EXTRACTION OF MATERIALS FROM A LIQUID MEDIUM BY ADVANCED MINERALIZATION PROCESSING

Description

BACKGROUND OF THE INVENTION

This invention is directed to a process for extracting desired materials from a liquid medium. The desired metals are extracted through advanced mineralization processing by adjusting a unique parameter, the effective alkalinity, determined based on the modified alkalinity in the liquid medium, to a preset value and recovering the desired element as a precipitate. The precipitate is formed through direct and indirect interactions of the available anionic species with the material in the liquid medium, which is continuously replenished from the surroundings.

The present disclosure relates to a system and process for rapid, economical, and environmentally friendly extraction of materials like alkali metals from liquid media, which include but are not limited to geothermal brines, surface/subsurface brines, underground water, seawater, lake/river/pond water, mineral dissolved liquids (natural/artificial), eluates, concentrates, acid mine drainage, tailings ponds, and water produced from oil & gas production, abandoned mine lands, enhaced oil recovery, coal bed methane recovery, carbon sequestration, and other industrial activities such as desalination, liquid purification, waste water cleaning, sewage treatment, and rock/clay mining, (hereafter “liquid”). The mineral dissolved liquids, eluates, and concentrates may be liquid solutions with such mineral or its constituents dissolved in them, including water or brines that may have been acidified or basified, and solutions rich in chlorine, sulfur, phosphorous, and hydroxide. Some hydroxide solutions such as NaOH and KOH have very high boiling points above 1,000° C. Some liquid solutions may come from those resulting from leaching processing, which is one of the most common practices to extract materials from solid minerals and ores, by chemically dissolving them into acidic or basic (alkaline) solutions.

Currently, the extraction and production of alkali metal minerals such as lithium carbonate from liquid media like brines is conducted in two steps: (1) through a lithium concentration step, which is performed by an evaporation pond route or direct lithium extraction (DLE) techniques; followed by (2) mineralization steps (such as carbonation, hydration, and electrolysis) typically at separate facilities where final solid products are generated, commonly by precipitation in various ways, from the liquid produced at the concentration step. Traditional and emerging DLE approaches to concentrate lithium, such as ion exchange, membranes, adsorption, solvent, and nano-filters, which can produce a lithium mineral (e.g., chloride, sulfate, phosphate, etc.) concentrate or eluate to be mineralized are becoming more promising to replace the predominant evaporation pond concentration step. These liquid solutions concentrated with desired materials may be also generated by acid/basic leaching of solids such as ores and minerals. Materials dissolved in the concentrated solution are then, in general, precipitated out by various methods including electrolysis, supersaturation (freezing, drying, etc.), and chemical reactions (carbonation, hydration, etc.). Carbonation of a liquid by advanced CO₂ gas injection into the liquid medium has been suggested in the past few decades by academia and industries for extraction of a variety of metals including lithium, magnesium, and calcium from the liquid media. For this approach to be practically effective, the process has been enhanced by thermodynamic manipulations; for example, pH modification, solid additives, or operation under supercritical conditions. The use of CO₂ microbubbles having a diameter of 50 microns or less was suggested in conjunction with solid additives to promote carbonation of a liquid to extract metals. The advanced injection of nanobubbles (<1 micron) of gases such as carbon dioxide, ozone, oxygen, air, and nitrogen has been suggested and widely practiced in the past few decades in various industries such as materials, agriculture, fishery, medical, pharmaceutical, environmental, biological, cleaning, and sanitation because the nanobubbles can influence the pH or improve the solubility limits (i.e., concentrations) of dissolved gas, the population of suspended gas (e.g., non-dissolved), the surface energy of trapped gas, the surface tension of liquid, wettability, and the charges (e.g., zeta potential) in the vicinity of the trapped gas, while providing the ability to be suspended in a liquid medium for an extended period of time (months to years). Because of such wide applications and uses, various advanced techniques of generating nanobubbles and their injection are commercially available worldwide.

