portion, such as at least 50%, in some cases at least 70%, and in certain embodiments at least 90%. In certain embodiments, 100% of the exogenous flux comprising aluminum and/or iron comprises one or more compounds removed from the calcium-rich portion. In certain embodiments, exogenous fluxes, such as clays and the like, which are not generated at an early stage of the process, are used, as is known in the art. Whether or not exogenous flux is present, and, if present, what amount can be determined, at least in part, by the desired final composition (e.g., type of portland cement produced). In certain embodiments, a fluxing agent comprising an iron-containing compound and an aluminum-containing compound is used.

If only a second temperature is used, the process involves heating a product containing a dechlorinated calcium compound (e.g., including CaO in some cases) to 1200-1550 ℃, preferably no more than 1450 ℃, in the presence of a fluxing agent, thereby forming a clinker, such as portland cement clinker comprising dicalcium silicate and tricalcium silicate; in some cases, the clinker or intermediate further comprises tricalcium aluminate and/or tetracalcium aluminoferrite. If an intermediate temperature is used, the temperature may be, for example, 900-1100 ℃, such as 950-1050 ℃; the temperature may be, for example, 1100-1300 ℃, such as 1150-1250 ℃; the temperature may be, for example, 1400-1600 ℃, such as 1450-1550 ℃. In an exemplary embodiment, the temperatures are 850, 1000, 1200, and 1500 ℃ in that order, each maintained for 1 hour. These are merely exemplary and one skilled in the art can determine the optimal or desired temperature sum.

During the heating process, a base, such as one or more calcium bases, used in the renewable base precipitation step, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 98%, or 99% of the amount of base used in the renewable base precipitation step.

At the end of the process, clinker may be retained, wherein the clinker may have a diameter of millimeters, for example 0.5-50mm, or 1-40mm, or 1-30mm; however, other dimensions are acceptable for further processing.

Accordingly, provided herein is a clinker, such as portland cement clinker comprising dicalcium silicate and tricalcium silicate, wherein the dicalcium silicate and tricalcium silicate are derived from non-limestone materials, such as non-limestone rock and minerals, for example, in a method as described herein. In certain embodiments, the calcium and silicate are derived from the same starting material, e.g., the same non-limestone material, e.g., non-limestone rock and/or mineral. As used herein, "dicalcium silicate" (also referred to herein as belite), C2S) and "tricalcium silicate" (also referred to herein as alite, C3S) include meanings known in the cement and concrete generation arts, e.g., tricalcium silicate may contain minor amounts of other ingredients, such as 3-4% substituent oxides; in addition to CaO and SiO2, dicalcium silicate may contain small amounts of other oxides.

Also provided herein are concretes comprising cement (e.g., portland cement, e.g., OPC) produced by one or more of the processes described herein, i.e., produced in a process that does not require calcination of limestone. In certain embodiments, the concrete may also comprise cement produced by conventional processes, i.e. processes requiring calcination of limestone, such as portland cement, e.g. OPC.

Also provided is a composition comprising calcium chloride (CaCl) ₂ ) A method of producing clinker from calcium compound solids, the method comprising: (a) Will contain CaCl ₂ Dechlorination of the calcium compound solids to produce a dechlorinated composition comprising Ca and having less than 10% w/w Cl; and (b) heating the dechlorinated composition in the presence of a fluxing agent to produce clinker. The clinker may comprise dicalcium silicate and tricalcium silicate, such as portland cement clinker, e.g., OPC clinker. The CaCl 2-containing composition may also contain silica; for example, the molar ratio of Ca to Si may be 1.0 to 5.0, preferably 2.0 to 4.0, more preferably 2.5 to 3.25.

Regeneration of leaching agents

Block S170 includes regenerating the leaching agent for replenishing the leaching agent implemented in the decomposition of the non-limestone material. In some variations, regenerating the leachable agent S170 may simply include adding a new leachable agent to replace the previously consumed leachable agent. Additionally or alternatively, a process (e.g., thermal, chemical, or electrical stimulation) may be performed in regenerating the leachable agent S170.

In embodiments where the leaching agent comprises a strong acid (e.g., HCl), at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 98%, or 99% of the initial acid, e.g., initial HCl, may be regenerated at the end of all acid regeneration steps (e.g., HCl regeneration). In a preferred embodiment, at least 80% of the initial HCl is regenerated. In another preferred embodiment, at least 90% of the initial HCl is regenerated. To provide sufficient acid, e.g., sufficient HCl, for subsequent treatment of the non-limestone material, a quantity of unrenewed strong acid, e.g., HCl, may be added back, i.e., topped up with strong acid, e.g., HCl.

In many variations, regenerating the leachable agent S170 may occur in conjunction with the block S160 as part of the decomposition process. For example, in one example, or may be evident thermal decomposition. For example, in one implementation, the calcium sulfite is thermally decomposed to produce calcium oxide and calcium silicate, while sulfur dioxide is regenerated.

Additionally or alternatively, regenerating the leaching agent may be a different process. For example, calcium sulfate can be thermally decomposed to produce calcium oxide or calcium silicate and sulfur dioxide. The sulphur dioxide must then be converted to sulphuric acid to regenerate the leachable agent.

Production of clinker or cement

In some variations, the method may include a cement generation step. That is, in variations in which the decomposition includes a calcium compound product (e.g., calcium oxide, dicalcium silicate, and/or tricalcium silicate), the method may include block S180, which includes producing cement from the calcium compound product. As previously mentioned, the type of cement produced may be implementation specific (e.g., ordinary portland cement). In many variations, producing cement may include curing/sintering calcium compound products and is used to produce cement. In other variations, producing cement S180 from the calcium compound product may include directly producing calcium silicate by thermal decomposition of silica or electrochemical intercalation into the calcium compound product. Alternatively, other processes may be performed to produce cement, wherein the process may depend on the type of calcium compound product and the desired cement yield.

In one embodiment, a method is provided that includes contacting a non-limestone material with a leaching agent to produce a pulp, and obtaining a calcium-rich liquid fraction and a calcium-depleted solid fraction from the pulp. See, for example, fig. 3. In a preferred embodiment, the non-limestone material comprises calcium and the acid is hydrochloric acid, producing a calcium-rich liquid fraction comprising calcium chloride. In certain embodiments, the non-limestone material comprises rocks and/or minerals, such as one or more rocks and minerals described herein. In certain embodiments, the method comprises treating a calcium-rich liquid portion comprising calcium chloride to produce a solid comprising calcium chloride, and dechlorinating the solid comprising calcium chloride to produce a dechlorinated solid comprising a calcium compound. In certain embodiments, the dechlorinated solids comprising calcium compounds are treated to produce clinker, which in some cases may be further treated to produce cement, such as ordinary portland cement. Various parameters of materials and/or conditions may be set, adjusted, and/or selected to produce a clinker that is processed into cement having desired properties, such as compositional properties, such as dicalcium silicate and/or tricalcium silicate and/or other components, and the like, within a desired concentration range, as described herein. The calcium-depleted solids portion may be separated from the calcium-enriched liquid portion. In certain embodiments, the non-limestone starting material comprises both calcium and silicon, and the calcium-depleted solid portion comprises silica, such as amorphous silica; the calcium depleted solids portion may be further processed for use as a Supplemental Cement Material (SCM), for example, by operations such as flushing, drying, and storage for further use. See, for example, fig. 4. The solids may also undergo processing, for example, to produce particles having a desired size or range of sizes. In certain embodiments, the calcium-rich liquid portion comprising calcium chloride comprises a non-calcium salt, such as an aluminum salt, an iron salt, and/or a magnesium salt, and treating the calcium-rich portion comprises treating the liquid to precipitate one or more insoluble aluminum, iron, or magnesium compounds. See, for example, fig. 5. The precipitation process typically includes contacting at least the calcium-rich liquid portion with a base, such as a calcium base, for example a calcium base comprising calcium silicate, such as dicalcium silicate and/or tricalcium silicate; in certain embodiments, at least some of the calcium base is provided by a subsequent operation, such as dichloride and/or maturation. In certain embodiments, the only precipitation step is a base precipitation step. Alternatively, the precipitation may also include one or more thermal hydrolysis steps, typically prior to the alkali precipitation, to precipitate the aluminum and/or iron compounds. A one-step thermal hydrolysis step may be used in which both aluminum and iron compounds may be precipitated, or a two-step thermal hydrolysis process may be used in which an aluminum compound is precipitated in the first step and an iron compound is precipitated in the second step; if thermal hydrolysis is used, typically the alkaline precipitation produces mainly magnesium species. The one-step and two-step thermal hydrolysis may be performed as described elsewhere. Depending on whether thermal hydrolysis is used or not and the magnesium content of the starting material, e.g. Ca/Mg ratio, more or less alkali may be used, so if the material from the final process is used as an alkali source, the amount may be e.g. 1/20 of the clinker (if the starting material is Ca: mg 20: 1) or even 1/2 of the clinker (e.g. if the starting material is 1: 1), but the material consumed early in the process may be replaced later in the process. Some HCl may be regenerated during the precipitation step. After one or more precipitation steps, the insoluble solids may be separated from the calcium-rich liquid comprising calcium chloride, and the calcium-rich liquid is partially dehydrated to produce solids comprising calcium chloride. The solid comprising calcium chloride may then be dechlorinated (see, e.g., fig. 6), e.g., by combining with silica, e.g., to provide a ratio of Ca to Si molar ratio of 1-4, e.g., 2-4, in a preferred embodiment 2.45-3.25, and in a more preferred embodiment 2.5-3.25, and heated in the presence of steam, e.g., 5-100% by volume steam. Some or all of the silica may be provided by a calcium-depleted solids portion, such as at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99%, or 100%. Some or all of the steam may be provided by a dehydration step, for example at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99%, or 100%. Dechlorination may be performed under the conditions described herein to produce a dechlorinated solid comprising a calcium compound; the dechlorinated solids may contain less than 10%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or 0.1%, preferably less than 5%, in some cases more preferably less than 1% w/w Cl. Dechlorination also produces HCl, which may be returned to the step of contacting the non-limestone material with acid. The dechlorinated solids may comprise one or more calcium silicate, such as dicalcium silicate or the like; dicalcium silicate may be present, for example, at least 1%, 5%, 10%, 20%, 30% or 40%, for example at least 5% w/w. Little or no CaO may be present in the dechlorinated solids, e.g. less than 10%, 5%, 3%, 2% or 1% w/w. The dechlorinated solids comprising calcium may be treated to produce clinker, for example by heating in the presence of a fluxing agent (see e.g. fig. 7), for example a fluxing agent comprising aluminium and an iron compound, for example aluminium and an iron oxide (which as used herein comprises a hydroxide). The conditions for producing clinker may be as described herein. In certain embodiments, some or all of the fluxing agent is provided by one or more precipitations, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99%, or 100%. In certain embodiments, some or all of the fluxing agent is provided by one or more exogenous substances, such as clay, or the like, for example, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99%, or 100%. The clinker thus produced comprises hydraulic calcium silicate, such as at least dicalcium silicate and tricalcium silicate; the conditions of the various steps (e.g., ca: si ratio for dechlorination and clinker production, flux composition for clinker production, etc.) may be adjusted to produce clinker having desired proportions of dicalcium silicate and tricalcium silicate, e.g., 40-70%, preferably 50-65%, e.g., 52-63%, tricalcium silicate (C3S); and 10-35%, such as 15-25%, dicalcium silicate (C2S). The clinker may also comprise tricalcium aluminate, e.g. 5-12%, and/or tetracalcium aluminoferrite (C4 AF), e.g. 6-12%. The process may also include processing the clinker to produce cement, such as portland cement, e.g., OPC. The cement thus produced can be used to produce concrete, for example by mixing with aggregate and water, and in some cases with SCM. Aggregate and/or SCM may also be produced from non-limestone materials. Setting and hardening are generally similar or identical to conventionally produced cements of the same composition, for example produced by calcining limestone followed by sintering the product. The processing may include classification and screening, for example, by crushing, grinding or milling, etc., and may also include adding one or more additional substances, such as gypsum.

Fig. 11 shows an exemplary process utilizing a single precipitation step (calcium base precipitation, where some or all of the calcium base is produced in the process). FIG. 12 shows an exemplary process of thermal hydrolysis precipitation followed by alkali precipitation using one or more of these.

In certain embodiments, insoluble magnesium species, such as magnesium silicate, magnesium hydroxide, etc., produced during the precipitation step of the above-described process or other processes described herein may be used to sequester carbon dioxide, such as atmospheric carbon dioxide and/or carbon dioxide that is a component of the flue gas produced in one or more combustion steps, to produce energy for the process (and in some cases, also sequester other components, such as SOx, NOx, and/or other components); the carbon dioxide reacts with the magnesium species to produce magnesium carbonate. In certain embodiments, the magnesium species may be placed in a body of water, such as the ocean, where they may form magnesium bicarbonate, thereby sequestering carbon dioxide twice the yield of magnesium carbonate; they may also produce a cushioning effect.

It will be appreciated that the methods provided herein may produce less carbon dioxide than conventional methods of producing cement that typically require calcination of limestone and sintering; calcination produces carbon dioxide from limestone, and both calcination and sintering combust from fuel to heat the material to produce carbon dioxide. Processes such as those provided herein do not use starting materials that contain significant amounts of calcium carbonate, and do not actually require any calcium carbonate, although some calcium carbonate may be present in non-limestone materials. Depending on the starting material (e.g., materials with higher magnesium content may produce more magnesium species to sequester carbon dioxide), particularly the fuel used to power the various steps (heating, etc.), as well as other factors (e.g., transportation, etc.), the carbon dioxide produced may be less than 80%, 70%, 60%, 50%, 40% or 30% of the amount of carbon dioxide produced in a conventional process using limestone to produce the same amount of equivalent cement. In certain embodiments, such as if coal is used as a fuel, methods such as those provided herein may produce less than 500kg carbon dioxide per 1000kg of cement produced. In certain embodiments, such as if natural gas is used as a fuel, methods such as those provided herein may produce less than 300kg carbon dioxide per 1000kg of produced cement. If one or more magnesium species produced in the process is used to sequester carbon dioxide, for example from flue gas, the atmosphere and/or when placed in a body of water such as the ocean, the carbon dioxide produced may be less than 250, 200, 150, 100 or 50kg carbon dioxide per 1000kg of cement produced. In certain embodiments, the process is carbon neutral or even carbon negative, e.g., at least 50, 75, 100, 125, 150, 200, 250, 300, 400, or 500kg carbon dioxide per 1000kg of cement produced; typically, if magnesium species are placed in a body of water (e.g., the ocean), either a small positive or a large negative carbon value will be produced, as bicarbonate can be produced, isolating two CO2 s per Mg. It will be appreciated that the reduced amount of carbon dioxide, or even negative carbon dioxide, compared to conventional processes may be converted to carbon credits. Such credit may be based on avoided carbon dioxide (e.g., as compared to a conventional process that produces the same amount of equivalent cement), and in some cases also on sequestered carbon dioxide (e.g., based on magnesium species produced in the process). The carbon dioxide produced and the carbon dioxide avoided and/or sequestered may be appropriately monitored/calculated and safeguarded to ensure compliance with existing standards and regulations.

Here, an exemplary implementation of the above method is given. These examples illustrate different potential implementations of the method without any additional limitations to the method. Although not explicitly included in all examples, any example may include additional enrichment steps (e.g., block S120) as needed or necessary, depending on the non-limestone material obtained.

In the first embodimentIn an example, obtaining a non-limestone material S110 includes obtaining a silicate rock material. Dissolving the non-limestone material S130 includes adding a hydroiodic acid (HI) first acid as a leaching agent. Thus, silicate rock material dissolves in HI. Separating the calcium-depleted portion from the calcium-enriched portion S140 includes separating a solid portion (mainly SiO ₂ ) Separated from the liquid portion; and then SiO ₂ Dried and packaged as SCM. The SCM may then be stored and packaged, sold, or used in any desired manner. Separating the calcium-containing compound from the calcium-rich fraction S140 includes precipitating the metal-containing compound. This occurs by: slowly add CaSiO ₃ And then adding Ca (OH), ca ₂ SiO ₄ 、Ca ₃ SiO ₅ Electrochemically generated hydroxide or NaOH, or a similar sufficiently strong base, to neutralize the HI first acid; precipitation of Al (OH) ₃ 、Fe(OH) _x And Mg (OH) ₂ The method comprises the steps of carrying out a first treatment on the surface of the Formation of CaI ₂ The method comprises the steps of carrying out a first treatment on the surface of the And then lowering the temperature to precipitate CaI ₂ And H ₂ O. The decomposition of the calcium compound S160 and the regeneration of the leaching agent S170 occur simultaneously by thermal decomposition of the calcium compound. Thermal decomposition of CaI ₂ Thus CaO, caSiO can be formed ₃ 、Ca ₂ SiO ₄ Or Ca ₃ SiO ₅ And regenerating the HI first acid. In cement production implementations, the first example may further include sintering the calcium oxide, including: caO and SiO in kiln ₂ 、Al(OH) ₃ And Fe (OH) _x Sintering to form the ordinary portland cement. In addition, the examples may include using Mg (OH) ₂ Scrubbing flue gas to produce MgCO ₃ . Additionally or alternatively, mg (OH) ₂ Can be placed in a waste heap where it can contact air and slowly convert to MgCO ₃ 。

In a second example, obtaining a non-limestone material S110 includes obtaining a silicate rock material. Dissolving the non-limestone material S130 includes adding hydrochloric acid (HCl) first acid. Thus, silicate rock material is dissolved in hydrochloric acid (HCl). Separating the calcium-depleted portion from the calcium-enriched portion S140 includes separating a solid portion (mainly SiO ₂ ) Separated from the liquid portion; and then SiO ₂ Dried and packaged as SCM, wherein the SCM can be used as desired (e.g., for cement generationFor storage, for sale). Separating the calcium-containing compound from the calcium-rich fraction S140 includes precipitating the metal-containing compound. This occurs by: slowly add CaSiO ₃ The method comprises the steps of carrying out a first treatment on the surface of the Addition of Ca (OH) Ca ₂ SiO ₄ 、Ca ₃ SiO ₅ Or a similar strong base, thereby neutralizing the HCl first acid; precipitation of Al (OH) ₃ 、Fe(OH) _x And Mg (OH) ₂ The method comprises the steps of carrying out a first treatment on the surface of the CaCl formation ₂ . Then adding leaching agent SO ₂ Thereby precipitating CaSO ₃ And regenerating HCl. The decomposition of the calcium compound S160 and the regeneration of the leaching agent S170 occur simultaneously by thermal decomposition of the calcium compound. Thus, caSO is thermally decomposed ₃ Can form CaO and CaSiO ₃ 、Ca ₂ SiO ₄ Or Ca ₃ SiO ₅ And regenerating SO ₂ . In cement production implementations, the second example may further include sintered calcium oxide, including: caO and SiO in kiln ₂ 、Al(OH) ³ And Fe (OH) _x Sintering to form the ordinary portland cement. In addition, the examples may include using Mg (OH) ₂ Scrubbing flue gas to produce MgCO ₃ . Additionally or alternatively, mg (OH) ₂ Can be placed in a waste heap where it can contact air and slowly convert to MgCO ₃ . Example two can be particularly useful for having high concentrations of Ca (OH) ₂ Is carried out by a single machine.

In a third example, obtaining a non-limestone material S110 includes obtaining a silicate rock material. Dissolving the non-limestone material S130 includes adding hydrochloric acid (HCl) first acid. Thus, silicate rock material is dissolved in hydrochloric acid (HCl) first acid. Separating the calcium-depleted portion from the calcium-enriched portion S140 includes separating a solid portion (mainly SiO ₂ ) Separated from the liquid portion; and then SiO ₂ Dried and packaged as SCM. Separating the calcium-containing compound from the calcium-rich fraction S150 includes precipitating the metal-containing compound. This occurs by: slowly add H ₂ SO ₄ Thereby forming CaSO ₄ And HCl; and additional HCl is added to precipitate metal chlorides (e.g., alCl) ₃ 、FeCl _x 、MgCl ₂ ). Decomposition of the calcium compound S160 may occur by thermal decomposition of the calcium compound. Namely, caO and CaSO are mixed ₄ Thermally decompose andregenerated SO ₂ . The regeneration leaching agent S170 occurs by thermally decomposing the metal-containing compound in the presence of water. I.e. AlCl ₃ 、FeCl _x 、MgCl ₂ And the HCl first acid is regenerated. In cement production variants, the third example may also include the use of Al ₂ O ₃ 、Fe ₂ O ₃ And SiO ₂ Thermal decomposition of CaSO ₄ Thereby producing ordinary portland cement and SO ₂ . In addition, the examples may include using Mg (OH) ₂ Scrubbing flue gas to produce MgCO ₃ . Additionally or alternatively, mg (OH) ₂ Can be placed in a waste heap where it can contact air and slowly convert to MgCO ₃ 。

In a fourth example, obtaining a non-limestone material S110 includes obtaining a silicate rock material. Dissolving the non-limestone material S130 includes adding hydrochloric acid (HCl) first acid. Thus, silicate rock material is dissolved in hydrochloric acid (HCl) first acid. Separating the calcium-depleted portion from the calcium-enriched portion S140 includes separating a solid portion (mainly SiO ₂ ) Separated from the liquid portion; and then SiO ₂ Dried and packaged as SCM. Separating the calcium-containing compound from the calcium-rich fraction S140 includes precipitating the metal-containing compound. This occurs by: naOH was slowly added to neutralize the first acid and precipitate Al (OH) ₃ 、Fe(OH) _x And Mg (OH) ₂ And forms NaCl; electrolysis of NaCl, thereby regenerating NaOH and forming H ₂ And Cl ₂ The method comprises the steps of carrying out a first treatment on the surface of the From H using synthesis units ₂ And Cl ₂ HCl was prepared. The synthesis unit comprises a typical synthesis unit for chlor-alkali processes. For example, for an HCl synthesis unit, the synthesis unit may include a synthesis unit using H ₂ Burning chlorine. In a cement-producing variant, the fourth example may further include a sintered calcium product comprising: caOH is put into kiln ₂ With SiO ₂ 、Al(OH) ₃ And Fe (OH) _x Sintering to form the ordinary portland cement. In addition, the examples may include using Mg (OH) ₂ Scrubbing flue gas to produce MgCO ₃ . Additionally or alternatively, mg (OH) ₂ In the waste heap where it can contact air and slowly convert to MgCO ₃ 。

In a fifth example, an organic acid or a biological acid is used as the leaching agent. In this example, obtaining a non-limestone material S110 includes obtaining a silicate rock material. Dissolving the non-limestone material S130 includes adding a leaching agent that is an organic acid first acid (e.g., oxalic acid). Any organic acid (e.g., oxalic acid) can selectively leach other metals (e.g., al, fe, and Mg) leaving most of the calcium compounds, or (unlike oxalic acid) selectively leach calcium leaving other metals. Separation of leached metal-organic acid complexes (e.g., metal oxalates) may be separated from waste source non-limestone materials using flotation. The organic acid metal complex may then be oxidized (e.g., burned) to produce carbon dioxide and metal oxide. Alternatively, if the calcium is leached, the calcium oxide may be oxidized and sintered to produce cement. Regenerating the organic acid leaching agent may include using engineered microorganisms, carbon dioxide, and sunlight. In implementations where calcium remains in the waste rock, the process steps may be repeated to better leach and precipitate the calcium.

