CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of United States Provisional Application Serial Number 62/706,871, filed September 15, 2020, which is fully incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

[0001] The present invention relates to a novel process for the beneficiation of ores and solid waste material.

BACKGROUND OF THE INVENTION

[0002] Many ores comprise of a mix of various types ofparticles-having different chemical nature and economical value. Removing of the less valuable particle, will leave behind a concentrate of the valuable particles. This action enables its processing and reduces the processing costs. It is of great interest to develop cost effective processes for the concentration of the more valuable components present in the ore.

[0003] There are methods such as Floatation technologies that separate between ore particles of different composition from one other. The main difficulty in those technologies is the use of surfactants that ultimately become pollutants of lakes and water bodies and the fact that the waste fraction comprises also particles of undesirable components, such as heavy metals and other piousness materials.

[0004] Other methods comprise physical separation technologies such as magnetics separation methods, separation of particles by density, centrifugation cyclone type units etc.

[0005] The present invention deals with beneficiation of ores and solid waste materials, by leaching of components comprising divalent cations carbonates, or oxides or hydroxides or salts of weaker acids. The leaching is applied using an acid strong enough to efficiently attack the solids, such as HCl and other acids.

[0006] The use of an acid for leaching of the solids is expected to increase the production costs and to produce a large volume of liquid waste that should be disposed of at high cost. Such removal results in the contamination of the environment. [0007] The present invention comprises also a method for the conversion of the formed liquid waste into carbonate salts of divalent cations that might be sold to generate revenue. Moreover, the present invention provides an inexpensive process in which the strong acid that was used in the leaching of those divalent cations, to get a salt of the strong acid, can be produced from that salt and recycled. The result is a decrease in production costs and in the amount of produced waste.

[0008] In WO2020035854A1 to Vitaer, it was demonstrated that by using a formulation that comprises an OWB (Organic weak base), water and a hydrophilic solvent, the salt of strong acid reacts with CO2 and OWB (organic weak base) as presented in Step 1 ,

[0009] Step 1. 2*OWB + M(II)X2 + H2O + CO2 ===== 2*OWB*HX + M(II))CO3 (in the presence of hydrophilic solvent)

[00010] Step 2 Removal of the hydrophilic solvent

[00011] Step 3. OWB*Strong acid ===== OWB +HCl (Acid release)

[00012] In the present patent we eliminate the need for removal of the hydrophilic solvent and for the separation between the strong acid and OWB. By doing so, there is a considerable simplification of the process and a significant reduction in the production costs.

[00013] The process in the present patent becomes:

[00014] Step 2.1. Leaching of solid/Ore Solid (or Ore)+ OWB*HX ===== M(II)X2 + OWB

[00015] Step 2.2. M(II)X2 + CO2 + H2O + 2*OWB ===== 2*OWB*HX + M(II)CO3

[00016] In the process, HX is a strong acid, OWB is a weak organic base, M(II)X2 is a salt of a divalent cation and a strong acid and the Ore/solid contains a divalent cation in the form of a carbonate salt and/or oxide and or a weak acid.

As seen above, in the present patent the solid or Ore comprises leaching of a divalent cation in the form of a carbonate salt and/or oxide and or a weak acid. And there is no need to separate the hydrophilic solvent, if present, or the separation of the strong acid from OWB before the leaching step.

[00017] In the present patent, it was very surprisingly found that a process in which in one stage OWB is a sufficiently strong base to extract a strong acid from a salt and in the next step, the strong acid present in the OWB* strong acid can be used efficiently for leaching of divalent cation from ores or waste streams. This finding eliminates the need for removing of the hydrophilic solvent before reacting the strong acid with the ore. In parallel, there is no need to release the strong acid from OWB*strong acid. The present patent simplifies the process and reduces production costs.

[00018] In the mining industry there are many examples in which the ore comprises both tri or/and four valent cation oxides (or salts) along with CaCO3 or Ca-Mg Carbonates. In such cases, there is a need to separate between the carbonates and the three/four valent oxides (or salts). Similarly, there are cases that the ore comprises also silicates that one wants to separate from the ore or separate between the silicate and the carbonate salts.

[00019] Another example for the need for the technology described in the present invention is with phosphate ore. In many cases the ore is mixed with CaCO3. In cases in which the fraction of CaCO3 in the ore is high, it is consumed, during leaching, large quantities of acids thus increasing the production costs to a level in which it’s not worthwhile to mine those ores. The present inventions enable the digestion of the carbonate ores (and also hydroxide ores), while the ores comprising the product are practically not digested. The result of the digestion is a solution comprising a salt of the strong acid from which the strong acid can be recycled to the leaching-digestion step, directly, in the form of OWB*Strong acid.

[00020] The present invention enables a process for the reducing the volume of fly-ash to be disposed of while extracting of valuable products from the fly ash and recycling the acid, in the form of OWB*strong acid for leaching.