The process enables a rapid, economical, and environmentally friendly extraction of elements, accomplished through mineralization of the liquid with one or more of a plurality of different anionic species as facilitated by adjustment of the effective alkalinity. Adjustment of the effective alkalinity of the liquid, if conducted using the invention, causes or promotes mineralization to generate the final product from the liquid, for example, carbonate minerals. The invention generates the final product directly from the liquid without requiring a preceding concentration step (e.g., evaporation pond and DLE). The invention effectively complements the existing concentration steps if applied to concentrates and eluates produced from the evaporation pond and DLE processes.

Element extraction occurs substantially instantaneously generating a target mineral directly in the source liquid upon adjusting the effective alkalinity, thereby eliminating the need for a post-mineralization step. Additionally, the present invention effectively eliminates the need for transporting resource materials (e.g., ores, brines, etc.) from a mining site or intermediate products (e.g., concentrates, eluates, etc.) from a concentration site, to a mineralization facility, thereby resulting in a significant reduction in economic and environmental burdens (limited production rates, local freshwater consumptions, fuel consumptions, CO₂ emissions, etc.) in the extraction and production process. It is also envisioned that, if applied to lithium extraction, for example, giga/mega factories for lithum battery manufacturing would be built at the source of lithium extraction, eliminating burdens from long-distance transportation. Therefore, it is useful to have a low capital and environmentally benign process for extracting materials ‘directly’ from a liquid medium.

BRIEF SUMMARY OF THE INVENTION

The present invention applies to the extraction of a wide variety of different elements from liquids. For example, the disclosed method can extract materials from liquids, which can be mineralized by the disclosed method, including alkali metals (e.g., Li, Na, K, Rb, Cs), alkaline earth metals (e.g., Be, Mg, Ca, Sr, Ba), transition metals (e.g., Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rh, Pd, Ag, Cd, Hg), post transition metals (e.g., Al, Ga, In, Sn, Pb), metalloids (e.g., Si, Ge, As, Sb), precious metals (e.g., Ir, Pt, Au), rare earth metals (e.g., Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), actinides (e.g., Th, U), or mixtures thereof. For example, lithium carbonate and other carbon-containing forms of lithium can be formed and extracted based on the effective alkalinity adjustment. In some embodiments, some materials may be extracted from the liquid as byproducts, along with the primal material by tuning the effective alkalinity for those elements.

The method includes selecting and adjusting the effective alkalinity determined based on the modified alkalinity in a quantity of liquid to a preset value. Alkalinity, in general, is a measurement of dissolved alkaline substances, which may represent the capacity of a liquid medium to neutralize acids so that the pH does not abruptly change. The effective alkalinity, as defined in this disclosure, is used to activate existing anions and cations to cause a new state of equilibrium (or metastable equilibrium) in a liquid medium and with respect to a surrounding gas to enable precipitation of the target cations without needing to purposefully modify the pH of the liquid medium. The process facilitates direct and indirect interactions of anionic species and precusors to anionic species, available in the liquid medium and surroundings such as air, with the target element. The target element forms the mineral mostly using anionic species or its precusors from the liquid, which is continuously replenished from the surroundings. Alkalinity, in general, may be expressed in units of concentration. For the purposes of this disclosure, the concentration of the following species are considered in the effective alkalinity determination, which may be as an individual, a combination, or a total: carbonate and other carbonic species (e.g., CaCO₃, CaMg(CO₃)₂, CO₃²⁻, HCO₃⁻); silicate and other silicon species (e.g., SiO₂, SiO(OH)₃⁻); borate and other boron species (e.g., B(OH)₄⁻); hydroxide species (e.g., OH⁻); and chlorine species (e.g., HOCl, HCl). In some embodiments, alkalinity is modified, which is a partial total alkalinity defined in this disclosure as the balanced concentrations: [HCO₃⁻]+2[CO₃²⁻]+[CaCO₃]+[CaMg(CO₃)₂]+[B(OH)₄⁻]+[OH⁻]+2[PO₄³⁻]+[HPO₄²⁻]+2[PO₄³⁻]+[SiO(OH)₃⁻]+[NH₃]+[HS⁻]−[H⁺]−[HSO₄⁻]−[HF]−[H₃PO₄]−[HNO₂])−[HOCl]−[HCl].