In a sixth example, obtaining a non-limestone material S110 includes obtaining a silicate rock material. Dissolving the non-limestone material S130 includes using an electrolytic cell to decompose water or salt to produce acid at the anode and base at the cathode and react the acid with the non-limestone material. Thus, the silicate rock material is dissolved in the first acid generated by electrolysis, which may be hydronium ions, HCl, HBr and any sufficiently strong acid. Separating the calcium-depleted portion from the calcium-enriched portion S140 includes separating a solid portion (mainly SiO ₂ ) Separated from the liquid portion; and then SiO ₂ Dried and packaged as SCM. Separating the calcium-containing compound from the calcium-rich fraction S140 includes precipitating the metal-containing compound. This occurs by: slowly adding a base, which is generated at the cathode by water or salt decomposition, and which may be hydroxide ions, naOH, ca (OH) ₂ Or any other base strong enough to neutralize the first acid and precipitate Al (OH) ₃ 、Fe(OH) _x 、Mg(OH) ₂ Finally Ca (OH) ₂ . In a cement-producing variant, the sixth example may further include a sintered calcium product comprising: caOH is put into kiln ₂ With SiO ₂ 、Al(OH) ₃ And Fe (OH) _x Sintering fromAnd ordinary portland cement is formed. In addition, the examples may include using Mg (OH) ₂ And/or other magnesium compounds to produce MgCO ₃ . Additionally or alternatively, mg (OH) ₂ And/or other magnesium compounds are placed in the waste heap where they can contact air and slowly convert to MgCO ₃ 。

In a seventh example, obtaining a non-limestone material S110 includes, for example, obtaining non-limestone rock and/or mineral, such as silicate rock material. Any suitable starting material may be used so long as it contains a sufficient amount of calcium to provide the desired end product, such as a final clinker or cement, such as portland cement. If a method is used that also produces a Supplemental Cementitious Material (SCM), the starting material will also contain one or more compounds that can provide a final material that contains amorphous (non-crystalline) compounds that can be used as SCM. These may include amorphous silica, in which case the starting material will also comprise silicon. However, other materials may provide amorphous compounds that act as SCMs, such as amorphous iron and alumina compounds, as known in the art; in these cases, the starting material includes the necessary starting elements. In certain embodiments that produce both clinker or cement (e.g., portland cement) and SCM, the starting material includes non-limestone rock and/or minerals that include non-limestone materials, such as calcium and silicon, such as rock and/or minerals that include calcium silicate. When rock and/or minerals are used, any suitable rock and/or minerals may be used, such as one or more of basalt, gabbro, pyroxene, clinohte, siecarock, amphibole, or combinations thereof. Other suitable rocks and/or minerals are as described herein or will be apparent to those skilled in the art.

Generally, non-limestone materials, such as rock and/or minerals, are treated to provide a calcium-rich fraction comprising one or more calcium salts and a generally solid calcium-depleted fraction. The calcium-depleted fraction, such as solids, may be removed. In certain embodiments, the solid comprises an amorphous compound, such as amorphous silica, and may be used as an SCM. The calcium-rich portion may be a solution comprising a calcium salt, and may also comprise non-calcium salts, such as Fe, al, mg (e.g., chlorides thereof), and/or other salts. In some cases, the nature and concentration of the non-calcium salt is such that no further processing of the calcium-rich fraction is required, as its content can be converted into an acceptable end product, such as clinker or cement, e.g. portland cement. This may be the case, for example, if the starting material comprises or consists of silica powder. In other cases, the nature and concentration of the non-calcium salt requires that one or more of them be removed from the solution. In this case, the calcium-rich fraction is treated to reduce the concentration of non-calcium salts, for example to a level acceptable for producing a final product, such as a final clinker or cement, for example a portland cement product. The solution is then treated to bring the one or more calcium salts into solid form and the one or more calcium salts can be treated to produce a further product; for example, at least dicalcium silicate and tricalcium silicate are provided by decomposition, for example in proportions suitable for clinker or cement, such as portland cement. One or more of the above treatments may be used to regenerate one or more starting materials; for example, if the starting material comprises an acid, such as a strong acid, at least a portion of the acid may be regenerated. The material may be further processed, for example to bring it to a suitable size or size range, for example for use as portland cement. The process may be any suitable type of process, such as batch processes, continuous processes (e.g., including one or more countercurrent processes), semi-continuous processes, and the like, as known in the art.

Non-limestone materials, such as rock and/or mineral materials, are contacted with a strong acid to form a slurry comprising acid and non-limestone materials, such as rock and/or mineral. Any suitable strong acid may be used, for example HCl, HBr, HI, H ₂ SO ₄ Or HNO (HNO) ₃ . In certain embodiments, the strong acid comprises HCl. For convenience, the remainder of the process will be described in terms of HCl; as will be apparent to those skilled in the art, if another acid is used in addition to or as an alternative to HCl, then appropriate adjustments may be made to accommodate the additional/alternative acids.

Dissolving the non-limestone material S130 includes adding hydrochloric acid (HCl). Thus, non-limestone materials, such as rock and/or minerals, such as silicate rock materials, are dissolved in hydrochloric acid (HCl). In certain embodiments, the proportion of the strong acid comprising HCl is at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99% of the strong acid. In a preferred embodiment, at least 90% of the strong acid is HCl. In a more preferred embodiment, at least 95% of the strong acid is HCl. In a more preferred embodiment, at least 98% of the strong acid is HCl. In an even more preferred embodiment, 99-100% of the strong acid is HCl, e.g., 100% of the strong acid is HCl. Any suitable concentration of strong acid may be used, such as HCl, for example 5-40%, 10-37%, 10-30%, 15-35%, 17-23%, 20-30% wt/wt, or about or exactly 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, for example about or exactly 20%. In a preferred embodiment, the HCl is 10-37%. In a more preferred embodiment, the HCl is 15-35%. The ratio of solid non-limestone material (e.g., rock and/or mineral) to liquid (acid) in the initial slurry may be any suitable ratio; it will be appreciated that some solid rock and/or minerals will immediately begin to dissolve in the acid and that these ratios will change as the solids dissolve into solution. Suitable initial ratios may be within the following ranges: 5% solids/95% liquid to 40% solids/60% liquid, e.g., 10% solids/90% liquid to 30% solids/70% liquid; in a preferred embodiment, 15% solids/85% liquid to 25% solids/75% liquid, e.g., 20% solids/80% liquid.

The pulp is treated to dissolve at least a sufficient amount of calcium compounds in non-limestone materials (e.g. rock and/or minerals) into solution to provide a satisfactory end product, for example conversion to clinker or cement, for example portland cement. In certain embodiments, at least 50%, 60%, 70%, 80%, 90% or 95%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90% of the calcium in the starting material goes into solution. The treatment may be performed during an open or at least non-pressurized process to the atmosphere. The treatment may include heating and/or maintaining the slurry at a temperature or temperature range for a period of time. In general, the duration and/or temperature of the treatment may be used to provide the desired dissolution. Maintaining the pulp at a suitable temperature range including 60-115 ℃, 70-115 ℃, 80-115 ℃, 90-115 ℃, 100-115 ℃, 60-112 ℃, 70-112 ℃, 80-112 ℃, 90-112 ℃, 100-112 ℃, 60-110 ℃, 80-110 ℃, 90-110 ℃ or 100-110 ℃; it will be appreciated that the boiling temperature of the HCl solution may be higher than 100 ℃ due to the high concentration of HCl present and when the material is dissolved in the liquid phase. Thus, in certain embodiments, the temperature is at least 95, 96, 97, 98, 99, or 100 ℃; in a preferred embodiment, the temperature is at least 90 ℃; in a more preferred embodiment, the range temperature is at least 95 ℃; in a more preferred embodiment, the temperature is at least 98 ℃; and in an even more preferred embodiment, the temperature is at least 100 ℃. In certain embodiments, the maximum temperature is 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, or 115 ℃; in a preferred embodiment, the maximum temperature is 105 ℃; in a more preferred embodiment, the maximum temperature is 108 ℃; in another more preferred embodiment, the maximum temperature is 110 ℃. In certain embodiments, the temperature is reached and/or maintained at 100-115%. In certain embodiments, the temperature is reached and/or maintained at 100-110 ℃. Any suitable duration of treatment may be used. This may depend to some extent on the calcium content of the starting material, e.g. non-limestone rock and/or minerals; materials with lower calcium content may take longer to treat to obtain the desired amount of calcium salt in solution. Thus, the duration of the treatment may be at least 1, 2, 3, 4, 5, 6, 7, 8 or 10 hours and/or no more than 2, 3, 4, 5, 6, 7, 8, 10, 12, 15, 20, 24, 30, 36, 40, 48, 60 or 72 hours. In certain embodiments, the duration may be 2-24 hours, such as 4-18 hours or even 4-12 hours or less. In certain embodiments, the duration may be from 6 to 72 hours, such as from 4 to 48 hours, or from 4 to 36 hours, or from 4 to 24 hours. The slurry may be agitated during the treatment, such as stirring, for example, at 10-1000RPM, 20-800RPM, 50-500RPM, 50-400RPM, or 100-300 RPM. In a preferred embodiment, the slurry is stirred at 50 to 400RPM, more preferably 100 to 300 RPM. Other agitation methods known in the art may be used.

A calcium-depleted fraction (solids) and a calcium-enriched fraction (liquids) are produced from the pulp. See, for example, fig. 3.

Separating the calcium-depleted portion from the calcium-enriched portion S140 includes separating a solid portion, which may be primarily SiO, from a liquid portion ₂ Such as amorphous silica, and/or other amorphous materials suitable for use as SCM, such as pozzolans; and then optionally rinsed, then dried and in some cases solid fractions, such as SiO ₂ The package is SCM. Further details concerning the process of generating SCM (e.g., pozzolan) are given below. When the solid portion comprises silica, a portion of the solid portion may be directed to a dechlorination and/or curing process, as described below.

Further processing the calcium-rich fraction; in certain embodiments, the end result of the further treatment is the production of clinker or cement, such as hydraulic cement, e.g., portland cement, e.g., ordinary Portland Cement (OPC), and typically regenerating acid. In addition, depending on the treatment of the calcium-rich fraction, certain non-calcium species may be produced, such as species containing one or more of iron, aluminum and/or magnesium. Further processing may depend on the possible composition of the calcium-rich fraction, which in turn may depend at least in part on the starting material.

In general, the calcium-rich fraction will contain non-calcium salts in addition to the calcium salt, also referred to herein as metal compounds, and the subsequent procedure may depend on the ratio of non-calcium salts (metal compounds) to calcium salts, or the desired ratio, which may be based at least in part on the starting materials. If the proportion of the one or more non-calcium salts is above a certain threshold in the calcium-rich portion, the calcium-rich portion may be treated to remove at least a portion of the one or more non-calcium salts, e.g., to bring the level of calcium salts in the calcium-rich portion below the threshold. The threshold value may be determined by, for example, the desired composition of the end product, e.g., cement, e.g., hydraulic cement, e.g., portland cement, e.g., OPC. For example, certain non-calcium species, such as derivatives of iron, aluminum and/or magnesium salts, may be permitted to be present in hydraulic cements, such as portland cements, e.g., OPC, but only below a certain level, typically depending on the type of cement (e.g., ASTM type 1, 2, 3, 4 or 5, or similar standards) and/or the standard to be met, as the standard may vary depending on the geographical location. The threshold may be based at least in part on the desired level of non-calcium salt derived materials (e.g., aluminum, iron, and/or magnesium species) in the final clinker or cement, such as a further processed portland cement (e.g., OPC) product.

Thus, the calcium-rich fraction may contain soluble non-calcium salts, such as salts of Al, fe and/or Mg, which may also be referred to as metal-containing compounds. Separating the calcium-containing compound from the calcium-rich fraction S150 includes precipitating soluble non-calcium salts (metal-containing compounds). In certain embodiments, this includes a one-step thermal decomposition (thermal hydrolysis) process. In certain embodiments, this includes a multi-step thermal decomposition (thermal hydrolysis) process, such as a two-step thermal decomposition process. In certain embodiments, this includes adding a base. In certain embodiments, one-step thermal decomposition (thermal hydrolysis) and addition of a base are used. In certain embodiments, two-step thermal decomposition (thermal hydrolysis) and addition of a base are used. In certain embodiments, only the addition of base is used. Generally, at least some of the strong acid, e.g., HCl, is also regenerated in the process.

In certain embodiments, the calcium-rich portion is raised to and/or maintained at a temperature or temperature range (one-step thermal decomposition or thermal hydrolysis) to form a set of insoluble non-calcium materials that can be removed from the calcium-rich portion. The temperature or temperature range may be a temperature at which one or more non-calcium salts (e.g., at least iron and aluminum salts) form insoluble materials (e.g., insoluble iron and aluminum materials). Other non-calcium salts that may form insoluble materials include boron salts, lithium salts, rubidium salts, cesium salts, strontium salts, barium salts, and/or radium salts. The temperature may be any suitable temperature or temperature range, for example at least 140, 145, 150, 155, 160, 165, 170, 175, or 180 ℃ and/or no more than 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, or 195 ℃; in certain embodiments, the calcium-rich fraction is heated to 140-195 ℃; in a preferred embodiment, the calcium-rich fraction is heated to 140-185 ℃; in a more preferred embodiment, the calcium-rich fraction is heated to 150-185 ℃, or even 175-185 ℃. In certain embodiments, the calcium-rich portion is heated to at least 140 ℃, such as at least 150 ℃, such as at least 160 ℃, and in certain cases at least 170 ℃. Any suitable method of bringing the calcium-rich portion to and/or maintaining it at the desired temperature may be used; heating the solution and/or maintaining it at a certain temperature Methods of temperature or temperature ranges are well known in the art. The calcium-rich solution may be maintained at or near the desired temperature for a suitable duration, such as at least 0, 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, or 10 hours, and/or no more than 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, 10, or 15 hours. In certain embodiments, the calcium-rich portion is maintained at or near the desired temperature for 10 minutes to 5 hours, such as 30 minutes to 4 hours, and in some cases 1 to 3 hours. HCl gas is driven off when the calcium-rich fraction is heated and/or maintained at a high temperature. Part or all of this gas may be captured and dissolved in an aqueous medium to regenerate HCl; in certain embodiments, HCl gas is captured and returned to an aqueous medium, such as HCl solution, which is used or will be used as a leaching agent for treating subsequent calcium-containing material. Insoluble material produced by increasing the temperature may be separated from the remaining calcium-rich fraction by any suitable means, such as centrifugation, filtration, and the like. The insoluble material may include one or more compounds of aluminum and/or iron, such as Al (OH) ₃ 、Al ₂ O ₃ 、AlO(OH)、Fe(OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc.

In certain embodiments, a two-step thermal decomposition process is used. This is achieved by: firstly, performing two-step thermal decomposition (two-step thermal hydrolysis); the mixture is first heated to a temperature or temperature range such that an aluminum salt, such as AlCl ₃ Formation of insoluble aluminium species, e.g. Al (OH) ₃ 、Al ₂ O ₃ AlO (OH) and the like, but iron salts, e.g. FeCl ₂ And/or FeCl ₃ Without formation of insoluble material, e.g. Fe (OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc., or substantially no insoluble material is formed. In certain embodiments, the first temperature is less than 150 ℃, or less than 145 ℃, or less than 140 ℃. In certain embodiments, the first temperature is 130-145 ℃, 131-144 ℃, 132-141 ℃, 133-139 ℃, or 135-137 ℃, such as about or exactly 136 ℃, or such as about 140 ℃. Can be used to makeThe calcium-rich portion reaches the desired temperature and/or is maintained at the desired temperature. The calcium-rich solution may be maintained at or near the desired temperature for a suitable duration, such as at least 0, 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, or 10 hours, and/or no more than 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, 10, or 15 hours. In certain embodiments, the calcium-rich portion is maintained at or near the desired temperature for 10 minutes to 5 hours, such as 30 minutes to 4 hours, and in some cases 1 to 3 hours. The process results in the formation of insoluble compounds of aluminum, such as alumina (e.g., forming Al (OH) ₃ 、Al ₂ O ₃ AlO (OH), etc.). HCl is also regenerated as described for the one-step thermal decomposition process. Insoluble aluminum compounds (e.g., alumina compounds) can then be separated from the calcium-rich partial solution; they may be further processed, for example dried. The remaining solution is then brought to a second temperature or temperature range at which one or more non-calcium salts, e.g. at least iron salts, form insoluble materials, e.g. Fe (OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc. The temperature may be any suitable temperature or temperature range, for example at least 140, 145, 150, 155, 160, 165, 170, 175, or 180 ℃ and/or no more than 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, or 195 ℃; in certain embodiments, the remaining solution is heated to 140-195 ℃; in a preferred embodiment, the remaining solution is heated to 150-190 ℃; in a more preferred embodiment, the remaining solution is heated to 175-185 ℃. In certain embodiments, the remaining solution is heated to at least 145 ℃, such as at least 170 ℃, in certain cases at least 175 ℃, such as a second heating step to about 180 ℃. Any suitable method of bringing the calcium-rich portion to and/or maintaining it at the desired temperature may be used. The calcium-rich solution may be maintained at or near the desired temperature for a suitable duration, such as at least 0, 1, 2, 5, 10, 20, 30, 40, or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, or 10 hours, and/or no more than 1, 2, 5, 10, 20. 30, 40 or 50 minutes or 1, 1.5, 2, 2.5, 3, 4, 5, 7, 10 or 15 hours. In certain embodiments, the calcium-rich portion is maintained at or near the desired temperature for 10 minutes to 5 hours, such as 30 minutes to 4 hours, and in some cases 1 to 3 hours. This temperature is used to cause the formation of insoluble iron compounds, such as iron oxides (e.g., forming Fe (OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ Etc.) and simultaneously regenerating the HCl first acid as in the first heating step. Insoluble Fe, such as oxidized Fe, may then be separated from the calcium-rich partial solution; it may then be further processed, for example dried.

In certain embodiments, the calcium-rich fraction is treated with one or more bases to form a set of insoluble non-calcium materials that can be removed from the calcium-rich fraction. HCl may also be regenerated during the base addition. In certain embodiments, this is the only process used to cause the formation of insoluble non-calcium species (precipitated metal compounds). In certain embodiments, a one-step thermal decomposition process is used and a base is added. In certain embodiments, a two-step thermal decomposition process is used and a base is added. The base or bases may be any suitable base or bases, provided that the base or bases are strong and in an amount sufficient to precipitate the desired amount of the metal compound. In certain embodiments, the base comprises a calcium base. In certain embodiments, the one or more bases comprise one or more substances produced as a product in the process, such as a calcium base, e.g., caO, ca (OH) ₂ Or CaSi, such as dicalcium silicate or tricalcium silicate. In certain embodiments, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95% of the one or more bases comprise one or more products produced in the process, such as calcium bases, e.g., caO, ca (OH) ₂ Or CaSi, such as dicalcium silicate or tricalcium silicate. In certain embodiments, 100% of the one or more bases comprise one or more products produced in the process, such as calcium bases, e.g., caO, ca (OH) ₂ Or CaSi, such as dicalcium silicate or tricalcium silicate. Some or all of the added base may be regenerated in other steps of the process,for example, calcium salt decomposition such as CaO, dicalcium silicate and/or tricalcium silicate. In certain embodiments, a base is added to the calcium-rich fraction in a one-step process to precipitate all desired compounds, such as to precipitate Al, fe, and Mg compounds. In some processes, the base is added after some non-calcium salts (metal compounds) precipitate, for example by a one-or two-step thermal decomposition process; in such cases, sufficient base is added to precipitate the remaining metal compounds or a portion thereof (e.g., the remaining Fe and Mg compounds, or the remaining Mg compounds, or a portion thereof). In certain embodiments, a base is added to precipitate Mg compounds. The precipitate may include one or more magnesium compounds, such as Mg (OH) ₂ Magnesium silicate hydrate, magnesium aluminum silicate and/or other magnesium compounds. The precipitate may be separated from the remaining calcium-rich fraction by any suitable method, such as the methods described herein. The precipitate may be further processed, for example by drying. The magnesium precipitate may be used to react with carbon dioxide, such as in a flue gas, for example, a flue gas produced as part of a process for powering the entire process (e.g., a flue gas from natural gas or coal combustion); and/or with atmospheric carbon dioxide and/or other carbon dioxide sources, such as bodies of water, e.g., carbon dioxide in the ocean, to produce magnesium-carbon dioxide products, e.g., mgCO ₃ (and/or bicarbonate in the case of a body of water) to sequester carbon dioxide. The amount of carbon dioxide sequestered thereby may reduce the total amount of carbon dioxide produced by the overall process, in some cases enough to render the overall process carbon neutral or even carbon negative. In addition, other substances in the flue gas, such as substances that need to be removed from the flue gas, such as SOx and/or NOx, may react with the Mg precipitates, in some cases reducing the content of one or more substances below what is required for the release of the flue gas into the atmosphere. Additionally or alternatively, the magnesium precipitate may sequester carbon dioxide from the atmosphere; any suitable arrangement may be used for this purpose. In certain embodiments, the magnesium precipitate optionally processed to increase surface area may simply be deposited in a pile, laid on the ground in layers, or distributed in other suitable ways, and allowed to sequester atmospheric carbon dioxide for any suitable period of time, which may be Is several days, several weeks, several months, one year or more.