[00021] In other processes in the chemical and biotechnological industry acids and/or bases are added and waste salts are produced. The present invention provides a means to reduce the amount of this waste and reuse the acid and or base.

[00022] The increase in CO ₂ level in the atmosphere has a significant contribution to the global heating problem. The present invention gives a method for the fixation of CO ₂ as a carbonate salt thus reducing both air pollution and environmental pollution.

In this patent:

OWB = Organic weak base. Wherein a weak base, in this patent is a base having a pK1/2 that is lower than 4.

[00023] In the present patent, pK1/2 is the pH in an aqueous phase that is in contact with a phase comprising OWB*HCl and OWB at OWB*HCl / (OWB + OWB*HCl) of 0.5. [00024] To date, the only way to split a salt comprising a strong acid involves thermal decomposition of the salt at temperatures of from a few to many hundreds of degrees or through use of electrical energy via electro-dialysis. The process described in the present invention enables such a split using OWB and CO ₂ at moderate temperature level.

[00025] The process suggested here can be used for the assimilation of CO ₂ in carbonate salts by splitting of strong acid salts into the acid and the carbonate salt There is an urgent need in many industries for such a process. Developing methods for this operation will lead to the reduction of the amount of waste produced in those industries.

[00026] Processes have been suggested to separate weak acids from their salts to obtain the free weak acid:

[00027] US 5,510,526 to Baniel, demonstrated splitting sodium lactate (a sail of weak acid) and forming sodium bicarbonate as the conjugated base. Baniel found a way to efficiently combine tri-alkyl amine several driving forces to enable his process; thermal energy, the (chemical) crystallization energy of NaHCO, the (chemical energy) of high reagent concentration, the (mechanical) energy of CO2 pressurization and the thermal sensitivity of carboxylic acid extraction (U. S. patent 4,275,234).

[00028] Several patents demonstrated the extraction of free HCI from diluted solutions and for the later recovery of concentrated HCI by stripping of the amine:

[00029] (Baniel and Jansen, US patent application No. 2012/0134912; Baniel and Eyal, US patent application No. 2010/0093995, US patent application No. 2011/0028710 and EP 2 321 218 A1; Baniel, Eyal and Jansen, WO 2010/064229 A2; Coenen, Kosswig, Hentschel and Ziebarth, US patent No. 4,230,681 ; Willi Ziegenbein, Ferdinand von Praun, US patent No, 4,272,502 A; DeVries, US patent No. 4,640,831 A), demonstrate that HCI can be extracted from its acid solution using the Weak base extractant TEHA (Tri ethyl hexyl amine). The extracted HCI is released from TEHA by heating the loaded extractant at 140°C- 170°C to give HCI gas of low vapor pressure or by back extraction to give HCI solution. This process can be used only on separation of free strong acid but not on a salt of a strong acid.

[00030] Asuncion Aranda (CA2973558A1) has demonstrated that in the presence of CO ₂ , CaCl ₂ can be split by TOA (Tri octyl amine) which is a medium strength base, to give CaCCE and TOA*HCl. Since TOA is a too strong base, it holds strongly the strong acid and therefore, Back-Extraction of the extracted strong acid gives a very dilute HCl solution. In order to overcome the difficulty, it was suggested to wash the extracted HCl with a base. In this process, an expensive base is used and a waste salt is produced (and therefore the process does not reduce the amount of waste salts. It was also suggested to use weaker amine extractants such as TEHA to extract HCl from CaCl ₂ but such extraction was not tried in that patent and trial done by us gave negative results.

[00031] In WO2020035854A1 it was demonstrated that by using a formulation that comprises of OWB, water and a hydrophilic solvent, a salt of strong acid can react with CO2 and OWB (organic weak base) as presented in eq. 1, to give a carbonate salt and OWB*strong acid. By removing the hydrophilic solvent, the basicity of the OWB is reduced and the free strong acid can be released at reasonable concentration (a concentration that is economically feasible for using in leaching or other applications.

[00032] The steps of changing the formulation by removing the hydrophilic solvent and releasing of the acid increase both investment costs and the production costs. In the invasion presented here, it is demonstrated that the core process described in PCT International Patent Application Publication Number WO2020035854A1 can be applied without the release of the hydrophilic solvent and the strong acid from the formulation. This method can be applied only in Leaching of solids selected of solids comprising of oxides, hydroxides, carbonates, bicarbonates or salts of weak acids.

Eq. 1 2*OWB + M(II)X2 +water + CO ₂ ====== 2*OWB*HX + M-carbonate or M- bicarbonate

[00033] Wherein:

OWB is an organic weak base;

HX is a strong acid having at least one proton with pK1/2 lower than 2; and

MX is a divalent cation salt of strong acid.