The effective alkalinity (A_eff) in this disclosure is a unitless parameter and defined as: {(the modified alkalinity of a liquid)+(protonation donors)}/{(the sum of concentrations of anions with charges of 2- or higher)+(the sum of concentrations of dissolved species in the liquid)}. ‘Anions with charges of 2- or higher’ means anions with charges of 2-, 3-, 4-, and so on.

In some embodiment, the effective alkalinity may be simplified as the ratio of the alkalinity to the concentration of dissolved species. In some embodiments, the effective alkalinity may be simplified as the ratio of the alkalinity to the concentration of gaseous species in the gaseous environment where the liquid is exposed to or in contact with. The gaseous environment may be surrounding the liquid, surrounded by the liquid, or in contact with the liquid. In this case, the effective alkalinity can be further adjusted by controlling the concentration of the gaseous species in the gasuous environment using thermodynamic equilibrium. For example, 400 ppm CO₂ in air in a closed environment may be diluted by adding other gases such as nitrogen, argon, and oxygen, or increased by adding CO₂in the surrounding environment.

In the first embodiment, the preset effective alkalinity is preferably in the range of 0.0001-260. In the second embodiment, the effective alkalinity is more preferably in a range of 0.002-160. In the third embodiment, the effective alkalinity in the 0.1-26 range is most preferred.

The effective alkalinity expressed this way can effectively enable the determination of desired carbonation and/or mineralization for target materials. A non-limited example includes:

A eff = { ( [ HCO 3 - ] + 2 [ CO 3 2 - ] + [ CaC ⁢ O 3 ] +  [ ⁠ CaMg ( CO 3 ) 2 ] + [ ⁠ B ( OH ) 4 - ] + [ ⁠ OH - ] + 2 [ PO 4 3 - ] + [ ⁠ HPO 4 2 - ] + 2 [ ⁠ PO 4 3 - ] + [ SiO ( OH ) 3 - ] + [ NH 3 ] + [ ⁠ HS - ] - [ ⁠ H + ] - [ ⁠ HSO 4 - ] -  [ HF ] - [ ⁠ H 3 ⁢ PO 4 ] - [ HNO 2 ] ) - [ HOCl ] - [ HCl ] ) + ( [ H + ] ) } ⁠ / { ( 2 [ CO 3 2 - ] + 2 [ PO 4 3 - ] + [ HPO 4 2 - ] + 2 [ PO 4 3 - ] ) + ( CaCO 3 + CaMg ( CO 3 ) 2 + SiO 2 + CO x + N 2 + NO x + SO x + O x + H 2 ⁢ S + C x ⁢ H y + S x + P x ⁢ O y ) } Eq . 1

Note the total alkalinity component in this equation, if charges and protons are balanced, should not be affected by the pH, temperature, and pressure. Theoretical, estimated, or predicted concentrations may be used for some species if not available or as desired. The effective alkalinity may be time dependent and a determined, estimated, or measured value at a particular timing may be used. Exemplified calculations of the A_eff in brines using Eq. 1 are given in Table 1 where concentrations of constituents of each brine sample are given in mg/L. For example, for Brine 1, the A_eff is 1.053.

When the effective alkalinity is optimally adjusted, the following exemplified elemental

reaction in the case of carbonation is expected:

( 2 / x ) ⁢ M x + + C 4 + + 3 ⁢ O 2 - = M ( 2 / x ) ⁢ CO 3 Eq . 2

Unlimited resource examples for M^x+ may include M ions, MCl, MOH, MOH·H₂O, M_(2/x)CO₃, M₂O, and M-bearing minerals such as silicate, nitride, nitrate, phosphide, phosphate, chloride,

sulfide, and sulfate, where M represents elements described in [0006]. Unlimited resource examples for C⁴⁺ may include carbonic species, carbonates, bicarbonate, air, syngas, and trapped air. Unlimited resource examples for O²⁻ may include carbonic species, carbonates, bicarbonate, NO_x, SO_x, syngas, oxygen-bearing ions, oxygen-bearing compounds, dissolved oxygen, trapped oxygen, air, and trapped air.