Reducing carbon dioxide production

Thus, a process of producing clinker or cement (e.g., portland cement and/or SCM) as described herein does not result in as much carbon dioxide production as a standard process; indeed, in certain embodiments, the processes described herein may be carbanionic. The clinker or cement produced by the processes disclosed herein, e.g., portland cement and/or SCM, may be used as is commonly used for clinker or cement, e.g., portland cement and/or SCM, e.g., for concrete, mortar, stucco, grout, and the like. Because the methods described herein produce less carbon dioxide than conventional methods of producing portland cement, and in some cases may even be carbonaceous, replacing some or all of the standard clinker or cement (e.g., portland cement) with clinker or cement produced by the processes described herein (e.g., portland cement) may result in a reduction in the carbon footprint of the concrete or other product; indeed, in some cases, the concrete may even be carbon negative. As does SCM. In embodiments where clinker or cement (e.g., portland cement, SCM, and in some cases aggregate) is produced at one site and blended into concrete at that site, carbon reduction is further achieved due to reduced (or no) transport of the various components. Because the amount of carbon dioxide avoided and/or sequestered by using clinker or cement (e.g., portland cement and/or SCM) produced in the processes described herein in place of standard clinker or cement (e.g., portland cement and/or SCM) can be calculated based on inputs and outputs, etc., as is known in the art, carbon credits can be obtained based on the avoided/sequestered carbon dioxide. Accordingly, provided herein is a method of obtaining carbon credit, the method comprising performing one or more of the processes described herein for producing clinker or cement (e.g., portland cement, and in some cases SCM), and using the clinker or cement (e.g., portland cement, and in some cases SCM) as a substitute for clinker or cement produced by standard methods (e.g., portland cement, and in some cases SCM), evaluating carbon dioxide produced and consumed in the processes described herein, determining an amount of carbon dioxide avoided and/or sequestered compared to concrete produced by standard methods with clinker or cement (e.g., portland cement, and in some cases SCM), and obtaining carbon credit based on the amount.

In certain embodiments using a one-or two-step thermal decomposition process, precipitating the metal compound may then include adding a base, such as described above, for example, a calcium base (e.g., caO, ca (OH) ₂ Or CaSi) to precipitate magnesium from the calcium-rich portion, effectively leaving only calcium compounds, or calcium compounds and metal compounds, at a level low enough to be acceptable in one or more end products of the process. More HCl can be regenerated in the alkaline precipitation step.

In general, the calcium chloride content of the calcium-rich fraction after removal of the metal compounds is very high, e.g. at least 90%, in some cases at least 95%, or even at least 99% of the calcium chloride. The calcium-rich fraction is also typically highly concentrated, e.g. 40% CaCl ₂ 60% water to 70% CaCl ₂ 30% water, or 50%/50% to 60%/40%, or even 55%/45% to 60%/40%.

Whether produced by an acid dissolution step, a one-step thermal decomposition, a two-step thermal decomposition, an alkali addition, or any suitable combination thereof, the resulting calcium compound remaining in the calcium-rich portion may then be treated to produce one or more additional products, such as clinker or cement, e.g., portland cement. This may include removing water from the remaining calcium-rich fraction containing calcium compounds to provide a calcium-rich fraction containing one or more calcium compounds (e.g., one or more calcium salts, such as CaCl ₂ ) And treating the solids, for example converting them into a dechlorinated calcium product, and thus into clinker, for example clinker for use in the production of portland cement, the clinker comprising dicalcium silicate and tricalcium silicate.

The water may be removed from the calcium-rich portion by any suitable method, such as heating to evaporate the water into steam; some or all of the generated steam may be used in further processes requiring steam, as described below. The resulting calcificationThe composite solids comprise one or more calcium salts, e.g. CaCl ₂ And are also referred to herein as "solids comprising calcium chloride" and may also comprise non-calcium salts, such as iron, aluminum, and/or magnesium salts, and/or other salts, provided that they are present in an amount that does not render the end product unsuitable for its intended use, for example as clinker or cement, such as portland cement, and/or interfere with the process used to produce the clinker or cement, such as portland cement.

The calcium compound solids (solids comprising calcium chloride) may be processed to produce particles of a desired size for further processing, such as by tabletting, grinding, or other suitable methods. It may then be treated to decompose the calcium-containing compound, for example to CaO and/or other calcium-containing dechlorinated products and regenerate HCl; to produce clinker, such as for portland cement, the clinker may be further heated (sintered) in the presence of fluxes, such as fluxes providing Si, fe and Al, to produce clinker, which may be further processed to produce cement, such as portland cement.

In certain embodiments, the calcium compound solid (solid comprising calcium chloride) is in the presence of steam, silica, and optionally an exogenous flux, e.g., containing aluminum (e.g., al (OH) ₃ ) And/or iron (e.g. Fe (OH) _x ) Is heated in the presence of an exogenous flux. Typically, fluxing agents are not necessary, but may be added at this step for convenience. In certain embodiments, some or all of the silica, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99% of the silica, or 100% of the silica is silica produced from a non-limestone material, e.g., non-limestone rock and/or minerals, e.g., in an earlier step of the process, e.g., in the production of SCM (volcanic ash) as described herein. In certain embodiments, some or all of the exogenous fluxing agents, such as at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99% fluxing agents, or 100% fluxing agents are iron and aluminum oxides, hydroxides, and possibly other suitable compounds produced from non-limestone rock and/or minerals, such as, for example, in In an earlier step of the process, for example from the calcium-rich fraction, as insoluble salts are precipitated as described herein. It will be appreciated that the calcium compound solids (solids comprising calcium chloride) may comprise one or more substances that can act as fluxing agents, but it is generally preferred to add an exogenous fluxing agent. The heating may be performed in one step at a temperature high enough to decompose the calcium-containing solids and age/sinter the resulting compound with a fluxing agent. In the simplest case, the calcium compound solids are heated in the presence of steam to a temperature high enough to decompose the calcium compounds, produce HCl, and heated (e.g., sintered) with an endogenous fluxing agent to a temperature high enough to produce clinker. In a preferred embodiment, the heating may be performed in two or more steps with successively higher heat, and the exogenous fluxing agent (if used) is present in all or only part of the steps (e.g., heating, e.g., curing, such as sintering).

As previously described, the calcium compound solid (solid comprising calcium chloride) comprises calcium chloride; in certain embodiments, it comprises at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 92%, 95%, 96%, 97%, 98% or 99%, such as at least 90%, in some cases at least 95% calcium chloride. The decomposition process dechlorinates calcium chloride in the solid, e.g. at least 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.5%, 99.9%, 99.91%, 99.95% or 99.99% of the calcium chloride in the solid, i.e. the amount of chloride in the starting material is driven off, preferably at least 90%, more preferably at least 95%, even more preferably at least 99%. Surprisingly, it has been found that at least 99%, 99.5%, 99.9% or even 99.95% of the calcium chloride can be dechlorinated and that these dichloride levels are such that the chloride content of the final product is sufficiently low to meet the standards for portland cement, e.g. the chloride content is less than 1%, or less than 0.1%, without further treatment. In a preferred embodiment, at least 99% of the calcium chloride in the solids is dechlorinated; in a more preferred embodiment, at least 99.9% of the calcium chloride in the solids is dechlorinated; in a more preferred embodiment, at least 99.95% of the calcium chloride in the solids is dechlorinated.

In certain embodiments, the calcium compound solids (solids comprising calcium chloride) are heated in the presence of steam to one or more temperatures or temperature ranges, wherein the one or more temperatures or temperature ranges are sufficient to drive the discharge of chlorine gas from the solids; the chlorine combines with protons in the steam to regenerate HCl, which may be recycled as described previously. At the same time, the calcium chloride is converted to a dechlorinated calcium compound, which may or may not include calcium oxide. One general reaction may be

CaCl ₂ +H ₂ O→CaO+2HCl

More generally, the reaction can be expressed as:

CaCl ₂ +SiO2+H ₂ o→calcium silicate and other substances +2HCl

Intermediate compounds such as calcium chloride silicate, calcium aluminum chloride silicate compounds, and other compounds may be formed, and when the process reaches higher temperatures, monocalcium silicate and dicalcium silicate may be formed. CaO may be present but is not necessarily present. Thus, in certain embodiments, the process produces a product comprising dicalcium silicate in an amount of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80wt%, in some cases at least 30%, such as at least 50%, while comprising less than 30, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1wt% cao, in some cases less than 10%, such as less than 5%. Generally, the dichloride product will contain little or no tricalcium silicate, such as less than 20%, 15%, 10%, 5%, 3%, 2%, 1%, 0.5% or 0.1%, such as less than 5%. In certain embodiments, the resulting product comprises at least 30% dicalcium silicate and less than 10% CaO, in some cases less than 0.5% tricalcium silicate. The product may then be further processed to produce clinker.

Thus, in certain embodiments, a process for producing clinker (e.g., clinker convertible to cement, such as portland cement) is provided, wherein the process comprises 1) providing a composition comprising dicalcium silicate, such as in an amount of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80wt%, in some cases at least 30%, such as at least 50%, while comprising less than 30, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1wt%, in some cases less than 10%, such as less than 5%, caO, e.g., a composition comprising at least 30% dicalcium silicate and less than 10% CaO; in preferred embodiments, the composition contains little or no tricalcium silicate, such as less than 5% or less than 1%, even less than 0.5%; and 2) treating the composition under conditions that produce clinker (curing), such as clinker that can be processed into portland cement (e.g., OPC). In certain embodiments, the process of step 2) includes heating the composition to a temperature of, for example, 1200-1600 ℃ in the presence of a fluxing agent comprising aluminum and/or iron compounds, for example aluminum and/or iron oxides, as described more fully below. Some or all of the fluxing agent may be produced during the production of the composition of step 1). The resulting clinker comprises, for example, at least 10, 20, 25, 30, 35, 40, 45, 50, 55 or 60% w/w, in a preferred embodiment at least 50% tricalcium silicate.

Although it is possible to carry out the decomposition and curing at one temperature, it is preferred to carry out the decomposition and curing in a multi-step process at a continuously higher temperature, wherein the material may be maintained at a given temperature for a certain duration, for example 0.5-5 hours, or 0.75-4 hours, or 1-3 hours, for example 1, 2 or 3 hours. This increases the efficiency and yield of the dichlorination and the process achieves surprisingly high levels of dechlorination, as discussed elsewhere. Additionally or alternatively, the temperature may gradually increase from one temperature to the next. The heating may be performed in any suitable system, such as a fluidized bed or kiln; in a preferred embodiment, the heating is performed in a kiln, such as a rotary kiln.

Accordingly, provided herein is a process for dechlorinating calcium chloride, the process comprising heating calcium chloride to a first temperature in the presence of steam, silica, and optionally a fluxing agent comprising iron and/or aluminum compounds (e.g., one or more of these iron and/or aluminum compounds), followed by 1) maintaining the calcium chloride and other components at the first temperature for a first duration to produce a first set of one or more products comprising at least HCl, and removing HCl; heating the remaining first set of one or more products to a second temperature in the presence of steam to a second higher temperature and maintaining the one or more products and steam at the second temperature to produce a second set of one or more products comprising HCl and removing HCl; optionally, an additional step of heating to, for example, a third temperature, followed in certain embodiments even to a fourth temperature, and maintaining at each temperature for a duration to produce a set of products (one of which is HCl); the temperature, aluminum and/or iron compounds, silica, and duration may be as described; or 2) gradually heating the calcium chloride and other components from a first temperature to a second, higher temperature, wherein the heating rate is slow enough to allow a desired degree (e.g., maximum) of HCl production; wherein the calcium chloride is at least 95% dechlorinated, in a preferred embodiment at least 99.9% dechlorinated, and in a more preferred embodiment at least 99.95% dechlorinated to produce a dechlorinated calcium product.

In certain embodiments, solid compositions are provided that comprise 1) a solid comprising calcium chloride, such as at least 50%, 60%, 70%, 80%, 90% or 95% calcium chloride, such as at least 90%, in preferred embodiments at least 95% calcium chloride; 2) Solids comprising silica, such as at least 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% silica, such as at least 60%, preferably at least 75%, more preferably at least 80%; and optionally 3) a fluxing agent comprising one or more iron compounds, such as Fe (OH) ₂ 、Fe(OH) ₃ 、FeO(OH)、FeO、FeO ₂ 、Fe ₂ O ₃ One or more of the above, and/or one or more aluminum compounds, such as Al (OH) ₃ 、Al ₂ O ₃ One or more of AlO (OH). In certain embodiments, the solid comprising calcium chloride comprises at least 80% calcium chloride and the solid comprising silica comprises at least 60% silica. In certain embodiments, the solid comprising calcium chloride comprises at least 90% calcium chloride and the solid comprising silica comprises at least 80% silica. Typically, the solids are combined such that the Ca-Si molar ratio is between 2.5 and 3.25. The composition may have the following proportions (wt%) of the components:50-90% calcium chloride solids; 10-40% silica solids; 0-4% of an iron compound (if used) used as a fluxing agent; 0-4% of an aluminum compound (if used) as a fluxing agent. In a preferred embodiment, the ratio is 60-85% calcium chloride solids; 15-30% silica solids; 1-3% of an iron compound (if used) used as a fluxing agent; 1-3% of an aluminum compound (if used) as a fluxing agent. In a more preferred embodiment, the proportion is 70-80% calcium chloride solids; 15-25% silica solids; 1-2% of an iron compound (if used) used as a fluxing agent; 1-2% of an aluminum compound (if used) as a fluxing agent. In certain embodiments, all components are derived from a single source, such as a single source comprising non-limestone rock and/or minerals. In certain embodiments, a composition comprising a calcium chloride-containing solid and a silica-containing solid is produced by the processes described herein, e.g., treating a non-limestone starting material by acid dissolution and further processing to produce the calcium chloride-containing solid, and adding the silica-containing solid to the calcium chloride-containing solid in a desired ratio, e.g., a Ca-Si molar ratio of between 2.5 and 3.25. The solid comprising silica may be any suitable solid; in certain embodiments, some or all of the solids are produced during the production of solids comprising calcium chloride, for example, as calcium-depleted solids from the acid dissolution step.

The calcium compound solid is preferably heated to and maintained at a first temperature in the presence of steam and typically silica and optionally a fluxing agent, or is heated to the first temperature in a ramp manner, or both, for example, the first temperature of HCl may be treated according to methods known in the art. In certain embodiments, the solid is heated to no more than 1250 ℃, such as 750-1250 ℃, 800-1250 ℃, in some cases 850-1000 ℃, in some cases 900-1250 ℃, preferably 1000-1250 ℃, even more preferably 1100-1250 ℃, in the presence of steam, silica, and optionally aluminum and iron containing compounds to produce HCl and dechlorinated calcium products. The solid mixture can be heated rapidly to 700-750 ℃. When the temperature reaches 700, 705, 710, 715, 720, 730, 740 or 750 ℃, preferably 700 ℃ or 720 ℃, the heating rate should generally not exceed 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70 or 100 ℃/min, preferably not exceed 30 ℃/min, even more preferably not exceed 20 ℃/min, and more preferably not exceed 10 ℃/min until the temperature reaches 800, 850, 900, 950 or 1000 ℃, preferably 1000 ℃. Without being bound by theory, it is believed that in the range of about 700 to about 1000 ℃, calcium chloride will melt, which is undesirable and will reduce the amount of chlorine driven off, and maintaining the heating at a controlled rate instead favors the reaction between calcium and silica and the production of HCl, producing a product that will allow more chlorine to be driven off. The process may be maintained ("soaked") at one or more temperatures for a duration of 1-180 minutes, such as 5-120 minutes, such as 10-120 minutes. Example 4 gives an exemplary soaking temperature and time, however, these are merely exemplary. Additionally or alternatively, the temperature may be raised in a continuous manner, at a constant or varying rate. Such improvement can be determined by routine experimentation. The steam may be present in any suitable concentration, for example 5-100vol%. When T is more than 300℃, steam flow can be started

The solids may be heated in any suitable manner and system; such as a fluidized bed or kiln. In this and other steps, the silica may be combined with a calcium compound, such as CaCl ₂ Is present in any suitable ratio; for example, a 100-105g sample may contain about 80g CaCl ₂ About 20g of silica and optionally about 1-3g of aluminum and iron compounds. This is merely exemplary and it is understood that the ratio of the various components may vary depending on the criteria of the type of portland cement to be produced, which criteria will be apparent to one of ordinary skill in the art, e.g., a higher ratio of calcium to silica may produce a final product having a higher ratio of C3S than C2S.

The decalcified product (in some cases a CaO-containing product, but in other cases containing little or no CaO) may then be heated to a second temperature, and optionally, then to a third temperature, and in some cases also to a fourth temperature, typically also in the presence of one or more lower temperature vapors, silica or a compound formed from silica and calcium, and optionally aluminum and/or iron compounds that act as fluxing agents; at one or more temperatures, such as higher temperatures, steam may not be present. Thus, the dechlorinated calcium product (e.g. CaO-containing or CaO-free product) is cured, i.e. to produce clinker (which in some cases is sintered), e.g. in the presence of silica and optionally fluxes, e.g. aluminum and/or iron-containing fluxes, to produce clinker, e.g. portland cement clinker. The fluxing agent may include materials produced in an earlier step of the process, such as aluminum and/or iron compounds removed from the calcium-rich portion, as described above. In certain embodiments, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the exogenous flux comprising aluminum and/or iron comprises one or more compounds removed from the calcium-rich portion, such as at least 50%, in some cases at least 70%, and in certain embodiments at least 90%. In certain embodiments, 100% of the exogenous flux comprising aluminum and/or iron comprises one or more compounds removed from the calcium-rich portion. The presence or absence of the exogenous fluxing agent, and, if present, the amount thereof, may be determined, at least in part, by the desired final composition (e.g., clinker or cement, such as the type of portland cement produced). In certain embodiments, a fluxing agent comprising an iron-containing compound and an aluminum-containing compound is used.

If only a second temperature is used, the process involves heating the decalcified product (in some cases, caO-containing product, but in other cases little or no CaO) to 1200-1550 ℃, preferably no more than 1450 ℃, in the presence of silica and optionally a fluxing agent, thereby forming portland cement clinker comprising dicalcium silicate and tricalcium silicate; in some cases, the clinker also comprises tricalcium aluminate and/or tetracalcium aluminoferrite. If an intermediate temperature is used, the temperature may be, for example, 900-1100 ℃, such as 950-1050 ℃; the temperature may be, for example, 1100-1300 ℃, such as 1150-1250 ℃; the temperature may be, for example, 1400-1600 ℃, such as 1450-1550 ℃. In an exemplary embodiment, the temperatures are 850, 1000, 1200, and 1500 ℃ in that order, each maintained for 1 hour. These are merely exemplary and one skilled in the art can select the optimal temperature and duration by routine experimentation.

In certain embodiments, a method of producing clinker from solids comprising calcium chloride is provided, wherein the method comprises reacting a mixture comprising CaCl ₂ Dechlorination of the solids of to produce a dechlorinated composition comprising Ca and having less than 10% w/w Cl; and heating the dechlorination composition in the presence of a fluxing agent to produce clinker, for example clinker for portland cement production, for example clinker comprising dicalcium silicate and tricalcium silicate.

In certain embodiments, provided herein is a method of producing clinker, the method comprising heating a composition comprising dicalcium silicate and no more than 20%, 15%, 10%, 5%, 2% or 1% CaO, such as no more than 10% CaO, in the presence of a fluxing agent to produce clinker. The composition may contain less than 5%, 4%, 3%, 2%, 1%, 0.5% or 0.1% tricalcium silicate and the clinker comprises at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60% tricalcium silicate. The fluxing agent may comprise aluminum and/or iron oxides.

A method of producing clinker and Supplemental Cement Material (SCM) from a starting material comprising a non-limestone material, the non-limestone material comprising calcium and silicon, the method comprising (i) dissolving the non-limestone material in HCl to produce a calcium-enriched liquid fraction comprising calcium chloride and a calcium-depleted solid fraction comprising silica; (ii) Generating SCM from a calcium-depleted solids portion comprising silica; and (iii) producing clinker from the calcium-rich liquid fraction comprising calcium chloride.

Clinker, such as portland cement clinker, may be further processed (e.g., treated) to produce particles within a desired size range in combination with calcium sulfate, and the like.

At the end of all acid regeneration steps (e.g., HCl regeneration), at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 98%, or 99% of the initial acid (e.g., initial HCl) may be regenerated. In a preferred embodiment, at least 80% of the initial HCl is regenerated. In another preferred embodiment, at least 90% of the initial HCl is regenerated. To provide sufficient acid, e.g., sufficient HCl, for subsequent treatment of the non-limestone material, a quantity of unrenewed strong acid, e.g., HCl, may be added back, i.e., topped up with strong acid, e.g., HCl.

In a seventh example, as previously described, decomposing the calcium compound S160 and regenerating the leaching agent S170 may occur simultaneously with the thermal decomposition for precipitating iron and aluminum. In a cement-producing variant, the seventh example may further include treating a calcium product clinker, such as a sintered calcium product, comprising: in the kiln, dechlorinated calcium compounds (e.g. CaO, caOH ₂ Etc.) with SiO ₂ 、Al(OH) ₃ And Fe (OH) _x Curing (e.g., sintering) to form a clinker, such as that used for ordinary portland cement. In addition, the examples may include the use of insoluble Mg compounds (e.g., mg (OH) produced in the process ₂ ) Scrubbing flue gas to produce MgCO ₃ . Additionally or alternatively, insoluble Mg compounds produced in the process, such as Mg (OH) ₂ Placed in a waste heap where it can contact air and slowly convert to MgCO ₃ . Additionally or alternatively, insoluble Mg compounds produced in the process may be placed into a body of water, such as the ocean; bicarbonate may also be formed during this process.

Method for producing Supplementary Cementitious Material (SCM)

In certain embodiments, methods for producing SCM (e.g., pozzolan) from non-limestone materials (e.g., rocks and/or minerals) are provided. Generally, the methods involve exposing a non-limestone material (e.g., non-limestone rock and/or mineral) to a leaching agent (e.g., a strong acid), for example, dissolving certain components of the non-limestone material to produce a liquid leachate while leaving a solid leachate residue comprising one or more amorphous materials (e.g., pozzolans) that may act as SCMs, and separating the solid leachate residue from the liquid leachate; an optional further step may include treating the SCM to remove liquid leachate, for example by rinsing, treating the SCM to dry it and/or treating the SCM to produce SCM of a desired size range.

The non-limestone material may be any suitable material provided that it contains one or more compounds that provide a final material that contains amorphous (non-crystalline) species that can be used as an SCM. These may include amorphous silica, in which case the starting material will also contain silicon-based materials, such as silica, silicates, silica compounds and/or silicate compounds. However, other materials may provide amorphous compounds that act as SCMs, such as amorphous iron and aluminum materials, as known in the art; in these cases, the starting material includes the necessary starting elements. In general, the term "amorphous material" as used herein includes materials that may exist as one or more crystalline polymorphs or amorphous polymorphs, which may be referred to as amorphous polymorphs, or amorphous materials. In certain embodiments, the non-limestone material comprises silicon. In certain embodiments, the non-limestone material comprises siliceous rock and/or minerals. In certain embodiments, the non-limestone material comprises rocks and/or minerals containing non-silicon species used as materials to produce amorphous species (e.g., iron-containing and/or aluminum-containing species); in addition to silicon, these species may also be present, or in some cases, as the primary or sole source of amorphous species in the final SCM. In certain embodiments, the non-limestone material, such as rock and/or mineral, comprises calcium silicate. Exemplary suitable non-limestone rocks and/or minerals include basalt, gabbro, pyroxene, clinohte, sika, amphibole, or combinations thereof. Other suitable non-limestone materials may be as described elsewhere herein.

Non-limestone materials, such as rock and/or minerals, may be processed to provide particles in a desired size range. Any one or more suitable processes may be used, such as crushing and sieving. Suitable size ranges include 1-500u, 5-300u, 10-200u, 20-130u, 45-90u, or combinations thereof. In a preferred embodiment, the size range is 20-130u. In a more preferred embodiment, the size range is 45-90u.

The non-limestone material, such as rock and/or minerals, is contacted with a leaching agent, which may be any suitable leaching agent, such as those described herein. In certain embodiments, the leaching agent comprises a strong acid and the contacting produces a pulp comprising acid and rock and/or minerals. Any suitable leaching agent may be used, for example a strong acid, such as HCl, HBr, HI, H SO4 or HNO3. In certain embodiments, the strong acid comprises HCl. In certain embodiments, the only acid used is HCl. For convenience, the remainder of the process will be described in terms of HCl; as will be apparent to those skilled in the art, if another acid is used in addition to or as an alternative to HCl, then appropriate adjustments may be made to accommodate the additional/alternative acids.

Any suitable concentration of HCl may be used, such as 5-40%, 10-37%, 10-30%, 15-35%, 17-23%, 20-30%, or about or exactly 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, such as about or exactly 20%. In a preferred embodiment, the HCl is 10-37%. In a more preferred embodiment, the HCl is 15-35%.

The ratio of solid non-limestone material (e.g., solid rock and/or mineral) to liquid (acid) in the initial slurry may be any suitable ratio; it will be appreciated that some solid rock and/or minerals will immediately begin to dissolve in the acid and that these ratios will change as the solids dissolve into solution. Suitable initial ratios may be within the following ranges: 5% solids/95% liquid to 40% solids/60% liquid, e.g., 10% solids/90% liquid to 30% solids/70% liquid; in a preferred embodiment, 15% solids/85% liquid to 25% solids/75%, e.g., 20% solids/80% liquid. In certain embodiments, provided herein are pulp compositions comprising solid non-limestone rock and/or mineral and a liquid leachable agent (e.g., a strong acid, such as HCl), wherein the pulp comprises solids and liquids in the following ratios: 5% solids/95% liquid to 40% solids/60% liquid, e.g., 10% solids/90% liquid to 30% solids/70% liquid; in a preferred embodiment, 15% solids/85% liquid to 25% solids/75%, e.g., 20% solids/80% liquid. In certain embodiments, the solid non-limestone rock and/or mineral comprises at least 60%, 70%, 80%, 90% or 95% of particles having a size in the range of 1-500u, 5-300u, 10-200u, 20-130u, 45-90u, or a combination thereof. In a preferred embodiment, the size range is 20-130u. In a more preferred embodiment, the size range is 45-90u. In certain embodiments, the leaching agent is a strong acid, such as HCl, and is present at a concentration of 10-40%, such as 10-35%, in some cases 15-35%, or even 20-30%.

The slurry is treated so that at least some, and preferably most, of the non-amorphous material, such as non-silica material, etc., dissolves into the solution, leaving behind a solid rich in amorphous material, such as amorphous silica. The treatment may be performed during an open or at least non-pressurized process to the atmosphere. In general, the duration and/or temperature of the treatment may be used and may be adjusted, for example, according to the starting material. Maintaining the pulp at a suitable temperature range including 60-115 ℃, 80-115 ℃, 90-115 ℃, 100-115 ℃, 60-112 ℃, 80-112 ℃, 90-112 ℃, 100-112 ℃, 60-110 ℃, 80-110 ℃, 90-110 ℃ or 100-110 ℃; it will be appreciated that as more material dissolves in the liquid phase, the boiling temperature of the HCl solution will increase. Thus, in certain embodiments, the temperature is at least 95, 96, 97, 98, 99, or 100 ℃; in a preferred embodiment, the temperature is at least 90 ℃; in a more preferred embodiment, the range temperature is at least 95 ℃; in a more preferred embodiment, the temperature is at least 98 ℃; and in an even more preferred embodiment, the temperature is at least 100 ℃. In certain embodiments, the maximum temperature is 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, or 115 ℃; in a preferred embodiment, the maximum temperature is 105 ℃; in a more preferred embodiment, the maximum temperature is 108 ℃; in another more preferred embodiment, the maximum temperature is 110 ℃. Thus, in certain embodiments, the temperature is maintained between 100 ℃ and 110 ℃.

Any suitable duration of treatment may be used. This may depend to some extent on the starting material, e.g. non-limestone rock and/or minerals. Thus, the duration of the treatment may be at least 1, 2, 3, 4, 5, 6, 7, 8 or 10 hours and/or no more than 2, 3, 4, 5, 6, 7, 8, 10, 12, 15, 20, 24, 30, 36, 40, 48, 60 or 72 hours. In certain embodiments, the duration may be 2-24 hours, such as 4-18 hours or even 4-12 hours or less. In certain embodiments, the duration may be from 6 to 72 hours, such as from 4 to 48 hours, or from 4 to 36 hours, or from 4 to 24 hours.

The slurry may be agitated during the treatment, such as stirring, for example, at 10-1000RPM, 20-800RPM, 50-500RPM, 50-400RPM, or 100-300 RPM. In a preferred embodiment, the slurry is stirred at 50 to 400RPM, more preferably 100 to 300 RPM. Other suitable forms of agitation may be used.

After a suitable treatment duration is reached, a solution (also referred to herein as leaching solution or parent leaching solution, or PLS) comprising salts of dissolved material from non-limestone material and an undissolved fraction of solids (also referred to herein as leachate residue) is produced. The leach liquor residue is separated from the leach solution. Any suitable method may be used, such as simply draining PLS, centrifugation, filtration, etc., such as the methods described herein.

The leachate residue typically contains one or more amorphous materials, such as one or more amorphous materials that may be used as an SCM (e.g., pozzolan). In certain embodiments where the starting material comprises silicon, the leach residue comprises amorphous silica. Additionally or alternatively, the leachate residue may contain other amorphous compounds, such as amorphous Fe and/or Al, e.g. amorphous alumina, amorphous iron oxide, etc., which may also be used as SCM, e.g. pozzolan. In certain embodiments, the leachate residue comprises at least 10, 20, 30, 40, 50, 60, 70, or 80wt% amorphous silica. The leach liquor residue is treated to remove some or all of the leach solution, for example by rinsing with water. It may then be dried. The dried leach liquor residue may be SCM and may be used as such or after further processing, such as further processing to reduce the size of the particles to a desired range, such as by crushing and sieving.

In certain embodiments where the starting material comprises silicon, the leach residue comprises amorphous silica. Additionally or alternatively, the leachate residue may contain other amorphous compounds, such as amorphous Fe, al and/or Mg compounds, e.g. amorphous alumina, amorphous iron oxide, amorphous magnesium oxide, etc., which may also be used as SCM, e.g. pozzolans.

Apparatus and method for controlling the operation of a device

In one aspect, provided herein are devices, e.g., devices suitable for performing one or more of the processes described herein. In certain embodiments, an apparatus for producing SCM (volcanic ash) from non-limestone materials (e.g., non-limestone rock and/or minerals) is provided that includes one or more leaching vessels, a separation system for separating solids produced in the leaching vessels from liquid, and a processing system for processing the separated solids to provide SCM. Additional components may include one or more energy sources for the processes performed by the apparatus, one or more systems for processing non-limestone material, such as non-limestone rock and/or minerals, to make it suitable for leaching (which may be the same as or typically different from the processing system used to process the separated solids). In some cases, the exact composition of the components may depend on the type of process being performed. For example, in a batch process, the leaching vessel may be a vessel, such as a tank, that contains a material that is capable of withstanding the temperature and acidity of the leaching process and is sufficiently watertight to contain acid (e.g., completely watertight) during leaching. In a continuous process, such as a countercurrent leaching process, the leaching vessel may include a first conveyor for conveying non-limestone material (e.g., non-limestone rock and/or minerals) in a first direction and a second conveyor for conveying a leaching agent, such as a strong acid, e.g., HCl, in an opposite direction, such that the two contact each other in countercurrent fashion, wherein the components in contact with the leaching agent comprise a material capable of withstanding the leaching agent and temperature used. Other arrangements for other types of leaching processes will be apparent to those of ordinary skill in the art. The separation system may include, for example, one or more centrifuges, filters, filter presses, and the like, as described elsewhere herein. The processing system may include a dryer, which may be any suitable dryer, even in some cases, a dryer that simply allows the SCM to dry in the atmosphere, or any other suitable dryer, such as a dryer that provides heat to the SCM to accelerate drying; such devices are well known in the art. The processing system may include an optional rinse for rinsing the leachant and leach solution from the SCM prior to drying. The processing system may also include one or more components, such as a crusher, ball mill, screen, and/or other components known in the art, for processing the SCM to produce particles of a desired size range or set of size ranges. The one or more energy sources may be a suitable arrangement of one or more of a connection to an energy grid (e.g., an electrical grid), a renewable energy source (e.g., solar, wind, geothermal, etc.), an energy storage device (e.g., a battery, a fossil fuel powered generator, such as a natural gas powered generator or a coal powered generator), other suitable generator, or any suitable combination thereof. In embodiments using fossil fuel powered generators, the energy source may also include a system to purify the flue gas produced by the fossil fuel powered generator to reduce SOx, NOx, and/or other regulated pollutants to acceptable levels, and/or to reduce the carbon dioxide content of the flue gas. In certain embodiments, such systems include equipment (described in detail below) for contacting the flue gas with magnesium compounds produced in the further processing of the calcium-rich portion, wherein the systems remove carbon dioxide, and in some cases SOx and/or NOx, from the flue gas.

In certain embodiments, an apparatus for producing clinker or cement (e.g., portland cement) from non-limestone materials (e.g., non-limestone rock and/or minerals) is provided that includes one or more leaching vessels, a separation system for separating a calcium-depleted solids portion produced in the leaching vessels from a calcium-enriched liquids portion, a processing system for removing non-calcium compounds and materials from the calcium-enriched portions, a system for precipitating solid calcium compounds from the calcium-enriched portions, a system for decomposing the solid calcium compounds into products containing dechlorinated products and treating to produce portland cement clinker, and a system for processing portland cement clinker into Cheng Bote blue cement. Additional components may include one or more energy sources for the processes performed by the apparatus, one or more systems for processing non-limestone material, such as non-limestone rock and/or minerals, to make it suitable for leaching (which may be the same as or typically different from the processing system used to process the separated solids). If SCM is also generated, the additional components described above are also included. The leaching vessel, separation system, energy source, system for processing non-limestone material (e.g., non-limestone rock and/or minerals) are as previously described. The processing system for removing non-calcium compounds and materials from the calcium-rich fraction may include one or more systems for heating and maintaining the calcium-rich fraction at a desired temperature or temperature range and/or a system for adding a base to the calcium-rich fraction, as well as a separation system for removing insoluble non-calcium compounds and materials from the calcium-rich fraction. Systems for heating a solution and maintaining it at a temperature are known in the art and may include any suitable arrangement, such as a heat source applied to the outside or inside of the leaching vessel, one or more temperature sensors, a control system, etc. The system for adding the base may include a delivery mechanism for delivering the base (e.g., base such as CaO, dicalcium silicate, and/or tricalcium silicate, which are later generated in the process) to the calcium-rich portion, measuring the amount of base, introducing the base, timing the reaction time, and the like. All components for these systems may be those well known in the art. In certain embodiments, the system for heating the calcium-rich fraction and for adding base to the calcium-rich fraction are both contained in the apparatus. A system for separating insoluble compounds and/or materials is described. If a strong acid (e.g., HCl) is used as the leaching agent and the strong acid (e.g., HCl) is regenerated, the apparatus may also include one or more components, such as systems well known in the art, for example, for capturing HCl gas and contacting it with an aqueous liquid to produce liquid HCl. The system for precipitating calcium-containing solids from the calcium-rich fraction may be as simple as a heat source for heating the calcium-rich solution to produce steam; optionally, a delivery system, such as one or more conduits or the like, may be included to deliver steam to the system to decompose the calcium-containing solids into portland cement clinker. The system for decomposing the calcium-containing solids into dechlorinated products and sintering Cheng Bote blue cement clinker may comprise one or more heat sources; one or more devices for introducing steam, silica and typically one or more aluminum and/or iron containing fluxes into the calcium containing solids; and an apparatus for containing sintered calcium-containing solids, such as a fluidized bed or kiln, preferably a rotary kiln. Optional systems for processing Cheng Bote portland cement clinker are well known in the art and may include crushers, ball mills, sieves, and the like. The system for decomposing solid calcium compounds may also include equipment for capturing regenerated acid (e.g., regenerated HCl) and transporting it back to the HCl source.

In certain embodiments, an apparatus for producing clinker is provided, such as clinker suitable for producing cement (e.g., portland cement) from non-limestone materials (e.g., rock and/or minerals) and/or other suitable starting materials described herein. Generally, such an apparatus includes at least a first processor configured to process a non-limestone starting material to produce a slurry containing one or more calcium compounds (e.g., caCl) ₂ ) Is operatively connected to a second processing machine configured to form clinker (e.g., clinker such as OPC clinker) from a solid composition comprising one or more calcium compounds (e.g., calcium chloride), and optionally to produce cement, e.g., OPC, from the clinker. See, for example, fig. 8.

The first processing machine may include a leacher operatively connected to one or more precipitators operatively connected to the dehydrator. See, for example, fig. 9. In certain embodiments using starting materials that can be used without precipitating non-calcium salts, the first system can comprise a leacher and a dehydrator without one or more precipitators.

The leacher may be configured to contact the non-limestone material with an acid to produce a first calcium-rich liquid fraction and a calcium-depleted solid fraction. It may be operatively connected to a material processing machine configured to process non-limestone starting material, for example configured to reduce the size of the non-limestone material and/or to sort the material into one or more size ranges, for example including a crusher and/or mill, and one or more classifying screens, or other suitably arranged material processing systems. The leacher typically includes a leaching vessel to hold and process the pulp produced from the acid and non-limestone materials. Any suitable material may be used as long as it is capable of withstanding the leaching conditions. The leacher may include a heating element and/or an agitator. It may be operatively connected to an acid reservoir. It may be operatively connected to a first separator, which may also be operatively connected to the precipitator, wherein the first separator may be configured to separate a calcium-rich liquid fraction from a calcium-depleted solid fraction and to direct the calcium-rich liquid fraction to the precipitator. The first separator may also be operatively connected to a solids processing system, such as for processing calcium-depleted solids, such as silica (which will be described as silica for convenience, but it will be understood that in some cases it may comprise other materials), including, for example, a flusher and a dryer. Some silica may be used for dechlorination and/or clinker, see below, in which case the solids processing system is operatively connected to the dechlorination and/or clinker to supply silica. Some silica may be used as SCM and the apparatus may also include one or more additional processors for further processing as needed or desired to produce one or more desired characteristics, such as particle size, storage, etc.

The precipitator may be configured to remove one or more non-calcium salts from the calcium-rich fraction by converting the one or more non-calcium salts into a solid form that is removed from the calcium-rich fraction. Typically, the settler is operatively connected to the separation system of the leaching vessel such that the calcium-rich liquid fraction moves from the separation system to the settler or, if multiple precipitation units are used, to the first precipitation unit in the series. The or each precipitation unit (if a plurality of precipitation units are used) is operatively connected to a second (and possibly third and/or fourth) separator for separating solids produced in the or each precipitation unit from the calcium-rich liquid fraction.

The precipitator includes a first precipitation unit that is a base precipitation unit configured to precipitate a first set of non-calcium compounds. The alkali precipitation unit may be operably connected to one or more alkali sources; the alkali source may comprise a calcium alkali source. The alkali precipitation is described in more detail elsewhere herein. In certain embodiments, at least a portion of the source of calcium alkali comprises a source operatively connected to the dechlorinating device and/or the ripener to receive one or more products therefrom. In certain embodiments, the settler comprises only a base precipitation unit; in these cases, the alkali precipitation typically precipitates aluminum, iron, and magnesium species, as also described in more detail elsewhere herein.

In certain embodiments, the precipitator further comprises a second precipitation unit, which is a thermal hydrolysis precipitation unit configured to precipitate a second set of non-calcium compounds from the calcium-rich liquid fraction; as described above, this may be operatively connected to a third separator for separating the second set of precipitated non-calcium compounds from the calcium-rich liquid fraction. In certain embodiments, the precipitator includes a third precipitation unit, which is a thermal hydrolysis unit for precipitating a third set of non-calcium compounds from the calcium-rich liquid fraction, and may be operatively connected to the fourth separator for separating the third set of precipitated non-calcium compounds from the calcium-rich liquid fraction. In certain embodiments, the second and third precipitation units are identical, and the second and third groups of precipitated non-calcium compounds are identical. For example, the second/third precipitation unit may be configured to perform one-step thermal hydrolysis, as described in more detail elsewhere herein, and the second/third set of precipitated non-calcium products may also include Al-and Fe-species, as also described in more detail elsewhere herein. In certain embodiments, the second and third precipitation units are different, and the second precipitation unit is configured to precipitate aluminum compounds by heating the calcium-rich liquid to a first temperature or temperature range, e.g., as described in more detail elsewhere herein, and the third precipitation unit is configured to precipitate iron compounds by heating the calcium-rich liquid to a second temperature or temperature range that is higher than the first temperature or temperature range, e.g., as described in more detail elsewhere herein. The apparatus may also include one or more units for delivering one or more non-calcium precipitated products to the clinker and/or dechlorination apparatus. These typically include aluminum compounds and iron compounds that can be used as fluxing agents in the cookers.

The precipitator is operatively connected to the dehydrator to deliver calcium-rich liquid from which non-calcium compounds have been removed to the dehydrator.

The dehydrator is configured to remove water from the calcium-rich liquid portion from the precipitator to produce solids comprising one or more calcium compounds (e.g., calcium chloride), for example, by heating the calcium-rich liquid to evaporate the water until a desired dry level is reached. The dehydrator may comprise a heating element. In certain embodiments, the dehydrator may comprise equipment, such as equipment comprising a conduit, configured to convey steam generated in the dehydrator to the dechlorination device and optionally to the cooker. The solid product produced by the dehydrator is a solid comprising one or more calcium compounds (including calcium chloride) that may be present in one or more hydrated states, e.g., anhydrous, monohydrate, etc. Depending on the starting materials and processing, the CaCl2 content of the solids may be greater than 80%, 90%, 95% or 98%. It is desirable to configure the dehydrator to produce a lower hydration state of calcium chloride, such as anhydrous calcium chloride, because further steps will require less energy to drive off the remaining water. Further processing equipment may be connected to the dehydrator, for example, to reduce the size of the solids by producing particles, flakes, etc. from the solids.

The second processor includes a dechlorination apparatus and a clinker apparatus (cement kiln). See, for example, fig. 10. The dechlorination apparatus is operatively connected to the dehydrator and receives solids comprising calcium chloride (which may be further processed en route to the dechlorination apparatus) configured to dechlorinate the solids comprising CaCl2 to produce dechlorinated solids comprising calcium compounds. The dechlorination apparatus is operatively connected to a clinker apparatus configured to heat the dechlorinated solids in the presence of a fluxing agent to produce clinker. The dechlorination apparatus and the cooking apparatus may be one unit. In a preferred embodiment, the dechlorination and clinker are separate units. In a preferred embodiment, one or both of the dechlorinated and/or cooked means comprises a rotary kiln; in a more preferred embodiment, the dechlorination and clinker apparatus each comprise a rotary kiln.