The effective alkalinity adjustment can be performed by controlling concentrations of

species mentioned in Eq. 1, Eq. 2, [0007], and [0011] by any known means including physical techniques (e.g., flotation, filters, membranes, etc.), chemical approaches induced by, for example, nitrification, denitrification, carbonation, decarbonization, sulfide reduction, sulfide oxidation, or any combination of those. For example, carbonation and decarbonization can be performed by controlling carbonic species. The carbonic species can originate from, produced by, or controlled by interactions with carbonic solids, gases, and liquids, or those containing carbonic species such as alkali carbonates, ultrafine gaseous carbonic spheroids having a diameter of ≤999 nanometers, dissolved carbonic gases, air, and respective ions. The carbonic species can be removed by any existing means, such as flotation, filters and membranes, known chemical approaches, and a combination of those. The effective alkalinity can be adjusted in the same ways with one or more different species mentioned in Eq. 1, Eq. 2, [0007], and [0011], other than carbonic species, or a combination thereof. In some embodiments, a preset value of the effective alkalinity is adjusted tuning for the target element and the final product form such as carbonate, sulfate, nitrate, etc. In some embodiments, species whose concentrations are to be adjusted to adjust the effective alkalinity is preselected for the target element and the final product form such as carbonate, sulfate, nitrate, etc. In some embodiments, the target element is more than one material that co-form by the effective alkalinity adjustment.

In some embodiments, the effective alkalinity is adjusted to extract species or elements mentioned in Eq. 1, Eq. 2, [0007], and [0011] from a liquid medium by precipitating along with the target material mentioned in [0006]. In some embodiments, the effective alkalinity is adjusted to fix, capture, store, or sequester species or elements mentioned in Eq. 1, Eq. 2, [0007], and [0011] such as carbon, nitrogen, and sulfur, in the precipitated solid, by precipitating out along with the target material. In some embodiments, the effective alkalinity is adjusted to remove toxic materials containing at least one element mentioned in [0006] such as Hg and As from a liquid by precipitating those with the target material. In some embodiments, the effective alkalinity is adjusted to suppress the formation of undesired precipitate to reduce scaling and corrosion on or of the components that are in contact with the liquid. In some embodiments, the effective alkalinity is adjusted to clean a liquid medium by removing undesired materials containing at least one element mentioned in [0006] from a liquid by precipitating those with the target material.

To demonstrate the invention, synthetic brines of lithium concentration in the range of 0.016 wt. %-0.025 wt. % (160-250 ppm Li) with 2% salinity (20,000 ppm NaCl), containing other dissolved solids of K, Ca, Si, Cl, and Mg, were prepared and tested. The lithium was introduced as LiCl to simulate natural brine materials. At each test, the effective alkalinity was adjusted to approximately 0.01. Temperature of the brines was adjusted to 15° C. (or higher) by exchanging heat with a metal plate. Approximately 10 minutes after the effective alkalinity adjustment at each test, the brine sample was drained through a sieve and particles formed in the brine larger than 45 micron were collected and subjected to scanning electron microscopy, energy dispersive X-ray spectroscopy, and laser induced breakdown spectroscopy. The particles collected were analyzed and found to be predominantly lithium carbonate. No impurity from the dissolved solids (K, Ca, Si, Cl, and Mg) was detected to a ppm level. The presence of sodium precipitates was also noted among the collected particles. The overall Na/Li ratio collectively was drastically reduced to approximately 0.19. Resulting yields of lithium are presented as a percent lithium recovery in FIG. 1. Up to 82% lithium was extracted and recovered as ‘lithium carbonate’ directly in the synthetic brines without using post-mineralization steps.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representative experimental outcome showing lithium yields from synthetic brines.

FIG. 2 is a process flow diagram for the extraction of a target metal from a liquid resource.