The dechlorination reactor is configured to produce a dechlorinated solid comprising a calcium compound and less than 20, 15, 10, 8, 7, 6, 5, 4, 3, 2 or 1wt% cl. Methods and systems for dechlorinating a solid comprising calcium chloride to a low chloride level may be as described herein; for example, the dechlorinating device may be configured to keep the heating rate low enough when the material reaches a threshold temperature, e.g. 700-750 ℃, below 1, 2, 3, 5, 7, 10, 15, 20, 30, 40, 50, 60 or 80 ℃ up to another temperature, e.g. 800-1000 ℃. Additionally or alternatively, the dechlorination device may be configured to maintain the material at one or more temperatures for one or more durations, and/or to regulate and/or maintain heating at one or more desired ramp rates. The dechlorination apparatus is operatively connected to one or more sources of steam and one or more sources of silica. One of the steam sources may be a dehydrator. The one or more silica sources may comprise a first processor or portion thereof, for example, calcium-depleted solids separated from the calcium-enriched portion at a first separator, which may be further processed, for example, by rinsing and drying, and then conveyed to a chlorine remover. Mixing silica with a solid comprising calcium chloride from a dehydrator; this may occur before the dechlorination device. The silica may be mixed in a desired ratio, for example in a Ca to Si molar ratio of from 1 to 4, preferably from 2 to 4, more preferably from 2.5 to 3.5, even more preferably from 2.5 to 3.25. HCl is produced by the dechlorination device, and the dechlorination device may be operably connected to the leacher to replenish HCl in the leacher, the acid reservoir, or both.

The clinker is configured to receive dechlorinated solids comprising calcium compounds from the dechlorinated machine and to further process the solids in the presence of a fluxing agent and optionally steam (at least at an early stage) to produce clinker. The maturation vessel heats the dechlorinated solids comprising calcium compounds mixed with the fluxing agent, for example, to one or more temperatures and/or for one or more durations, as described herein. One or more flux sources are operatively connected to the clinker aggregate. Any suitable fluxing agent may be used. In certain embodiments, some or all of the fluxing agent is contained in the first processing machine, such as one or more substances produced at one or more precipitation units of the settler, and the maturation means is operatively connected to the first processing machine, such as one or more precipitation units that produce aluminum and/or iron substances, including aluminum and/or iron oxides (which may include, for example, ai 2O3 and/or Fe2O 3). In certain embodiments, the fluxing agent comprises materials not produced in the process, such as clays and other materials known in the art, and the one or more flux sources comprise one or more other materials. In certain embodiments, the clinker aggregate is also used as a source of calcium alkali, wherein one or more products of the clinker aggregate (e.g., comprising dicalcium silicate and/or tricalcium silicate) are used as calcium alkali in the settler, and the clinker aggregate is operatively connected to the settler, such as an alkali precipitation unit.

In certain embodiments, the system further comprises a clinker processor configured to receive clinker from the clinker processor and to further process it, for example, to produce cement, for example, portland cement, for example, OPC. The clinker processor may be configured to adjust the size/size distribution of the clinker, for example, by grinding, milling, sieving, etc., and/or to introduce additional materials, such as gypsum. Clinker processors may also be configured to prepare processed materials, such as cements, e.g., OPC, for shipping and/or sale.

In certain embodiments, the clinker processor is operably connected to a concrete production facility that is generally in close proximity to a source of starting material (e.g., non-limestone material), wherein the concrete production facility uses cement from the clinker processor to produce concrete, and in certain embodiments, also uses aggregate produced from the same non-limestone material used to produce cement and/or SCM.

FIG. 13 illustrates one embodiment of a system and method for producing clinker from non-limestone materials. Starting materials, such as non-limestone materials described herein, e.g., non-limestone rock and/or minerals, are provided via a feed (1301) to a material processor (1302) including a crusher (1303) that processes the starting materials to include crushed particles of various sizes. The crushed particles are then conveyed through one or more screens (1304) that separate crushed particles of a desired size range from crushed particles greater than the desired size range. The larger than desired crushed particles are returned to the crusher (1303), optionally mixed with new starting material, for further processing. The crushed particles of the desired size range are then fed into a mill (1305), where the crushed particles are milled to a finer size. The milled particles are combined with an air stream (1306) and fed into a baghouse (1307), where the milled particles are separated from the air and fed into a hopper (1309), and clean air is discharged (1308).

The milled particles are then transferred from the hopper to a leacher (1310), where the milled particles are contacted with a leaching agent (e.g., an acid such as HCl) in a leaching tank (1311) to form a pulp. The leachable agent is provided by an acid tank (1312). Additional leachables may be added or removed (1313) from the acid tank (1312) as desired. The leaching tank (1311) may include an agitator/stirring element. The leaching tank may include one or more heating elements (not shown) to heat the pulp. The leaching system may include an acid recovery element (1314) that recovers the vaporized acid and returns it to the leaching tank (1311), and/or discharges it (1315). Water may be added to the acid storage tank from any suitable water source, such as a boiler/vapor recompression system (1316) to produce the desired concentration of acid. After suitable treatment, the treated pulp, which typically comprises a calcium-rich liquid fraction and a calcium-depleted solid fraction, may be transferred through a first separator, in this example comprising a leaching filter (1317), to separate the calcium-depleted solid fraction from the calcium-rich liquid fraction. Water (1318) and/or any other suitable fluid may be added to the leaching filter at any time, for example, for flushing the calcium-depleted solids portion. The calcium depleted solids portion may be transferred to kiln (1319) for drying. In general, the solid calcium-depleted fraction comprises silica, and some or all of the solid fraction may be used as a silica source at a later stage of the process (e.g., during dechlorination). Additionally or alternatively, some or all of the solid portion may be further processed, such as to obtain a desired size range, to provide a Supplementary Cementitious Material (SCM) that may be sold and/or used in combination with cement produced during the manufacture of, for example, concrete.

The calcium-rich liquid fraction from the first separator, e.g. the chlorine leaching (1317), is then sent to a precipitation unit, which is a thermal hydrolysis precipitation unit, in this embodiment a molten salt hydrolysis chamber (1320) for heating with or without pretreatment to remove water, naCl and/or KCl from the leachate (1321). Molten salt hydrolysis chambers, such as thermal hydrolysis chambers (1320), treat the calcium-rich liquid portion at one or more temperatures for a predetermined duration at each temperature to facilitate conversion of soluble species including iron and/or aluminum, such as to convert iron chlorides and/or aluminum chlorides to insoluble species, which may include oxides, such as iron and/or aluminum oxides. The treated calcium-rich liquid fraction is then cooled in a quench (1322) and mixed with water in a mixer (1323). According to the treatment scheme, insoluble aluminum and iron species, such as oxides, may be recovered after treatment (1324), such as in a separator, such as during the addition of water in the mixer (1323). The treated calcium-rich liquid fraction is then transferred to a precipitation unit, which is an alkaline precipitation unit comprising a precipitation vessel (1325), wherein the treated calcium-rich liquid fraction is contacted with one or more alkaline chemicals such that soluble magnesium species (e.g., magnesium chloride) are converted to insoluble magnesium species (e.g., magnesium oxide) and precipitated. The alkali may be treated in a digester (1326) prior to contacting the treated leachate. Insoluble precipitated magnesium material (e.g., magnesia material) is then separated from the treated calcium-rich liquid portion by a separator (e.g., comprising a series of settling units (1327) and/or filters (1328)) and optionally rinsed with water or any other suitable liquid (1329). In certain embodiments (not shown), the system does not include a thermal hydrolysis chamber, and the precipitation unit, which is a base precipitation unit, is used to precipitate aluminum, iron, and/or magnesium species.

The treated calcium-rich liquid fraction may be transferred to an acid storage tank, such as an acid reservoir (1312) and/or a dehydrator (1330), where the calcium-rich liquid fraction is dehydrated, leaving behind a solid comprising calcium chloride, typically comprising high concentration calcium chloride in one or more hydrated states. The solids comprising calcium chloride, which may be in one or more hydrated states, are then conveyed to a dechlorination reactor (1331), mixed with one or more suitable silicate materials (e.g., silica from the calcium-depleted solids portion) and heated in the presence of steam to convert the calcium chloride-comprising solids to dechlorinated solids comprising calcium compounds, such as described elsewhere herein, while regenerating a leaching agent, such as HCl, which may be directed back to a leaching tank or acid reservoir. The dechlorinated solids comprising calcium compounds may be stored for later use (1332) and/or transferred to a clinker kiln (1333) for combination with a suitable fluxing agent for conversion to clinker. Some or all of the fluxing agent may contain insoluble metal species separated from the treated leach solution (1324), for example containing metal oxides, such as iron and/or aluminium oxides. After heat treatment in a clinker kiln (1333), the clinker is then transferred to a cooling unit (1334), and the cooled clinker can then be transferred to a mill (1335) for processing into cement. A portion of the dechlorinated solids comprising calcium compounds, clinker and/or cement may be used as some or all of the base for precipitating magnesium in the precipitation tank (1325). Some or all of the cement may be sold. A portion or all of the cement may be used to produce concrete, optionally in combination with a portion of the calcium-depleted solid fraction (acting as SCM) and/or with aggregate formed from the starting materials, for example during crushing and/or milling.

In certain embodiments, provided herein are concrete generating facilities comprising a source of cement and a source of aggregate, wherein both the cement and the aggregate are derived from the same material, such as the non-limestone materials described herein. The facility may also include a source of SCM, wherein SCM is also derived from the same material. The facility may include a mixer for mixing cement, aggregate, and optionally SCM to produce concrete. In certain embodiments, the system further comprises a source of cement produced by conventional methods (calcination and sintering), and in certain embodiments, this conventional cement is also provided to the mixer.

Description of the embodiments

In embodiment 1, there is provided a method for producing clinker, the method comprising: (a) Contacting a non-limestone material comprising calcium with hydrochloric acid to produce a calcium-depleted solid fraction and a calcium-enriched liquid fraction comprising calcium chloride; (b) Treating the calcium-rich liquid fraction to produce solids comprising calcium chloride; (c) Dechlorination of a solid comprising calcium chloride to produce a dechlorinated solid comprising a calcium compound; and (d) treating the dechlorinated solids comprising calcium to produce clinker. In embodiment 2, there is provided the method of embodiment 1, further comprising separating the calcium-depleted solids portion from the calcium-enriched liquid portion. In embodiment 3, there is provided the method of embodiment 1 or embodiment 2, wherein the calcium-rich liquid fraction comprises one or more non-calcium salts of magnesium, iron, and/or aluminum, and treating the calcium-rich liquid fraction comprises treating the liquid to precipitate one or more insoluble magnesium, iron, and/or aluminum compounds. In embodiment 4, there is provided the method of embodiment 3, wherein treating the calcium-rich liquid fraction comprises contacting the fraction with a base. In embodiment 5, there is provided the method of embodiment 4, wherein treating the calcium-rich liquid fraction comprises subjecting the fraction to thermal hydrolysis to precipitate aluminum and/or iron-containing insoluble compounds, removing the aluminum and/or iron-containing insoluble compounds, and then contacting the remaining calcium-rich liquid fraction with a base. In embodiment 6, there is provided the method of any preceding embodiment, further comprising partially dewatering the calcium-rich liquid to produce a solid comprising calcium chloride. In embodiment 7, there is provided the method of any preceding embodiment, wherein dechlorinating the solid comprising calcium chloride comprises heating the solid in the presence of steam and silica to produce a dechlorinated solid comprising calcium. In embodiment 8, there is provided the method of embodiment 7, wherein the calcium and silica are present in a molar ratio between 2.45 and 3.25 ca:si. In embodiment 9, there is provided the method of any preceding embodiment, wherein treating the dechlorinated solids comprising calcium to produce clinker comprises heating the solids with a fluxing agent. In embodiment 10, the method of embodiment 9 is provided, wherein the fluxing agent comprises aluminum and iron oxide. In embodiment 11, there is provided the method of any of the preceding embodiments, further comprising processing the clinker to produce cement.

In embodiment 12, there is provided a method for preparing a solid material comprising one or more magnesium compounds capable of reacting with and sequestering carbon dioxide, the method comprising: (a) Contacting a non-limestone starting material with an acid to produce a calcium-rich liquid fraction comprising magnesium and a calcium-depleted solid fraction; (b) Treating the calcium-rich liquid portion to precipitate one or more magnesium compounds capable of reacting with and sequestering carbon dioxide; (c) separating the magnesium-rich precipitate from the calcium-rich liquid fraction; and (d) washing and drying the magnesium-rich precipitate. In embodiment 13, the method of embodiment 12 is provided, further comprising separating one or more magnesium compounds capable of reacting with and sequestering carbon dioxide from the liquid. In embodiment 14, the method of embodiment 13 is provided, further comprising rinsing and drying the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide. In embodiment 15, there is provided the method of any one of embodiments 12 to 14, wherein the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide comprise magnesium oxide, hydroxide, oxyhydroxide, silicate hydrate, complex, or a combination thereof. In embodiment 16, there is provided the method of any one of embodiments 12 to 15, further comprising contacting one or more magnesium compounds capable of reacting with and sequestering carbon dioxide with carbon dioxide to sequester carbon dioxide as magnesium carbonate or magnesium bicarbonate. In embodiment 17, the method of embodiment 16 is provided, wherein the contacting comprises exposing one or more magnesium compounds capable of reacting with and sequestering carbon dioxide to a flue gas comprising carbon dioxide, such as a flue gas produced during a process to produce one or more magnesium compounds capable of reacting with and sequestering carbon dioxide, to produce magnesium carbonate. In embodiment 18, the method of embodiment 16 is provided, wherein the contacting comprises exposing one or more magnesium compounds capable of reacting with and sequestering carbon dioxide to air comprising carbon dioxide to produce magnesium carbonate. In embodiment 19, the method of embodiment 16 is provided, wherein the contacting comprises placing one or more magnesium compounds capable of reacting with and sequestering carbon dioxide in a body of water, such as a ocean, to react with carbon dioxide within the body of water to produce magnesium bicarbonate.

In embodiment 20, a method for obtaining carbon credits is provided, the method comprising: (a) The avoided net carbon dioxide (CO 2) value and/or the sequestered net CO2 value is calculated by: (i) Performing the method of any one of embodiments 1-18, 27-72, or 139-161; (ii) Tracking one or more sequestered CO2 amounts, one or more avoided CO2 amounts, and one or more CO2 outputs; (iii) Determining an amount of avoided CO2 and/or an amount of isolated CO2 based on the one or more isolated CO2 amounts, the one or more avoided CO2 amounts, and the CO2 output; and (b) obtaining carbon credit based on the value of CO2 avoided and/or sequestered in (a) (iii). In embodiment 21, there is provided the method of embodiment 20, wherein the avoided CO2 value is determined by: the same amount of cement was produced by a process comprising calcining limestone and compared to the amount of CO2 produced by the process of any of embodiments 1-18, 27-72 or 139-161. In embodiment 22, the method of embodiment 20 or 21 is provided wherein the value of sequestered CO2 is determined by sequestering CO2 with Mg compound and quantifying the amount of CO2 sequestered by a given amount of Mg compound. In embodiment 23, the method of embodiment 22 is provided, wherein at least a portion of the sequestered CO2 is atmospheric CO2.

In embodiment 24, a composition is provided comprising at least 50, 60, 70, 80, 90 or 95% w/w calcium chloride, for example at least 90%, in a preferred embodiment at least 95% calcium chloride; and at least 50, 60, 65, 70, 75, 80, 85, 90 or 95% silica, for example at least 60%, preferably at least 75%, more preferably at least 80% w/w. In embodiment 25, there is provided a composition of embodiment 24 comprising less than 10, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1% Cl w/w, in preferred embodiments less than 5%, in more preferred embodiments less than 1%. In embodiment 26, there is provided a composition of embodiment 24 or 25 comprising less than 20, 15, 10, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 or 0.1% CaO w/w, in preferred embodiments less than 5%, in more preferred embodiments less than 0.5%.

In embodiment 27, there is provided a method for dechlorinating a solid comprising calcium chloride, the method comprising (i) combining a solid comprising calcium chloride with a solid comprising silica; and (ii) heating the combined calcium chloride and silica to a temperature of 750-1250 ℃ in the presence of steam to produce HCl gas and a dechlorinated calcium product. In embodiment 28, the method of embodiment 27 is provided, wherein the temperature is 900-1250 ℃. In embodiment 29, the method of embodiment 27 is provided, wherein the temperature is 1000-1250 ℃. In embodiment 30, the method of embodiment 27 is provided, wherein the temperature is 1100-1250 ℃. In embodiment 31, there is provided the method of any one of embodiments 27 to 30, wherein when the temperature reaches 700-750 ℃, heating is continued at a rate of no more than 60, 50, 40, 30, 10, or 5 ℃/minute until a temperature of 800-850 ℃ is reached. In embodiment 32, there is provided the method of any one of embodiments 27 to 31, wherein the solid comprising calcium chloride is combined with the solid comprising silica such that a Ca-Si molar ratio of between 2.5 and 3.5 is achieved. In embodiment 33, there is provided the method of any one of embodiments 27 to 31, wherein the solid comprising calcium chloride is present at 50-90wt% and the silica is present at 10-40 wt%. In embodiment 34, there is provided the method of any one of embodiments 27 to 33, wherein the solid comprising calcium chloride comprises at least 80%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% calcium chloride, preferably at least 90%, more preferably at least 95%. In embodiment 35, there is provided the method of any one of embodiments 27 to 34, wherein the solid comprising silica comprises at least 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% silica, preferably at least 60%, more preferably at least 75%, even more preferably at least 80%. In embodiment 36, there is provided the method of embodiment 35, wherein the solid comprising calcium chloride comprises at least 90% calcium chloride and the solid comprising silica comprises at least 80% silica. In embodiment 37, there is provided the method of any one of embodiments 27 to 36, wherein the steam is present at 5-100 vol%. In embodiment 38, there is provided the method of any one of embodiments 27 to 37, wherein the chlorine content is reduced by at least 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98% or 99%, preferably at least 90%, more preferably at least 95%, even more preferably at least 99%. In embodiment 39, there is provided the method of any of embodiments 27 to 38, wherein the decalcified product comprises at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80wt% dicalcium silicate, preferably at least 15%, more preferably at least 25% dicalcium silicate, and less than 30, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1wt% CaO, preferably less than 10%, more preferably less than 5% CaO. In embodiment 40, the method of embodiment 40 is provided, wherein the dechlorinated calcium product comprises at least 15% dicalcium silicate and less than 10% CaO.

In embodiment 41, there is provided a method of producing clinker from solids comprising calcium chloride, the method comprising: (a) Dechlorination of a solid comprising calcium chloride to produce a dechlorinated composition comprising Ca and having less than 10% w/w Cl; and (b) heating the dechlorinated composition in the presence of a fluxing agent to produce clinker. In embodiment 42, the method of embodiment 41 is provided, wherein the clinker comprises dicalcium silicate and tricalcium silicate. In embodiment 43, the method of embodiment 41 or 42 is provided, wherein the clinker comprises portland cement clinker. In embodiment 44, there is provided the method of any one of embodiments 41-43, wherein the composition comprising calcium chloride further comprises silica. In embodiment 45, the method of embodiment 44 is provided wherein the molar ratio of Ca to Si in the composition comprising calcium chloride and silica is from 1.0 to 5.0, preferably from 2.0 to 4.0, more preferably from 2.5 to 3.25. In embodiment 46, there is provided the method of any one of embodiments 41-45, wherein the composition comprising calcium chloride comprises at least 80%, 90%, 92%, 95%, 96%, 97%, 98% or 99% calcium chloride, preferably at least 80%, more preferably at least 90%, even more preferably at least 95%. In embodiment 47, there is provided the method of any one of embodiments 41 to 46, wherein the dechlorination composition comprises less than 30, 20, 10, 8, 5, 4, 3, 2, or 1% CaO, preferably less than 10%, more preferably less than 5%. In embodiment 48, there is provided the composition of any of embodiments 41-47, wherein the dechlorinated composition comprises no more than 10%, 8%, 6%, 5%, 4%, 3%, 2% or 1% Cl, preferably no more than 10%, more preferably no more than 5%, even more preferably no more than 1% by weight. In embodiment 49, there is provided the method of any of embodiments 41-48, wherein the dechlorination composition comprises at least 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40% dicalcium silicate, preferably at least 15%, more preferably at least 25%. In embodiment 50, there is provided the method of any one of embodiments 41-49, wherein dechlorinating the composition comprising calcium chloride comprises heating the composition. In embodiment 51, the method of embodiment 50 is provided, further comprising introducing steam when the composition comprising calcium chloride reaches a temperature of 300 ℃ or greater. In embodiment 52, there is provided the method of embodiment 51, wherein heating the composition comprising calcium chloride in the presence of steam comprises heating to a temperature of at least 750 ℃ and/or not more than 1250 ℃. In embodiment 53, the method of embodiment 52 is provided wherein the rate of heating is no more than 100, 80, 50, 40, 30, 25, 20, 15, 10, 5, or 1 °/min or slower between 700-750 ℃ and 800-1000 ℃. In embodiment 54, the method of any one of embodiments 41-53 is provided, wherein HCl is produced during the dechlorination process. In embodiment 55, the method of any one of embodiments 41-54 is provided, wherein the fluxing agent comprises iron and/or an aluminum compound. In embodiment 56, the method of embodiment 55 is provided wherein the aluminum compound comprises Al2O3 and/or the iron compound comprises Fe2O3. In embodiment 57, the method of embodiment 55 or embodiment 56 is provided, wherein the iron compound and/or aluminum compound and the composition comprising calcium chloride are produced from the same starting material. In embodiment 58, the method of embodiment 57 is provided, wherein the starting material comprises calcium-containing rock and/or minerals. In embodiment 59, the method of any one of embodiments 44-58 is provided, wherein the silica is produced from the same starting material as that used for the composition comprising calcium chloride. In embodiment 60, there is provided the method of any one of embodiments 41 to 59, wherein heating the dechlorinated composition in the presence of a fluxing agent comprises heating the composition to 1200-1600 ℃, preferably 1400-1600 ℃. In embodiment 61, the method of embodiment 60 is provided, comprising heating the composition to 1500-1600 ℃. In embodiment 62, the method of embodiment 60 is provided, comprising heating the composition to 1450-1500 ℃. In embodiment 63, there is provided the method of any one of embodiments 41-62, wherein the dichlorination and/or heating of the dechlorinated composition is performed in a kiln. In embodiment 64, the method of embodiment 63 is provided, wherein the kiln comprises a rotary kiln.

In embodiment 65, a method of producing clinker is provided that includes heating a composition comprising dicalcium silicate and no more than 20%, 15%, 10%, 5%, 2% or 1% CaO, such as no more than 10% CaO, in the presence of a fluxing agent to produce clinker. In embodiment 66, the method of embodiment 65 is provided, wherein the composition contains less than 5, 4, 3, 2, 1, 0.5, or 0.1% tricalcium silicate, preferably less than 1%, more preferably less than 0.1%, and the clinker comprises at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60% tricalcium silicate, preferably at least 20%, more preferably at least 50%. In embodiment 67, the method of embodiment 65 or 66 is provided, wherein the fluxing agent comprises aluminum and/or iron oxide.

In embodiment 68, there is provided a method of producing clinker and Supplemental Cement Material (SCM) from a starting material comprising a non-limestone material, the non-limestone material comprising calcium and silicon, the method comprising: (i) Dissolving a non-limestone material in HCl to produce a calcium-rich liquid fraction comprising calcium chloride and a calcium-depleted solid fraction comprising silica; (ii) Generating SCM from a calcium-depleted solids portion comprising silica; and (iii) producing clinker from the calcium-rich liquid fraction comprising calcium chloride. In embodiment 69, the method of embodiment 68 is provided, the method further comprising producing aggregate from the non-limestone material. In embodiment 70, the method of embodiment 68 or embodiment 69 is provided, further comprising producing cement from the clinker. In embodiment 71, the method of embodiment 70 is provided, further comprising combining the cement, aggregate, and water to produce the concrete. In embodiment 72, the method of embodiment 71 is provided, further comprising combining the SCM with cement, aggregate, and water to produce concrete.

In embodiment 73, an apparatus for producing clinker from non-limestone material is provided, the apparatus comprising (i) a first processor configured to process a non-limestone starting material to produce a solid composition comprising calcium chloride operably connected to (ii) a second processor configured to form clinker from the solid composition comprising calcium chloride. In embodiment 74, the apparatus of embodiment 73 is provided, wherein the first processor comprises (a) a leacher configured to contact the non-limestone material with acid to produce a first calcium-rich liquid fraction and a calcium-depleted solid fraction, operatively connected to (b) a settler configured to remove the one or more non-calcium salts from the calcium-rich fraction by converting the one or more non-calcium salts to a solid form removed from the calcium-rich fraction; and (c) a dehydrator configured to remove water from the calcium-rich liquid fraction from the precipitator to produce a solid comprising calcium chloride. In embodiment 75, the apparatus of embodiment 73 or embodiment 74 is provided, wherein the first processor further comprises a materials processor configured to process non-limestone starting materials, operatively connected to the leacher. In embodiment 76, the apparatus of embodiment 75 is provided, wherein the material processing machine is configured to reduce the size of the non-limestone material and/or to sort the material into one or more size ranges. In embodiment 77, the apparatus of any one of embodiments 74-76 is provided, wherein the first processor further comprises an acid storage tank operably connected to the leacher. In embodiment 78, the apparatus of any one of embodiments 74-77 is provided, wherein the leacher comprises a heating element. In embodiment 79, the apparatus of any one of embodiments 74-78 is provided, wherein the leacher comprises an agitator. In embodiment 80, the apparatus of any one of embodiments 74-79 is provided, wherein the leacher further comprises a first separator operatively connected to the leacher and the settler, configured to separate the calcium-rich liquid fraction and the calcium-depleted solid fraction, and to direct the calcium-rich liquid fraction to the settler. In embodiment 81, the apparatus of any one of embodiments 74-80 is provided, wherein the precipitator is operatively connected to a second separator to separate solids from the calcium-rich liquid fraction. In embodiment 82, the apparatus of any one of embodiments 74-81 is provided, wherein the precipitator comprises a first precipitation unit that is a base precipitation unit configured to precipitate a first set of non-calcium compounds. In embodiment 83, the apparatus of embodiment 82 is provided, further comprising one or more alkali sources operably connected to the first precipitation unit. In embodiment 84, the apparatus of embodiment 83 is provided wherein the one or more alkali sources comprise a calcium alkali source. In embodiment 85, the apparatus of any one of embodiments 82 to 85 is provided, wherein the precipitator comprises a second precipitation unit that is a thermal hydrolysis precipitation unit configured to precipitate a second set of non-calcium compounds from the calcium-rich liquid fraction. In embodiment 86, the apparatus of embodiment 85 is provided, wherein the second precipitation unit is operatively connected to the third separator to separate the second set of precipitated non-calcium compounds from the calcium-rich liquid fraction. In embodiment 87, the apparatus of embodiment 85 or embodiment 86 is provided, wherein the precipitator comprises a third precipitation unit, which is a thermal hydrolysis unit for precipitating a third set of non-calcium compounds from the calcium-rich liquid fraction. In embodiment 88, the apparatus of embodiment 87 is provided wherein the third precipitation unit is operatively connected to a fourth separator to separate the third set of precipitated non-calcium compounds from the calcium-rich liquid fraction. In embodiment 89, the apparatus of embodiment 87 or embodiment 88 is provided, wherein the second and third precipitation units are the same, and the second and third groups of precipitated non-calcium compounds are the same. In embodiment 90, the apparatus of embodiment 87 or embodiment 88 is provided, wherein the second precipitation unit and the third precipitation unit are different, and the second precipitation unit is configured to precipitate the aluminum compound by heating the calcium-rich liquid to a first temperature or temperature range, and the third precipitation unit is configured to precipitate the iron compound by heating the calcium-rich liquid to a second temperature or temperature range that is higher than the first temperature or temperature range. In embodiment 91, the apparatus of any one of embodiments 74 to 90 is provided, wherein the dehydrator comprises a heating element. In embodiment 92, the apparatus of any one of embodiments 73 to 91 is provided, wherein the second processing machine comprises (a) a dechlorination machine configured to dechlorinate solids comprising CaCl2 to produce dechlorinated solids comprising calcium compounds, operably connected to (b) a clinker machine configured to heat the dechlorinated solids in the presence of a fluxing agent to produce clinker. In embodiment 93, the apparatus of embodiment 92 is provided, wherein the dechlorination device is configured to produce a dechlorinated solid comprising a calcium compound and less than 20, 15, 10, 8, 7, 6, 5, 4, 3, 2, or 1wt% cl. In embodiment 94, the apparatus of embodiment 92 or embodiment 93 is provided, wherein the alkali source comprises dechlorinated solids from a dechlorinated machine and/or cement clinker from a cement kiln. In embodiment 95, the apparatus of any one of embodiments 92 to 94 is provided, wherein the dechlorinating device is operably connected to (1) one or more steam sources; and (2) one or more silica sources. In embodiment 96, the apparatus of embodiment 95 is provided, wherein the one or more steam sources comprise a dehydrator of the first processing machine. In embodiment 97, the apparatus of embodiment 95 or embodiment 96 is provided, wherein the one or more silica sources comprise a first processor or portion thereof. In embodiment 98, the apparatus of embodiment 97 is provided, wherein the first processor or portion thereof comprises a first separator. In embodiment 99, the apparatus of any one of embodiments 92 to 98 is provided, wherein the maturation vessel is operably connected to one or more sources of fluxing agent; in embodiment 100, the apparatus of embodiment 99 is provided wherein the one or more sources of fluxing agent comprise a first processor or portion thereof. In embodiment 101, the apparatus of embodiment 100 is provided, wherein the first processor or portion thereof comprises a settler. In embodiment 102, there is provided the apparatus of any one of embodiments 92 to 101, wherein the dechlorinating device and/or clinker device comprises a rotary kiln. In embodiment 103, an apparatus of any one of embodiments 92 to 102 is provided, further comprising a clinker processor for processing clinker from the clinker aggregate. In embodiment 104, the apparatus of any one of embodiments 73 to 102 is provided, further comprising a control system, wherein the control system comprises (i) one or more input sources from the first processing machine and/or the second processing machine; (ii) A processor for processing inputs from one or more input sources and providing outputs; and (iii) one or more actuators that receive the output and adjust one or more operations of the first and/or second machines. In embodiment 105, the apparatus of embodiment 104 is provided wherein the one or more input sources comprise one or more sensors, such as one or more temperature sensors, to detect the temperature of the leacher, dehydrator, dechlorinated machine and/or clinker or portion thereof. In embodiment 106, the apparatus of embodiment 104 or embodiment 105 is provided wherein the actuator comprises one or more actuators that regulate operation of heating elements for the leacher, dehydrator, dechlorinated and/or clinker.

In embodiment 107, there is provided a network comprising a plurality of devices of any one of embodiments 73 to 106, wherein the devices are spatially separated, and wherein the devices each send information to a common controller and/or multiple controllers.

In an embodiment 108, an apparatus for producing solids including calcium chloride from non-limestone material including calcium is provided, wherein the apparatus includes a processing machine configured to process non-limestone starting material to produce solids including calcium chloride. In embodiment 109, the apparatus of embodiment 108 is provided, wherein the processing machine comprises (a) a leacher configured to contact the non-limestone material with an acid to produce a first calcium-rich liquid fraction and a calcium-depleted solid fraction, operatively connected to (b) a precipitator configured to remove the one or more non-calcium salts from the calcium-rich fraction by converting the one or more non-calcium salts to a solid form removed from the calcium-rich fraction; and (c) a dehydrator configured to remove water from the calcium-rich liquid fraction from the precipitator to produce a solid comprising calcium chloride. In embodiment 110, the apparatus of embodiment 108 or embodiment 109 is provided, wherein the processor further comprises a materials processor configured to process non-limestone starting materials, operatively connected to the leacher. In embodiment 111, the apparatus of embodiment 110 is provided wherein the material processing machine is configured to reduce the size of the non-limestone material and/or to sort the material into one or more size ranges. In embodiment 112, the apparatus of any one of embodiments 109-111 is provided, wherein the processor further comprises an acid storage tank operably connected to the leacher. In embodiment 113, the apparatus of any one of embodiments 109-112 is provided, wherein the leacher comprises a heating element. In embodiment 114, the apparatus of any one of embodiments 109-113 is provided, wherein the leacher comprises an agitator. In embodiment 115, the apparatus of any one of embodiments 109-114 is provided, wherein the leacher further comprises a first separator operatively connected to the leacher and the precipitator, configured to separate a calcium-rich liquid fraction and a calcium-depleted solid fraction, and to direct the calcium-rich liquid fraction to the precipitator. In embodiment 116, the apparatus of any one of embodiments 109-115 is provided, wherein the precipitator is operatively connected to a second separator to separate solids from the calcium-rich liquid fraction. In embodiment 117, the apparatus of any one of embodiments 109-116 is provided, wherein the precipitator comprises a first precipitation unit that is a base precipitation unit configured to precipitate a first set of non-calcium compounds. In embodiment 118, the apparatus of embodiment 117 is provided, further comprising one or more alkali sources operably connected to the first precipitation unit. In embodiment 119, the apparatus of embodiment 118 is provided wherein the one or more alkali sources comprise calcium alkali sources. In embodiment 120, the apparatus of any one of embodiments 109-120 is provided, wherein the precipitator comprises a second precipitation unit that is a thermal hydrolysis precipitation unit configured to precipitate a second set of non-calcium compounds from the calcium-rich liquid fraction. In embodiment 121, the apparatus of embodiment 121 is provided, wherein the second precipitation unit is operably connected to the third separator to separate the second set of precipitated non-calcium compounds from the calcium-rich liquid fraction. In embodiment 122, the apparatus of embodiment 120 or embodiment 121 is provided, wherein the precipitator comprises a third precipitation unit, which is a thermal hydrolysis unit for precipitating a third set of non-calcium compounds from the calcium-rich liquid fraction. In embodiment 123, the apparatus of embodiment 122 is provided, wherein the third precipitation unit is operably connected to the fourth separator to separate the third set of precipitated non-calcium compounds from the calcium-rich liquid fraction. In embodiment 124, the apparatus of embodiment 122 or embodiment 123 is provided, wherein the second and third precipitation units are the same, and the second and third sets of precipitated non-calcium compounds are the same. In embodiment 125, the apparatus of embodiment 122 or embodiment 123 is provided, wherein the second precipitation unit and the third precipitation unit are different, and the second precipitation unit is configured to precipitate aluminum compounds by heating the calcium-rich liquid to a first temperature or temperature range, and the third precipitation unit is configured to precipitate iron compounds by heating the calcium-rich liquid to a second temperature or temperature range that is higher than the first temperature or temperature range. In embodiment 126, the apparatus of any one of embodiments 109-125 is provided, wherein the dehydrator comprises a heating element.

In embodiment 127, an apparatus for producing clinker from solids comprising calcium chloride is provided, wherein the apparatus comprises (a) a dechlorination device configured to dechlorinate solids comprising calcium chloride to produce dechlorinated solids comprising calcium compounds, operably connected to (b) a clinker device configured to heat the dechlorinated solids in the presence of a fluxing agent to produce clinker. In embodiment 128, the apparatus of embodiment 127 is provided, wherein the dechlorination device is configured to produce a dechlorinated solid comprising a calcium compound and less than 20, 15, 10, 8, 7, 6, 5, 4, 3, 2, or 1wt% cl. In embodiment 129, the apparatus of embodiment 127 or embodiment 128 is provided, wherein the dechlorination device is operably connected to (1) one or more steam sources; and (2) one or more silica sources. In embodiment 130, the apparatus of any one of embodiments 127 to 129 is provided, wherein the clinker is operably connected to one or more sources of fluxing agent; in embodiment 131, the apparatus of any one of embodiments 127 to 130 is provided, wherein the dechlorinating device and/or clinker device comprises a rotary kiln. In embodiment 132, the apparatus of any one of embodiments 127 to 131 is provided, further comprising a clinker processor for processing clinker from the cement kiln. In embodiment 133, the apparatus of any one of embodiments 127 to 132 is provided, further comprising a control system, wherein the control system comprises (i) one or more input sources from a dechlorinating device and/or a maturing device; (ii) A processor for processing inputs from one or more input sources and providing outputs; and (iii) one or more actuators that receive the output and adjust one or more operations of the dechlorinated and/or cooked device. In embodiment 134, the apparatus of embodiment 133 is provided wherein the one or more input sources comprise one or more sensors, such as one or more temperature sensors, to detect the temperature of the dechlorinated and/or clinker or portion thereof. In embodiment 135, the apparatus of embodiment 133 or embodiment 134 is provided wherein the actuator comprises one or more actuators that regulate operation of a heating element for the dechlorination and/or clinker.

In an embodiment 136, a system is provided comprising: (a) A first processor configured to produce cement from a non-limestone material; (b) A second processor configured to produce SCM from non-limestone material. In embodiment 137, the system of embodiment 136 is provided, further comprising (c) a third processor that produces aggregate from a non-limestone material. In embodiment 138, the systems of embodiments 136 and 137 are provided wherein the first and second processors are the same.

In embodiment 139, a method for producing clinker is provided, the method comprising (a) dissolving a non-limestone material comprising calcium in an acid to produce a calcium-enriched liquid fraction comprising calcium chloride and a calcium-depleted solid fraction; (b) separating the calcium-depleted solids portion from the calcium-enriched liquid portion; (c) producing a solid comprising calcium chloride from the calcium-rich liquid; and (d) treating the solids comprising calcium chloride to form clinker. In embodiment 140, the method of embodiment 139 is provided wherein the non-limestone material further comprises silicon. In embodiment 141, the method of embodiment 139 or embodiment 140 is provided, wherein the non-limestone material comprises rock and/or minerals. In embodiment 142, the method of embodiment 141 is provided wherein the non-limestone material comprising rocks and/or minerals comprises clinoptilolite, sika, pyroxene, faerionite, basalt, cuprocarrite, wolframite, quarry rock, mafic rock, ultramafic rock, or a combination thereof. In embodiment 143, there is provided the method of any one of embodiments 139 to 142, wherein no more than 40%, 30%, 20%, 15%, 10%, 5%, 4%, 3%, 2% or 1% of the calcium in the starting material is present in the form of calcium carbonate, preferably no more than 10%, more preferably no more than 5%. In embodiment 144, the method of any one of embodiments 139 to 143 is provided wherein the starting material further comprises aluminum, iron, and/or magnesium. In embodiment 145, the method of any of embodiments 139 to 144 is provided, wherein the method produces less than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5% of the emitted CO2 as compared to producing the same amount of hydraulic cement from limestone by a process comprising calcining limestone. In embodiment 146, the method of embodiment 145 is provided, wherein the method produces less than 80% of the emitted CO2. In embodiment 147, the method of embodiment 145 is provided, wherein the method produces less than 60% of the emitted CO2. In embodiment 148, the method of embodiment 145 is provided, wherein the method produces less than 40% of the emitted CO2. In embodiment 149, the method of any one of embodiments 139 to 148 is provided, wherein the method further produces Supplemental Cementitious Material (SCM), mg derivatives, and/or aggregate. In embodiment 150, the method of embodiment 149 is provided wherein the SCM, mg derivatives, and/or aggregate are produced from the same starting materials as are used to produce the cement. In embodiment 151, the method of any one of embodiments 139 to 151 is provided, wherein the acid comprises HCl, HBr, HI, HNO3 or a combination thereof. In embodiment 152, the method of embodiment 151 is provided, wherein the acid comprises at least 80%, 90%, 95%, 99%, or 100% HCl. In embodiment 153, the method of any one of embodiments 139-152 is provided wherein the concentration of the acid is 10-37%. In embodiment 154, the method of embodiment 153 is provided, wherein the concentration of the acid is 15-25%. In embodiment 155, the method of embodiment 153 is provided, wherein the concentration of the acid is 20%. In embodiment 156, the method of any one of embodiments 139-155 is provided, wherein producing a solid comprising calcium compounds comprising calcium chloride from the calcium-rich liquid comprises precipitating one or more compounds comprising aluminum, iron, and/or magnesium from the calcium-rich liquid. In embodiment 157, the method of any of embodiments 139-156 is provided, wherein producing a solid comprising calcium compound comprising calcium chloride from the calcium-rich liquid comprises dewatering the liquid to produce a solid comprising calcium chloride. In embodiment 158, the method of any of embodiments 139-157 is provided, wherein treating the solids comprising calcium chloride to form clinker comprises dechlorinating the solids comprising calcium chloride to produce dechlorinated solids comprising calcium compounds. In embodiment 159, the method of embodiment 158 is provided, wherein dechlorinating comprises heating the solid comprising calcium chloride in the presence of steam and silica. In embodiment 160, the method of embodiment 158 or embodiment 159 is provided, further comprising treating the dechlorinated solids comprising a calcium compound to produce clinker. In embodiment 161, the method of embodiment 160 is provided, wherein the treating comprises heating the dechlorinated solid comprising the calcium compound in the presence of a fluxing agent.

Throughout the specification, when compositions are described as having, comprising or including a particular component, or when processes and methods are described as having, comprising or including a particular step, it is additionally contemplated that compositions of the present invention consisting essentially of or consisting of the recited components are present, and that processes and methods in accordance with the present invention consist essentially of or consist of the recited processing steps.

In the present application, when an element or component is referred to as being included in and/or selected from a list of enumerated elements or components, it is understood that the element or component may be any of the enumerated elements or components, or the element or component may be selected from the group consisting of two or more of the enumerated elements or components.

Furthermore, it is to be understood that elements and/or features of the compositions or methods described herein may be combined in various ways without departing from the spirit and scope of the present invention, whether explicit or implicit herein. For example, when referring to a particular compound, the compound may be used in various embodiments of the compositions of the invention and/or the methods of the invention unless otherwise understood from the context. In other words, within the present application, embodiments have been described and depicted in a manner that enables writing and drawing of a clear and concise application, but it is intended and understood that the embodiments may be combined or separated in various ways without departing from the present teachings and invention. For example, it is to be understood that all features described and depicted herein are applicable to all aspects of the invention described and depicted herein.

The use of the terms "a" and "an" and "the" and similar referents 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 "cell" includes a plurality of cells, including mixtures thereof. Where plural forms are used for compounds, salts, and the like, this should be taken to also mean a single compound, salt, and the like.

It should be understood that the expression "at least one" individually includes each of the objects listed after the expression as well as various combinations of two or more of the listed objects unless otherwise understood from context and use. The expression "and/or" in relation to three or more of the listed objects should be understood to have the same meaning unless otherwise understood from the context.

The use of the terms "include," "comprises," "including," "has," "having," "has," "containing," "contains," "containing," or "containing" are generally understood to be open-ended and non-limiting, e.g., not excluding additional unrecited elements or steps, unless the context clearly dictates otherwise.

When the terms "about", "about" and the like are used prior to a quantitative value, the invention also includes the particular quantitative value itself, unless specifically stated otherwise. As used herein, the term "about" refers to a variation from the nominal value of ±10%, unless otherwise specified or inferred.

It should be understood that the order of steps or order in which certain operations are performed is not important so long as the invention remains operable. In addition, two or more steps or operations may be performed simultaneously.

The use of any and all examples, or exemplary language (e.g., "such as" or "comprising") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

Examples

Example 1

In this example, efficient leaching of calcium from non-limestone rock was demonstrated.

The following leaching parameters were used for Ca-containing rocks, ca extraction >90% as measured by inductively coupled plasma emission spectroscopy (ICP-OES). The calcium mass balance was turned off by X-ray fluorescence (XRF) measurements on the initial rock and leach residue.