DETAILED DESCRIPTION OF THE INVENTION

The disclosed process will become better understood by reviewing the following detailed description in conjunction with the figure. The detailed description and figure provide merely examples of the various inventions described herein. Those skilled in the art will understand that the disclosed examples may be varied, modified, and altered without departing from the scope of the inventions described herein. Many variations are contemplated for different applications and design considerations; however, for the sake of brevity, each and every contemplated variation is not individually described in the following detailed description.

The process illustrated in FIG. 2 can be operated either as a batch process or a continuous process. The process (100) described as applied to a liquid resource is illustrated in FIG. 2. A liquid resource (102) may be in a temperature range of 3-800° C., which may come with steam depending on the liquid temperature and surrounding environments, where the steam may exist in a temperature range of 30-680° C. The steam in this disclosure means the gaseous state of a liquid, which may include liquid droplets and its vapor at, above, and below its boiling point. First, a primary liquid is separated (104) from the liquid resource (102). In one embodiment where the primary liquid is a water based solution, has a temperature range of 3-95° C., and is exposed to the surrounding environment. In another embodiment, where the primary liquid is non-water based solution, the primary liquid has a temperature range of 100-800° C. Steam is generated from the liquid resource (102) using a boiler (120). Any known methods other than a boiler may be used to generate steam. The remaining liquid from the boiler (120) is transported to the primary stream and joins the primary liquid (104) at a preset ratio. If the steam is already available, for example, along with the liquid resource (102) or from a thermal plant, this step may be omitted or used as a supplemental step. Optionally, additional steam may be provided from the primary liquid (104) to a condenser (122), which can be prepared naturally (i.e., as present) or artificially by any known means. Hydraulic pressure, if available, from the liquid resource (102) or thermal sources may be utilized to move the liquid medium through the process or to generate electric power, which may be utilized within the system or stored for different purposes. Second, the liquid's effective alkalinity (A_eff) is adjusted toward a preset value at an effective alkalinity adjustment step (106), which may be repeated as desired or until the preset value is obtained. In some embodiments, the preset value may be readjusted at each repetition.

In one embodiment, a preset value for the effective alkalinity is determined in such a way that a total mass of available carbonic species (ionic, aqueous, and dissolved) in the liquid is less than that determined by the stoichiometry of the final product or byproduct as the carbonic species is continuously supplied (or replenished) from the surrounding environment. In one embodiment, a preset value for the effective alkalinity is determined in such a way that a total mass of available carbonic species (ionic, aqueous, and dissolved) in the liquid is equal to or higher than that determined by the stoichiometry of the final product or byproduct. In one embodiment, pH of the liquid does not increase after the completion of each alikalinity adjustment. In the first embodiment, alkalinity is preferably in the range of 2-200 mg/L CaCO₃. In the second embodiment, alkalinity is more preferably in a range of 100 to 500 mg/L CaCO₃. In the third embodiment, alkalinity in the 300 to 1,000 mg/L CaCO₃ range is most preferred.

Third, the liquid undergoes a heat exchanger step (108) to adjust the temperature of the liquid to a preset value where heat is exchanged within the system or externally, which may be repeated as desired or until a preset value is obtained. In some embodiments, the preset value is readjusted at each repetition. Heat exchange in this disclosure can be conducted by any known methods including counter flow or parallel flow heat exchangers such as tube and shell, direct liquid flow, direct gas flow, and radiators. In one embodiment, a preset temperature of the liquid is in a range of 3-95° C. In one embodiment, the preset temperature of the liquid is in a range of 10-80° C. In one embodiment, a preset temperature of the liquid is in a range of 20-60° C. In one embodiment where the liquid source (102) is non-water based, a preset temperature of the liquid is in a range of 120-600° C. Any heat, if harvested anywhere in the process, may be recycled or reused within the system where needed or stored for future use.