In all cases, the calcium yield of the rock was greater than 90% and the calcium yields of the skarn and the clinoptilolite were greater than 95% and 99%, respectively. Thus, HCl treatment can be used to extract high percentages of calcium from a variety of non-limestone rocks.

Example 2

In this example, preferential precipitation of non-calcium components from calcium-containing solutions is demonstrated.

By combining CaCl ₂ To the leachate produced as in example 1 was added to prepare a test solution of the following composition. The composition of the material is as follows:

by heating the above solution (trace elements not listed) to 150 ℃ for two hours, a solid is precipitated which is highly Ca-depleted and rich in iron and aluminum. These data indicate that non-Mg, non-Ca components can be substantially removed by hydrolysis. The precipitate composition as measured by XRF was:

Al ₂ O ₃	41.4
		Fe ₂ O ₃	20.5
CaO	2.98
		MgO	1.01
SiO ₂	0.756
		Cl	0.620
SO ₃	0.166
		TiO ₂	0.143
MnO	0.0582
		P ₂ O ₅	0.0431
K ₂ O	0.0320
		Cr ₂ O ₃	0.0231
loss on ignition (%):	32.23

it can be seen that the composition of the precipitant is highly rich in iron and aluminium components, whereas the calcium and magnesium components are very low in content, and thus demonstrate the selective removal of iron and aluminium by heating the solution.

Example 3

In this example, the production of dicalcium silicate and tricalcium silicate from compositions derived from non-limestone rock, as well as extremely high chloride consumption, was demonstrated.

CaCl is added with ₂ With SiO ₂ (produced by leaching of calcareous longrock) at 3: caCl of 1 ₂ ：SiO ₂ Mixing in a molar ratio. The material was placed in a crucible and maintained for one hour after being heated to 850 ℃, 1000 ℃, 1200 ℃ and 1500 ℃ in sequence using a steam atmosphere at all temperatures except 1500 ℃. Dicalcium silicate and tricalcium silicate are both produced in large amounts as measured by X-ray diffraction (XRD) (below).

Surprisingly, XRF showed CaCl ₂ Can dechlorinate to>99.5％

CaO	66.2
		SiO ₂	31.4
Al ₂ O ₃	1.89
		MgO	0.189
Fe ₂ O ₃	0.0519
		Cl	0.0348
ZrO ₂	--
		Loss on ignition (%):	0.28

thus, in this example, the production of solid materials comprising dicalcium silicate and tricalcium silicate, and chloride consumption, was demonstrated to a level well below portland cement standards.

Example 4

Laboratory production of portland cement clinker by alternative routes

The initial feed was CaCl ₂ 、SiO ₂ 、Fe ₂ O ₃ 、Al ₂ O ₃ In a molar ratio of Ca to Si in the range of 2.5 to 3.25, and adjusting Al ₂ O ₃ -Fe ₂ O ₃ In an amount to meet the specific portland cement/clinker requirements of the final product. The clinker is produced by the feeding through a 2-step high-temperature process, and the chemical composition requirements of various portland cements are met according to the initial ratio. The first step is dechlorination. During the dechlorination, the mixture is reacted with superheated steam (5% to 100% by volume) at a temperature in the range 750 ℃ to 1250 ℃. Additional dichlorination may occur at higher temperatures, such as during curing. Note that Al ₂ O ₃ And Fe (Fe) ₂ O ₃ Is not an essential component for dechlorination and may be added later. The purpose of the dechlorination is to reduce the Cl content to less than 5 wt.%, and preferably less than 1 wt.%. The dechlorinated product is then cured at a temperature in the range 1400 ℃ to 1600 ℃ to produce clinker meeting the OPC standard chemical, compositional and performance requirements. The curing of the dechlorinated product may also be carried out in the presence of water vapour, similar to the moisture content in the combustion fumes or higher, which may result in clinker containing less than 0.01% by weight of residual Cl. SUMMARY

Laboratory procedure for dichlorination

i. CaCl of known purity ₂ 、SiO ₂ 、Al ₂ O ₃ And Fe (Fe) ₂ O ₃ The samples were dried in a muffle/box oven at 300 ℃ for 2 hours to ensure the starting materials were dry.

The dried samples were weighed and mixed with the desired composition so that the Ca-Si molar ratio was between 2.5 and 3.25. Calculation of Al taking into account the theoretical mass loss during dechlorination ₂ O ₃ And Fe (Fe) ₂ O ₃ Is a combination of the amounts of (a) and (b).

Ball milling the samples overnight to ensure uniformity of chemical composition. The ball-milled mixture was then used as a feed sample for dechlorination.

Weigh the platinum crucible and dry the feed sample weighed in the crucible at 300 ℃ for 2 hours to ensure drying. The tube furnace was preheated to 300 ℃.

After 2 hours, the sample + crucible was weighed and placed in a tube furnace.

The tube furnace was then programmed to reach 850 ℃ at a heating rate of about 10 ℃/min. The first 'soak' temperature may be in the range of 750 to 1250 deg.c, depending on experimental objectives. The vapor stream begins at about 750 ℃ to 800 ℃. As long as T >300 ℃, the steam flow can be started in advance without adverse effects.

The rate of temperature rise may vary between 5 and 20C, but is typically limited by laboratory ovens and is not always in line with process requirements. The sample can be heated rapidly to about 700-700C without adverse effects. Typically, the heating from about 700 ℃ to about 1000 ℃ can be done more slowly to allow time for the CaCl2/SiO2 mixture to form a solid solution and react with H2O to dechlorinate and produce HCl (g). Heating at a rate of 10 c/min may meet the requirement of slow melting without premature melting before the CaCl2 fraction reacts with H2O (g) and SiO 2(s).

Peristaltic pumps were used to maintain the water flow to the steam generator so that the amount of water added was in stoichiometric excess during the experiment.

The heat treatment procedure typically consists of: soaking at 850 ℃ for 60 minutes, at 1000 ℃ for 60 minutes, and at 1100 ℃ for 120 minutes. However, the heat treatment cycle conditions are often varied. For example, the dichlorination reaction conditions vary between 750 to 1250 ℃ and have various intermediate elevated and soak temperatures.

After the reaction time at peak temperature, the water flow was stopped and the crucible was cooled in the furnace at 10 ℃/min. The crucible was taken out at around 600 ℃. This step is for safety and laboratory convenience. The sample itself can be taken from the oven at the end of the peak temperature without adverse effects.

The crucible containing the sample is weighed before transferring the sample into a gas tight scintillation vial.

General laboratory procedure for maturation

i. The platinum crucible was weighed and the dechlorinated sample weighed in the crucible was dried at 300 ℃ for 2 hours to ensure that the sample was dry. The tube furnace was preheated to 300 ℃.

After 2 hours, the sample + crucible was weighed and placed in a tube furnace.

The tube furnace is then programmed to reach 1500-1600 ℃ at a rate of rise of about 10 ℃/min. The curing temperature can range from 1400 to 1600 ℃. For gray OPC, the typical temperature is 1450-1500. For white OPC, typical temperatures are 1500-1600 ℃. The rate of temperature rise is based on laboratory equipment limitations. Curing may be achieved by placing the sample directly into a pre-heating furnace at the curing temperature, and/or the rate of temperature rise may be higher or the initial furnace temperature may be higher.

vapor/O ₂ The flow starts at about 350 ℃. The concentration of steam in the feed gas may vary between 0.5% and 10%. In addition, combustion flue gas can be used as steam and O ₂ Is not steam/O ₂ And (3) a mixture.

The heat treatment cycle typically comprises soaking at 1500 ℃ for 5 hours. The maturation time may vary, possibly as short as 15 minutes, depending on the conditions.

After the reaction time, the crucible is pulled from the tube furnace and placed on refractory bricks and quenched in air.

The crucible containing the clinker sample is weighed before transferring into an airtight scintillation vial.

The material was tested by XRF and the bosch calculation was performed. Table 1 lists the results of the various starting materials and final products.

Table 1 chemical analysis and bog calculation of feed, dechlorinated samples and clinker.

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Fig. 14 shows an exemplary optical micrograph of a clinker sample obtained in test 1. The alist (C3S) in both micrographs showed dark areas. Arrows in the right micrograph point to the ferrite and aluminate phases. The arrow on the left micrograph points to one of many small brown belite (C2S) inclusions.

This example shows that clinker having different proportions of C3S, C2S, C a and C4AF can be produced from calcium chloride, silica, alumina and iron oxide starting materials that meet ASTM standards for, for example, different types of cements.

Example 5

In this embodiment, the Supplementary Cementitious Material (SCM) is produced from rock; in one experiment, SCM meeting ASTM requirements for fly ash was produced; in another experiment, SCM meeting ASTM requirements for silicon powder was produced.

Figure 15 depicts a simplified process flow diagram of leaching of Ca-containing material. The process includes material receiving, crushing and grinding, leaching, liquid/solid separation, drying, and solids processing to meet ASTM standards. Each step is described in subsections.

Feed preparation

The size of the feed (calcareous feldspar from Greenland Canada, containing 77.6% anorthite (CaAl 2Si2O 8), 3.4% quartz (SiO 2), 1.2% muscovite or related mica KAl2 (AlSi 3O 10) (OH) 2, 0.4% kaolinite Al2Si2O5 (OH) 4 and 17.4% amorphous material) received ranged from 5 inches to hundreds of microns. Checking the visual moisture content of the received material; if it is moist or wet, it is dried in a drying oven at 110 ℃. Materials larger than 1000 microns are crushed to P80 in the range of 1200 to 1000 microns. The feed rock is then ground to P80 in the range 45 to 90 microns. The prepared rock was then subjected to initial composition analysis by X-ray fluorescence (XRF).

Leaching out

Reagent grade hydrochloric acid (HCl) was used as the leaching agent. Because of its corrosiveness, all materials of construction of the reaction vessel consist of borosilicate glass and polytetrafluoroethylene. The reflux condenser was connected to a circulating water cooler set between 15-20 ℃ for water and acid recovery. The heating mantle was connected to a temperature controller and the temperature in the reactor was measured using a type J thermocouple. Leaching of the calcium-containing feed rock proceeds as follows:

1. the target leaching conditions were 15-30% wt/wt HCl,10-30% wt/vol pulp density (ratio of solids weight to volume of leaching solution), 6 to 24 hours, 50 to 70% vol filling the reaction vessel. The leaching conditions for generating fly ash and silica fume were 20% HCl wt/wt, pulp density 27% (27 g feed rock per 100mL of leaching solution)

2. Once the leaching parameters are determined, the required feed rock amount is calculated and accurately measured to 0.1 to 1mg. The required volumes of reserve acid and water were also determined

3. The leaching agent was added to the reaction vessel and stirred slowly at 100 to 150 rpm. While stirring, feed rock was slowly added to the reactor through the solid feed port.

4. The vessel was closed and the stirring speed was increased to 200 to 300rpm to conduct the reaction. Heating to a target temperature range of 100 to 120 ℃ is started. Once the reaction mixture reaches the target temperature, the reaction is allowed to continue for a predetermined duration. For fly ash, the duration was 24 hours, after which the material was separated. For silica fume, leaching was carried out in the first step for 24 hours to give a residue, followed by leaching at the same acid concentration and pulp density for another 4 hours. At the end of the reaction, the heating was stopped and the reaction mixture consisting of leach mother liquor (PLS) and solids (residue), also called pulp, was cooled to 60 to 70 degrees.

Solid/liquid separation

The solid/liquid separation of the product is shown in fig. 15 and proceeds as follows:

1. a corrosion resistant tube connected to the adapter is placed at one end of the reactor vessel drain and within the corrosion resistant collection vessel. The reaction mixture is allowed to flow in a collection bottle, which is filtered or centrifuged

2. And (3) centrifuging:

a. PLS slurry was evenly distributed in centrifuge bottles and inserted into the centrifuge rotor.

b. The centrifuge is operated for 5 to 10 minutes

c. The supernatants were collected and processed to collect physical property data (density, pH, volume, rmV) and then aliquots were sent for chemical analysis.

3. Filtration

a. The filter assembly consisted of a filter flask, buchner funnel, various grades (3, 4, 5, 50) of filter paper and vacuum pump.

b. The filter paper was placed in a buchner funnel, wetted, and the pump was turned on to confirm that the seal was good.

c. The slurry was added to the hopper and separation occurred. The filtered leach mother liquor was collected, processed to collect physical property data (density, pH, volume, rmV) and then aliquots were sent for chemical analysis.

4. The filter cake/centrifuge particles are reslurried by adding water to about 25 to 50% by volume. Followed by another filtration or centrifugation step. The pH of the filter cake was monitored such that the end of filtration/centrifugation was marked by a filter cake pH of about 6-7

5. The filter cake/solid particles were collected into a drying tray and the wet weight was recorded.

Drying

The residual material collected from the S/L separation step was placed in a drying oven at 110℃for 24 to 48 hours prior to dry solids processing. At the end of the drying process, the dry weight of the filter cake is recorded and the moisture retention is calculated. The solids were deagglomerated using a mortar and pestle.

Analysis method

Sample preparation

Liquid portion

As shown in fig. 15, three streams were collected from the leaching process: PLS, washes and residues. Aliquots of the PLS and wash fractions were analyzed by inductively coupled plasma emission spectroscopy (ICP-OES).

Solid part

After collection, the residue was subjected to Loss On Ignition (LOI) analysis according to ASTM D7348. A portion of the oxidized residue sample was subjected to lithium borate melting, thereby producing glass beads and analyzed using X-ray fluorescence (XRF).

SCM Generation

The silica fume and fly ash specifications are provided in tables 1 and 2 of ASTM C1240 and C618, respectively. The following procedure was performed to meet SCM specifications:

1.325 mesh ASTM sieves were calibrated according to ASTM C430 using NIST 46h OPC fineness Standard

2. Three fineness tests were performed with the residual sample.

3. Based on the fineness results, the required grinding media and duration are determined to achieve the desired particle size.

4. The milling pot is obtained and filled with milling media until 40-50% of the volume is filled. The solids were added until approximately 1/2 inch above the media surface.

5. The pot containing the solid + medium was placed on a ball mill and ground.

6. Step 2 and inspection are repeated for dimensional testing.

7. Steps 2 to 6 may be repeated as required.

Fly ash and raw or calcined natural pozzolan standard Specification for concrete according to ASTM C618"

Supplementary Cement Material (SCM) was tested.

The "fly ash" samples were evaluated for compliance with the standard physical and compositional requirements of ASTM C618.

Mixing ratio and results

Table 2 (ASTM\C618) provides the results of analysis of the chemical composition of the samples. The proportions and flow rates of the test mortar samples are provided in table 3. The SCM content was 20% by weight of its mixture with portland cement (see: ASTM C618 and ASTM C311). The test results of the "fly ash" standard physical requirements are shown in Table 4 (ASTM C618).

TABLE 2 analysis of the composition of SCM samples (ASTM C618)

TABLE 3 mixing ratio of mortar samples (ASTMC 618) for determining the Water demand and the Strength Activity index

Material	Control sample	Test sample
			Portland cement (g)	500	400
SCM(g)	---	100
			Grading standard sand (g)	1375	1375
Water volume (ml)	242	234
			Flow (%), ASTM C1437	102	105

TABLE 4 physical Property test results (ASTM C618)

Flow (%), ASTM C1437 102 105scm "fly ash" samples meet the standard physical and compositional requirements of "class F" fly ash specified by ASTM C618

According to ASTM C1240' for

Standard specification for silica fume for cement mixtures "silica fume test was performed.

The "silicon powder" samples were evaluated for compliance with ASTM C1240 standard physical and compositional requirements.

Table 5 provides the analysis results of the sample chemistry (ASTM C1240). Table 6 provides the proportions and flow rates of the test mortar samples (ASTM C1240 and ASTM C311). Table 7 lists the test results (ASTM C1240) for the "silica fume" standard physical requirements.

TABLE 5 composition analysis results of silica powder samples (ASTM C1240)

TABLE 6 mixing ratio of mortar samples (ASTM C1240) for determining the index of accelerated pozzolan strength activity

Material	Control sample	Test sample (CH 21-269)
			Portland cement (g)	500	450
Silica flour (g)	---	50
			Grading standard sand (g)	1375	1375
Water volume (ml)	242	242
			Flow (%), ASTM C1437	108	102
HRWR(g)	--	0.26

TABLE 7 physical Property test results (ASTM C1240)

Silicon powder sample "silicon powder" meets the standard physical and chemical requirements specified by ASTM C1240.

This example shows that different types of SCMs meeting industry standards can be produced with non-limestone starting materials (in this case rocks and/or minerals), where SCMs meet industry standards for composition and function.

As will be recognized by those skilled in the art from the foregoing detailed description and from the accompanying drawings and claims, modifications and changes may be made to the embodiments of the invention without departing from the scope of the invention as defined in the appended claims.

Claims

1. A method of producing clinker, the method comprising:

(a) Contacting a non-limestone material comprising calcium with hydrochloric acid to produce a calcium-depleted solid fraction and a calcium-enriched liquid fraction comprising calcium chloride;

(b) Treating the calcium-rich liquid fraction to produce solids comprising calcium chloride;

(c) Dechlorination of the solids comprising calcium chloride to produce dechlorinated solids comprising calcium compounds; and

(d) The dechlorinated solids comprising calcium are treated to produce clinker.

2. The method of claim 1, further comprising separating the calcium-depleted solids portion from the calcium-enriched liquid portion.

3. The method of claim 1 or claim 2, wherein the calcium-rich liquid portion comprises one or more non-calcium salts of magnesium, iron, and/or aluminum, and treating the calcium-rich liquid portion comprises treating the liquid to precipitate one or more insoluble magnesium, iron, and/or aluminum compounds.

4. A method according to claim 3, wherein treating the calcium-rich liquid fraction comprises contacting the fraction with a base.

5. The method of claim 4, wherein treating the calcium-rich liquid fraction comprises subjecting the fraction to thermal hydrolysis to precipitate aluminum and/or iron-containing insoluble compounds, removing the aluminum and/or iron-containing insoluble compounds, and then contacting the remaining calcium-rich liquid fraction with the base.

6. The method of any one of the preceding claims, further comprising dewatering the calcium-rich liquid portion to produce the calcium chloride-containing solid.

7. The method of any one of the preceding claims, wherein dechlorinating the calcium chloride-containing solid comprises heating the solid in the presence of steam and silica to produce the calcium-containing dechlorinated solid.

8. The method of claim 7, wherein the calcium and silica are present in a molar ratio between 2.45 and 3.25ca: si.

9. The method of any one of the preceding claims, wherein treating the dechlorinated solids comprising calcium to produce clinker comprises heating the solids with a fluxing agent.

10. The method of claim 9, wherein the fluxing agent comprises aluminum and iron oxide.

11. The method of any one of the preceding claims, further comprising processing the clinker to produce cement.

12. A method of preparing a solid material comprising one or more magnesium compounds capable of reacting with and sequestering carbon dioxide, the method comprising:

(a) Contacting a non-limestone starting material with an acid to produce a calcium-rich liquid fraction comprising magnesium and a calcium-depleted solid fraction;

(b) Treating the calcium-rich liquid fraction to precipitate the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide;

(c) Separating the magnesium-rich precipitate from the calcium-rich liquid fraction; and

(d) The magnesium-rich precipitate is rinsed and dried.

13. The method of claim 12, further comprising separating the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide from the liquid.

14. The method of claim 13, further comprising rinsing and drying the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide.

15. The method of any one of claims 12 to 14, wherein the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide comprise magnesium oxide, hydroxide, oxyhydroxide, silicate hydrate, complex, or a combination thereof.

16. The method of any one of claims 12 to 15, further comprising contacting the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide with carbon dioxide to sequester the carbon dioxide as magnesium carbonate or magnesium bicarbonate.

17. The method of claim 16, wherein the contacting comprises exposing the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide to a flue gas comprising carbon dioxide, such as a flue gas produced during a process of producing the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide, to produce magnesium carbonate.

18. The method of claim 16, wherein the contacting comprises exposing the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide to air comprising carbon dioxide to produce magnesium carbonate.

19. The method of claim 16, wherein the contacting comprises placing the one or more magnesium compounds capable of reacting with and sequestering carbon dioxide in a body of water, such as a ocean, to react with carbon dioxide within the body of water to produce magnesium bicarbonate.

20. A method of obtaining carbon credits, the method comprising:

(a) The net carbon dioxide (CO) avoided is calculated by ₂ ) Value of (2) and/or sequestered net CO ₂ Is the value of (1):

(i) Performing the method of any one of claims 1-18, 27-72, or 139-161;

(ii) Tracking one or more sequestered COs ₂ Amount, amount of one or more avoided CO2 and amount of one or more CO ₂ Output quantity;

(iii) Determining the avoided CO based on the one or more sequestered CO2 amounts, the one or more avoided CO2 amounts, and the CO2 output ₂ Amount and/or sequestered CO ₂ An amount of; and

(b) Based on the CO avoided and/or sequestered in (a) (iii) ₂ Obtain a carbon credit.

21. The method of claim 20 wherein CO is avoided ₂ The value of (2) is determined by: producing the same amount of cement by a process comprising calcining limestone and CO produced by the process of any one of claims 1-18, 27-72, or 139-161 ₂ Is compared with the amount of (a).

22. A process as claimed in claim 20 or 21 wherein CO is sequestered by using Mg compounds ₂ And quantifying the CO sequestered by a given amount of Mg compound ₂ Is used to determine the amount of sequestered CO ₂ Is a value of (2).

23. The method of claim 22, wherein the sequestered CO ₂ At least a part of (a) is atmospheric CO ₂ 。

24. A composition comprising at least 50, 60, 70, 80, 90 or 95% w/w calcium chloride, for example at least 90%, in a preferred embodiment at least 95% calcium chloride; and at least 50, 60, 65, 70, 75, 80, 85, 90 or 95% silica, for example at least 60%, preferably at least 75%, more preferably at least 80% w/w.

25. The composition of claim 24 comprising less than 10, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 or 0.1% cl w/w, in preferred embodiments less than 5%, in more preferred embodiments less than 1%.