The steam from (120) undergoes heat extraction at the condenser (122), where the steam transforms to liquid, and further at the heat exchanger (126), where heat is exchanged within the system or externally to adjust the temperature of the liquid to a preset value. Heat from the condenser (122) may be recycled within the system or exchanged externally. The effective alkalinity (A_eff) in the condensed liquid is adjusted toward a preset value at an effective alkalinity adjustment step (124), which may be repeated as desired or until a preset value is obtained. In some embodiments, the preset value may be readjusted at each repetition. The condensed liquid after the heat exchanger step (126) joins the primary liquid from the heat exchanger step (108) at a preset ratio. In one embodiment, the preset ratio of the condensed liquid to the primary liquid is in the range of 1-15. In another embodiment, the preset ratio of the condensed liquid to the primary liquid is in the range of 0.05-1. In one embodiment, the steam utilization steps (120)-(126) are optional.

The effective alkalinity of the liquid after the heat exchanger step (108) is adjusted toward a preset value tuned for the target metal at an effective alkalinity step (112), which may be repeated as desired or until a preset value is obtained. In some embodiments, the preset value may be readjusted at each repetition. The liquid then undergoes a heat exchanger step (114) where heat is exchanged within the system or externally to adjust the temperature of the liquid to a preset value, which may be repeated as desired or until the preset value is obtained. In some embodiments, the preset value is readjusted at each repetition. The target material in the liquid with the adjusted effective alkalinity reacts with the anions or their precusors and precipitates out. The liquid with the precipitates undergoes a precipitate (ppt.) concentrator step (116) to concentrate solid materials and is separated from the liquid at a solid recovery step (117). In some embodiments, the ppt. concentrator step (116) and the solid recovery step (117) are repeated to enhance the recovery. In some embodiments where more than one material coprecipitates, those materials are further separated from one another after the separation from the liquid. In some embodiments, the ppt. concentrator step (116) and the solid recovery step (117) are performed at any timing throughout the process where at least one precipitate is available for concentration and separation. Concentration and separation can be performed by any conventional means, including gravitational, density, centrifuge, flotation, filtration, charge, surface tension, membrane, screening, absorption, adsorption, and electrostatic. After solid removal at the solid recovery step (117), part or all of the remaning liquid may be returned to the main stream before the alkalinity adjustment step (112) to maximize the recovery. The spent liquid (118) after the solid recovery step (117), which was not returned to the main stream may be injected underground at a liquid injection step (119) or transported to a reservoir or other storage units. In one embodiment where a liquid source is located underground, or if desired, part of or the entire material extraction process in this disclosure can be operated underground.

Optionally, impurities and byproducts may be precipitated and removed by adjusting the effective alkalinity to another preset value tuned for those materials at either or both of the effective alkalinity adjustment steps (106) and (112), which may be conducted as part of the repetition of the effective alkalinity adjustment step. If the target material was lithium, non-limiting examples of the byproducts may include calcium carbonate, magnesium carbonate, other non-lithium carbonates, calcium nitrate, magnesium nitrates, other non-lithium nitrates, sulfates, hydrates, hydroxides, and chlorides. In one embodiment, the byproduct forms independently of the target material. In another embodiment, the byproduct co-precipitate with the target material.

In one embodiment, species in addition to those mentioned in Eq. 1 may be included to induce the effective alkalinity via interactions with a liquid medium in the same way described in [0013], including the group consisting of air, Ar, He, H₂, H₂O, ammonia, chlorine, bromine, a halogen, biogas, ionized gas, isotopes of gaseous species, syngas, or a combination thereof.

The effective species in Eq. 1 selected may be a single effective species or a combination of those at a predetermined ratio to adjust the effective alkalinity. A final product may be a precipitate containing such species or part or none of the species. For example, suppose the effective alkalinity is adjusted to cause nitrogenic species to be more thermodynamically favored over carbonic species at the effective alkalinity adjustment step (112). In that case, the liquid undergoes nitrogenation other than carbonation, and the final product may be nitrate, nitride, or other nitrogen-bearing compounds. Similarly, other mineralization, such as sulfurization, phosphorylation, and hydration, may be induced by adjusting the effective alkalinity.

Optionally, conventional precipitation promoting techniques such as screening, aeration, agitation, and seeding can be also practiced before, during, and after either or both of the alkalinity adjustment steps (106) and (112) to facilitate the precipitation of the target material. Screening can be applied in the liquid state for modifying global or local concentration, segregation, or separation of one or more of the particular particulates or ions in the liquid, and can be performed by ion exchange, electrostatic, electrocharge, electric field, magnetic field, or electromagnetic field. Aeration can be conducted with air or other gases at preset flow rates and pressures. The gases

may contain any species mentioned in [0007], [0011], and [0012]. Agitation can be performed by mechanical stirring at preset revolution or oscillation rates or vibrations (mechanical, ultrasound, or wave) at preset frequencies. Seeding can be practiced with powders or particles at preset sizes and quantities or concentrations. Examples of the powders and particles include carbonate, hydroxide, nitrate, sulfate, etc. The powders and particles may contain any species mentioned in [0007], [0011], and [0012].

The effective alkalinity and temperature of a liquid can be individually readjusted to different preset values at each repetition. The number of repetitions and increment, interval, and duration at each repetition may be selected as desired.

In light of the discussion above, the best mode for practicing the invention comprises:

• • i. providing a liquid medium;
  • ii. adjusting the effective alkalinity in the liquid medium to a preset value in the range of 0.0001-260, using at least one effective alkalinity adjustment step;
  • iii. readjusting the effective alkalinity to different preset values in the range of 0.0001-260 at each repetition;
  • iv. adjusting the effective alkalinity by modifying concentrations of species bearing carbon, nitrogen, hydrogen, or oxygen in the liquid medium;
  • v. exchanging heat with the liquid medium to adjust liquid medium temperature to a preset value in the range of 10-80° C., using at least one heat exchanger step;
  • vi. readjusting the liquid medium temperature to different preset values in the range of 10-80° C. at each repetition;
  • vii. generating steam from the liquid medium;
  • viii. condensing the steam to liquid;
  • ix. harvesting heat from the condensing step and/or the liquid medium;
  • x. exchanging the heat with other heat exchangers and/or the liquid medium;
  • xi. the condensed liquid joins the primary liquid in the main process stream at a preset ratio;
  • xii. performing screening, aeration, agitation, or seeding, after any one of the alkalinity adjustment steps;
  • xiii. consequentially precipitating the material during processes ii through xii;

xiv. concentrating the precipitated material using at least one material concentration step; and

• • xv. separating the precipitated material using at least one material separation step.

DEFINITIONS

The following definitions apply herein, unless otherwise indicated.

For the purposes of this disclosure, carbonic species or reactant carbonic species includes: aqueous species with non-limiting examples including carbonic acid, bicarbonate, and carbonate; gaseous species such as carbon monoxide, carbon dioxide, and hydrocarbons; dissolved gaseous species; anionic forms of gaseous species; cationic forms of gaseous species; and protonated and deprotonated forms of gaseous species.

The disclosure above encompasses multiple distinct inventions with independent utility. While each of these inventions has been disclosed in a particular form, the specific embodiments disclosed and illustrated above are not to be considered in a limiting sense as numerous variations are possible. The subject matter of the inventions includes all novel and non-obvious combinations and sub-combinations of the various metals, features, functions, and/or properties disclosed above and inherent to those skilled in the art pertaining to such inventions. Where the disclosure or subsequently filed claims recite “a” element, “a first” element, or any such equivalent term, the disclosure or claims should be understood to incorporate one or more such metals, neither requiring nor excluding two or more such metals.

Applicant(s) reserves the right to submit claims directed to combinations and sub-combinations of the disclosed inventions that are believed to be novel and non-obvious. Inventions embodied in other combinations and sub-combinations of features, functions, metals and/or properties may be claimed through amendment of those claims or presentation of new claims in the present application or in a related application. Such amended or new claims, whether they are directed to the same invention or a different invention and whether they are different, broader, narrower, or equal in scope to the original claims, are to be considered within the subject matter of the inventions described herein.