26. A composition according to claim 24 or 25, comprising less than 20, 15, 10, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 or 0.1% cao w/w, in preferred embodiments less than 5%, in more preferred embodiments less than 0.5%.

27. A method of dechlorinating a solid comprising calcium chloride, the method comprising:

(i) Combining the solid comprising calcium chloride with a solid comprising silica; and

(ii) The combined calcium chloride and silica is heated to a temperature of 750-1250 ℃ in the presence of steam to produce HCl gas and a decalcified product.

28. The method of claim 27, wherein the temperature is 900-1250 ℃.

29. The method of claim 27, wherein the temperature is 1000-1250 ℃.

30. The method of claim 27, wherein the temperature is 1100-1250 ℃.

31. The method of any one of claims 27 to 30, wherein when the temperature reaches 700-750 ℃, heating is continued at a rate of no more than 60, 50, 40, 30, 10 or 5 ℃/minute until a temperature of 800-850 ℃ is reached.

32. The method of any one of claims 27 to 31, wherein the solid comprising calcium chloride is combined with the solid comprising silica such that a Ca-Si molar ratio of between 2.5 and 3.5 is achieved.

33. The method of any one of claims 27 to 31, wherein the solid comprising calcium chloride is present at 50-90wt% and silica is present at 10-40 wt%.

34. The method of any one of claims 27 to 33, wherein the solid comprising calcium chloride comprises at least 80%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% calcium chloride, preferably at least 90%, more preferably at least 95%.

35. The method of any one of claims 27 to 34, wherein the silica-containing solid comprises at least 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% silica, preferably at least 60%, more preferably at least 75%, even more preferably at least 80%.

36. The method of claim 35, wherein the calcium chloride-containing solid comprises at least 90% calcium chloride and the silica-containing solid comprises at least 80% silica.

37. The method of any one of claims 27 to 36, wherein the steam is present at 5-100 vol%.

38. The method of any one of claims 27 to 37, wherein the chlorine content is reduced by at least 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98% or 99%, preferably by at least 90%, more preferably by at least 95%, even more preferably by at least 99%.

39. A process according to any one of claims 27 to 38, wherein the dechlorinated calcium product comprises at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80wt% dicalcium silicate, preferably at least 15%, more preferably at least 25% dicalcium silicate, and less than 30, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1wt% cao, preferably less than 10%, more preferably less than 5% cao.

40. The method of claim 40, wherein the dechlorinated calcium product comprises at least 15% dicalcium silicate and less than 10% cao.

41. A method of producing clinker from solids comprising calcium chloride, the method comprising:

(a) Dechlorination of the calcium chloride-containing solid to produce a dechlorinated composition comprising Ca and having less than 10% w/w Cl; and

(b) The dechlorination composition is heated in the presence of a fluxing agent to produce clinker.

42. The method of claim [0093], wherein the clinker comprises dicalcium silicate and tricalcium silicate.

43. The method of claim [0093] or 42, wherein said clinker comprises portland cement clinker.

44. The method of any one of claims [0093] to 43, wherein the composition comprising calcium chloride further comprises silica.

45. A process as set forth in claim 44 wherein the molar ratio of Ca to Si in the composition comprising calcium chloride and silica is from 1.0 to 5.0, preferably from 2.0 to 4.0, more preferably from 2.5 to 3.25.

46. The method of any one of claims [0093] to 45, wherein the composition comprising calcium chloride comprises at least 80%, 90%, 92%, 95%, 96%, 97%, 98% or 99% calcium chloride, preferably at least 80%, more preferably at least 90%, even more preferably at least 95%.

47. The method of any one of claims [0093] to 46, wherein the dechlorination composition comprises less than 30%, 20%, 10%, 8%, 5%, 4%, 3%, 2% or 1% cao, preferably less than 10%, more preferably less than 5%.

48. The composition of any one of claims [0093] to 47, wherein the dechlorination composition comprises no more than 10%, 8%, 6%, 5%, 4%, 3%, 2% or 1% Cl by weight, preferably no more than 10%, more preferably no more than 5%, even more preferably no more than 1%.

49. The method of any one of claims [0093] to 48, wherein the dechlorination composition comprises at least 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40% dicalcium silicate, preferably at least 15%, more preferably at least 25%.

50. The method of any one of claims [0093] to 49, wherein dechlorinating the composition comprising calcium chloride comprises heating the composition.

51. The method of claim 50, further comprising introducing steam when the composition comprising calcium chloride reaches a temperature of 300 ℃ or greater.

52. The method of claim 51, wherein heating the composition comprising calcium chloride in the presence of steam comprises heating to a temperature of at least 750 ℃ and/or not more than 1250 ℃.

53. The method of claim 52, wherein the heating is at a rate of no more than 100, 80, 50, 40, 30, 25, 20, 15, 10, 5, or 1 °/min or slower between 700-750 ℃ and 800-1000 °.

54. The process of any one of claims [0093] to 53, wherein HCl is produced during said dechlorination.

55. The method of any one of claims [0093] to 54, wherein the fluxing agent comprises iron and/or an aluminum compound.

56. The method of claim 55, wherein the aluminum compound comprises Al2O3 and/or the iron compound comprises Fe2O3.

57. A process as set forth in claim 55 or claim 56 wherein said iron compound and/or said aluminum compound and said composition comprising calcium chloride are produced from the same starting material.

58. The method of claim 57, wherein the starting material comprises calcium-containing rock and/or minerals.

59. The method of any one of claims 44 to 58, wherein said silica is produced from the same starting material as that used for said composition comprising calcium chloride.

60. The method of any one of claims [0093] to 59, wherein said heating the dechlorination composition in the presence of a fluxing agent comprises heating the composition to 1200-1600 ℃, preferably 1400-1600 ℃.

61. The method of claim 60, comprising heating the composition to 1500-1600 ℃.

62. The method of claim 60, comprising heating the composition to 1450-1500 ℃.

63. The method of any one of claims [0093] to 62, wherein the dichloro-ing and/or the heating of the dechlorinated composition is performed in a kiln.

64. A method as set forth in claim 63 wherein the kiln comprises a rotary kiln.

65. A method of producing clinker, the method comprising heating a composition comprising dicalcium silicate and no more than 20%, 15%, 10%, 5%, 2% or 1% cao, such as no more than 10% cao, in the presence of a fluxing agent to produce clinker.

66. A method as claimed in claim 0148 wherein the composition contains less than 5%, 4%, 3%, 2%, 1%, 0.5% or 0.1% tricalcium silicate, preferably less than 1%, more preferably less than 0.1%, and the clinker comprises at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60% tricalcium silicate, preferably at least 20%, more preferably at least 50%.

67. The method of claim 0148 or 66, wherein the flux comprises aluminum and/or iron oxide.

68. A method of producing clinker and Supplemental Cement Material (SCM) from a starting material comprising a non-limestone material, the non-limestone material comprising calcium and silicon, the method comprising:

(i) Dissolving the non-limestone material in HCl to produce a calcium-rich liquid fraction comprising calcium chloride and a calcium-depleted solid fraction comprising silica;

(ii) Generating the SCM from the calcium-depleted solids portion comprising silica; and

(iii) Clinker is produced from the calcium-rich liquid fraction comprising calcium chloride.

69. A method as claimed in claim [0149], further comprising generating aggregate from the non-limestone material.

70. The method of claim [0149] or claim 69, further comprising producing cement from the clinker.

71. The method of claim 70, further comprising combining the cement, the aggregate, and the water to produce concrete.

72. The method of claim 71, further comprising combining the SCM with the cement, aggregate, and water to produce concrete.

73. An apparatus for producing clinker from non-limestone material, the apparatus comprising

(i) A first processing machine configured to process the non-limestone starting material to produce a solid composition comprising calcium chloride operably connected to

(ii) A second processor configured to form clinker from the solid composition comprising calcium chloride.

74. The apparatus of claim 73, wherein said first processing machine comprises

(a) A leacher configured to contact the non-limestone material with an acid to produce a first calcium-rich liquid fraction and a calcium-depleted solid fraction, operatively connected to

(b) A precipitator configured to remove one or more non-calcium salts from the calcium-rich fraction by converting the one or more non-calcium salts into a solid form that is removed from the calcium-rich fraction; and

(c) A dehydrator configured to remove water from the calcium-rich liquid fraction from the precipitator to produce the calcium chloride-containing solids.

75. An apparatus as claimed in claim 73 or claim 74, wherein the first processor further comprises a materials processor configured to process non-limestone starting materials, the materials processor being operatively connected to the leacher.

76. An apparatus as defined in claim 75, wherein the material processing machine is configured to reduce the size of the non-limestone material and/or sort the material into one or more size ranges.

77. The apparatus of any one of claims 74 to 76, wherein the first processor further comprises an acid storage tank operatively connected to the leacher.

78. The apparatus of any one of claims 74 to 77, wherein the leacher comprises a heating element.

79. An apparatus as claimed in any one of claims 74 to 78, wherein the leacher comprises an agitator.

80. The apparatus of any one of claims 74 to 79, wherein the leacher further comprises a first separator operatively connected to the leacher and the precipitator configured to separate the calcium-rich liquid fraction and the calcium-depleted solid fraction and to direct the calcium-rich liquid fraction to the precipitator.

81. The apparatus of any one of claims 74 to 80, wherein the precipitator is operatively connected to a second separator to separate the solids from the calcium-enriched liquid fraction.

82. The apparatus of any one of claims 74 to 81, wherein the precipitator comprises a first precipitation unit, the first precipitation unit being a base precipitation unit configured to precipitate a first set of non-calcium compounds.

83. The apparatus of claim 82, further comprising one or more alkali sources operably connected to the first precipitation unit.

84. The apparatus of claim 83, wherein the one or more alkali sources comprise calcium alkali sources.

85. The apparatus of any one of claims 82 to 85, wherein said precipitator comprises a second precipitation unit that is a thermal hydrolysis precipitation unit configured to precipitate a second set of non-calcium compounds from said calcium-rich liquid fraction.

86. The apparatus of claim 85, wherein the second precipitation unit is operably connected to a third separator to separate the second set of precipitated non-calcium compounds from the calcium-rich liquid fraction.

87. The apparatus of claim 85 or claim 86, wherein the precipitator comprises a third precipitation unit that is a thermal hydrolysis unit for precipitating a third set of non-calcium compounds from the calcium-rich liquid fraction.

88. The apparatus of claim 87, wherein the third precipitation unit is operably connected to a fourth separator to separate the third set of precipitated non-calcium compounds from the calcium-rich liquid fraction.

89. The apparatus of claim 87 or claim 88, wherein the second and third precipitation units are identical, and the second and third sets of precipitated non-calcium compounds are identical.

90. The apparatus of claim 87 or claim 88, wherein the second and third precipitation units are different, and the second precipitation unit is configured to precipitate aluminum compounds by heating the calcium-rich liquid to a first temperature or temperature range, and the third precipitation unit is configured to precipitate iron compounds by heating the calcium-rich liquid to a second temperature or temperature range that is higher than the first temperature or temperature range.

91. The apparatus of any one of claims 74 to 90, wherein the dehydrator comprises a heating element.

92. The apparatus of any one of claims 73 to 91, wherein the second processing machine comprises

(a) A dechlorination apparatus configured to dechlorinate the CaCl 2-containing solids to produce dechlorinated solids comprising calcium compounds, operably connected to

(b) A clinker pusher configured to heat the dechlorinated solids in the presence of a fluxing agent to produce clinker.

93. The apparatus of claim 92 wherein the dechlorination reactor is configured to produce a dechlorinated solid comprising a calcium compound and less than 20, 15, 10, 8, 7, 6, 5, 4, 3, 2, or 1wt% cl.

94. The apparatus of claim 92 or claim 93, wherein the alkali source comprises dechlorinated solids from the dechlorinated machine and/or cement clinker from a cement kiln.

95. The apparatus of any one of claims 92 to 94, wherein the dechlorinating device is operatively connected to

1. One or more steam sources; and

2. one or more silica sources.

96. The apparatus of claim 95, wherein the one or more steam sources comprise the dehydrator of the first processing machine.

97. The apparatus of claim 95 or claim 96, wherein the one or more silica sources comprise the first processor or a portion thereof.

98. The apparatus of claim 97, wherein the first processor or portion thereof comprises the first separator.

99. The apparatus of any one of claims 92 to 98 wherein the maturation means is operatively connected to one or more sources of flux.

100. The apparatus of claim 99, wherein the one or more flux sources comprise the first processing machine or portion thereof.

101. The apparatus of claim 100, wherein the first processor or portion thereof comprises the settler.

102. The apparatus of any one of claims 92 to 101 wherein the dechlorination device and/or the clinker device comprises a rotary kiln.

103. The apparatus of any one of claims 92 to 102 further comprising a clinker processor for processing clinker from the clinker aggregate.

104. The apparatus of any one of claims 73 to 102, further comprising a control system, wherein the control system comprises

(i) One or more input sources from the first processing machine and/or the second processing machine;

(ii) A processor for processing inputs from the one or more input sources and providing outputs; and

(iii) One or more actuators that receive the output and adjust one or more operations of the first and/or second machines.

105. The apparatus of claim 104, wherein the one or more input sources comprise one or more sensors, such as one or more temperature sensors, to detect the temperature of the leacher, the dehydrator, the dechlorinating device and/or the cooker or parts thereof.

106. The apparatus of claim 104 or claim 105, wherein the actuator comprises one or more actuators that regulate operation of heating elements for the leacher, the dehydrator, the dechlorination device and/or the clinker device.

107. A network comprising a plurality of devices of any one of claims 73 to 106, wherein the devices are spatially separated, and wherein the devices each send information to a common controller and/or controllers.

108. An apparatus for producing a calcium chloride-containing solid from a non-limestone material comprising calcium, wherein the apparatus comprises a processor configured to process the non-limestone starting material to produce the calcium chloride-containing solid.

109. The apparatus of claim 108, wherein the processing machine comprises

(c) A dehydrator configured to remove water from the calcium-rich liquid fraction from the precipitator to produce a solid comprising calcium chloride.

110. An apparatus as claimed in claim 108 or claim 109 wherein the processor further comprises a materials processor configured to process non-limestone starting materials, the materials processor being operatively connected to the leacher.

111. An apparatus as claimed in claim 110, wherein the material processing machine is configured to reduce the size of the non-limestone material and/or to sort the material into one or more size ranges.

112. The apparatus of any one of claims 109 to 111, wherein the processor further comprises an acid storage tank operatively connected to the leacher.

113. The apparatus of any one of claims 109 to 112, wherein the leacher comprises a heating element.

114. An apparatus as claimed in any one of claims 109 to 113, wherein the leacher comprises an agitator.

115. The apparatus of any one of claims 109 to 114, wherein the leacher further comprises a first separator operatively connected to the leacher and the precipitator configured to separate the calcium-rich liquid fraction and the calcium-depleted solid fraction and direct the calcium-rich liquid fraction to the precipitator.

116. The apparatus of any one of claims 109 to 115, wherein the precipitator is operatively connected to a second separator to separate the solids from the calcium-enriched liquid fraction.

117. The apparatus of any one of claims 109 to 116, wherein the precipitator comprises a first precipitation unit that is a base precipitation unit configured to precipitate a first set of non-calcium compounds.

118. The apparatus of claim 117, further comprising one or more alkali sources operably connected to the first precipitation unit.

119. The apparatus of claim 118, wherein the one or more alkali sources comprise calcium alkali sources.

120. The apparatus of any one of claims 109 to 120, wherein the precipitator comprises a second precipitation unit that is a thermal hydrolysis precipitation unit configured to precipitate a second set of non-calcium compounds from the calcium-rich liquid fraction.

121. The apparatus of claim 121, wherein the second precipitation unit is operably connected to a third separator to separate the second set of precipitated non-calcium compounds from the calcium-rich liquid fraction.

122. The apparatus of claim 120 or claim 121, wherein the precipitator comprises a third precipitation unit that is a thermal hydrolysis unit for precipitating a third set of non-calcium compounds from the calcium-rich liquid fraction.

123. The apparatus of claim 122, wherein the third precipitation unit is operably connected to a fourth separator to separate the third set of precipitated non-calcium compounds from the calcium-rich liquid fraction.

124. The apparatus of claim 122 or claim 123, wherein the second and third precipitation units are identical and the second and third sets of precipitated non-calcium compounds are identical.

125. The apparatus of claim 122 or claim 123, wherein the second and third precipitation units are different and the second precipitation unit is configured to precipitate aluminum compounds by heating the calcium-rich liquid to a first temperature or temperature range and the third precipitation unit is configured to precipitate iron compounds by heating the calcium-rich liquid to a second temperature or temperature range that is higher than the first temperature or temperature range.

126. The apparatus of any one of claims 109 to 125, wherein the dehydrator comprises a heating element.

127. An apparatus for producing clinker from solids comprising calcium chloride, wherein the apparatus comprises

(a) A dechlorination apparatus configured to dechlorinate the calcium chloride-containing solid to produce a dechlorinated solid comprising a calcium compound, operably connected to

128. The apparatus of claim 127, wherein said dechlorination reactor is configured to produce a dechlorinated solid comprising a calcium compound and less than 20, 15, 10, 8, 7, 6, 5, 4, 3, 2, or 1wt% cl.

129. The apparatus of claim 127 or claim 128, wherein the dechlorination device is operably connected to

1. One or more steam sources; and

2. one or more silica sources.

130. The apparatus of any one of claims 127 to 129, wherein the maturation means is operatively connected to one or more sources of flux.

131. The apparatus of any one of claims 127 to 130, wherein said dechlorination device and/or said clinker device comprises a rotary kiln.

132. The apparatus of any one of claims 127 to 131, further comprising a clinker processor for processing clinker from a cement kiln.

133. The apparatus of any one of claims 127 to 132, further comprising a control system, wherein the control system comprises

(i) One or more input sources from the dechlorination apparatus and/or the maturation apparatus;

(iii) One or more actuators that receive the output and adjust one or more operations of the dechlorinated device and/or the cooked device.

134. The apparatus of claim 133, wherein the one or more input sources comprise one or more sensors, such as one or more temperature sensors, to detect the temperature of the dechlorinated device and/or the cooked device or portion thereof.

135. The apparatus of claim 133 or claim 134, wherein the actuator comprises one or more actuators that regulate operation of heating elements for the dechlorinating device and/or the clinker device.

136. A system, the system comprising:

(a) A first processor configured to produce cement from a non-limestone material;

(b) A second processor configured to produce SCM from the non-limestone material.

137. The system of claim 136, further comprising (c) a third processor that produces aggregate from the non-limestone material.

138. The system of claim 136 and claim 137 wherein the first and second processors are identical.

139. A method of producing clinker comprising

(a) Dissolving a non-limestone material comprising calcium in an acid to produce a calcium-rich liquid fraction comprising calcium chloride and a calcium-poor solid fraction;

(b) Separating the calcium-depleted solids portion from the calcium-enriched liquid portion;

(c) Producing a solid comprising calcium chloride from the calcium-rich liquid; and

(d) Treating the solids comprising calcium chloride to form clinker.

140. The method of claim 139 wherein the non-limestone material further comprises silicon.

141. A method according to claim 139 or claim 140, wherein the non-limestone material comprises rock and/or minerals.

142. The method of claim 141, wherein the non-limestone material comprising rock and/or mineral comprises clinoptilolite, sika, gabbro, pyroxene, falcite, basalt, cuprocark, tungstope, quarry rock, mafic rock, ultramafic rock, or a combination thereof.

143. The process of any one of claims 139 to 142, wherein no more than 40%, 30%, 20%, 15%, 10%, 5%, 4%, 3%, 2% or 1% of the calcium in the starting material is present in the form of calcium carbonate, preferably no more than 10%, more preferably no more than 5%.

144. The process of any one of claims 139 to 143, wherein said starting material further comprises aluminum, iron, and/or magnesium.

145. The method of any one of claims 139 to 144 wherein the method produces less than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or 5% of discharged CO as compared to producing the same amount of hydraulic cement from limestone by a process comprising calcining the limestone ₂ 。

146. The method of claim 145, wherein the method produces less than 80% of emitted CO ₂ 。

147. The method of claim 145, wherein the method produces less than 60% of emitted CO ₂ 。

148. The method of claim 145, wherein the method produces less than 40% of emitted CO ₂ 。

149. The method of any one of claims 139 to 148, wherein the method further produces Supplementary Cementitious Material (SCM), mg derivatives, and/or aggregate.

150. The method of claim 149, wherein the SCM, mg derivatives, and/or aggregate are produced from the same starting materials as are used to produce the cement.

151. The method of any one of claims 139-151, wherein the acid comprises HCl, HBr, HI, HNO ₃ Or a combination thereof.

152. The process of claim 151, wherein said acid comprises at least 80%, 90%, 95%, 99% or 100% hcl.

153. The process of any one of claims 139 to 152 wherein the concentration of the acid is 10-37%.

154. The method of claim 153, wherein the concentration of the acid is 15-25%.

155. The method of claim 153, wherein the concentration of the acid is 20%.

156. The method of any one of claims 139-155, wherein producing a solid comprising calcium compounds comprising calcium chloride from the calcium-rich liquid comprises precipitating one or more compounds comprising aluminum, iron, and/or magnesium from the calcium-rich liquid.

157. The method of any one of claims 139-156, wherein producing a solid comprising calcium chloride-containing calcium compound from the calcium-enriched liquid comprises dewatering the liquid to produce the solid comprising calcium chloride.

158. The method of any one of claims 139-157, wherein treating the calcium chloride-containing solid to form clinker comprises dechlorinating the calcium chloride-containing solid to produce a dechlorinated solid comprising a calcium compound.

159. The method of claim 158, wherein dechlorinating comprises heating the solid comprising calcium chloride in the presence of steam and silica.

160. The method of claim 158 or claim 159 further comprising treating the dechlorinated solids comprising a calcium compound to produce clinker.

161. The method of claim 160, wherein treating comprises heating the dechlorinated solid comprising calcium compounds in the presence of a fluxing agent.