Eq. 2 OWB *HX+ ore/waste solids ======== OWB -i-a divalent cation salt of a strong acid

[00034] Or a direct contact between OWB*HX and the solids mentioned above [00035] Wherein the solids are selected of solids comprising of oxides, hydroxides, carbonates, bicarbonates or salts of weak acids.

[00036] The results obtained here and will presented in the next pages, show, that the selectivity between the leaching of divalent cations to that of tri/higher valent cations, cations, in the case of in the case in which OWB*HX is much higher than that with the free acid HX. The same can be said for the selectivity of leaching of salts of various weak acids.

[00037] For example, Aluminum or titanium oxide/hydroxide can be leached efficiently from fly ash by 2-4wt% HCl solution, the same as Calcium oxide/hydroxide/carbonates. When the HCl is present as OWB*HCl, the leaching Divalent / (trivalent or 4-valent) oxide or hydroxides, the selectivity becomes very high. The very high selectivity enables the leaching of CaC12 from Fly-ash, leaving behind the tri-four valent oxides/hydroxides, to get the CaC12 at much higher purity level.

[00038] Thus, the invention provides tools for the beneficiation of ores and solids by leaching with strong acids. When the acid comes in the form of OWB*strong acid, the divalent cations to higher valent ratio is much higher than when the strong acid is used as free acid. After leaching using OWB*HCl, the tri and/ higher valent cations can be leached at relatively higher purity by using the strong acid in the free state.

[00039] In the present invention, the reaction in Eq. 2 is demonstrated in the ore/solids:

1. Dolomite comprising of CaMg(CaO3)2.

2. Calcite comprising CaCO3 and various impurities

3. Dolomite CaFe(CO3)2

4. Fly ash comprising oxide and or/hydroxides

5. Phosphate rock comprising carbonates and or hydroxides and the combination thereof

6. Cu-Ore comprising of carbonates

7. A waste stream from a process for the separation Cu-rich fraction from Cu-ore

8. Salts comprising organic acid from chemical or biotechnology processes

9. A process for the production of sodium bicarbonate and HCl from NaCl

10. A process for production concentrated CO2 from flue gas

11. Processes for the assimilation of CO ₂ in carbonate salts of mono-valent and/or divalent cations [00040] The process suggested here, can be used as a process for the recrystallization of carbonates of di-valent cations. Divalent cation carbonates are salts of very low solubility and cannot be recrystallized just by dissolution of the salts in water or solvent and crystallizing it. The present process gives a cost-effective way to do so.

[00041] When ores or solids are processed, using conventional methods, to give a product stream and a waste stream comprising the divalent cations, the invention presented here can be applied to various solids of their processing, from the raw material ore through a solid waste stream or the product stream.

[00042] The applications as described herein are only part of the optional applications for the invention in the chemical industry, biotechnology industry for the production of organic acids, solids obtained by incineration of organic materials and treatment of dilute CO ₂ streams as urgently required for Global warming solutions and the skilled artisan will be aware of the versatility of applicability of the platform as described herein and its broad application potential.

SUMMARY OF THE INVENTION

[00043] In accordance with the processes, methods, and applications of this invention, it was surprisingly found that a strong acid bonded to an organic weak base (OWB) can react directly with various solids, without the need for releasing the strong acid from OWB*HCl.. This finding makes it possible to eliminate the need of removal of the hydrophilic solvent thus enabling a more cost-effective processes for the production of carbonates or bicarbonates from the salt of a strong acid.

[00044] In some aspects of the invention, this finding enables using a more basic OWB in the described reactions. Such processes are feasible not only using a very weak OWB such as TEHA, therefore, but also in using an OWB having a much higher pK value, which in turn represents other aspects of the invention.

[00045] Certain illustrative, non-limiting examples are provided herein, wherein the use of an OWB of basic nature that is greater than that of TEHA, enables the assimilation of CO ₂ at a much lower CO ₂ pressure than previously described (see for example, WO2020035854A1). In some aspects, this finding can be applied to processes/methodolgies/technolgies/systems for the release of a strong acid at significantly lower production costs. [00046] The above finding can be applied to a variety of processes/methodologies/fileds to enable environmentally friendly processes, which, in some aspects, saves on raw materials (acid and bases) finds application in such diverse fields such as mining, Fly ash treatment, inorganic chemistry, biotechnology and processes in industrial chemistry and others, as will be appreciated by the skilled artisan.

[00047] In other aspects of the invention, this finding can be applied in a variety of processes in combination with recycled free strong acid in processes in which mono and/or divalent cations are to be separated from solids comprising also tri and four valent cations.

[00048] In some embodiments, this invention provides process for the beneficiation of solids comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof, wherein the metal is a mono or divalent cation, the process comprising the steps of:

(a) combining at least one organic weak base (OWB), at least one salt of a strong acid wherein said salt is a carbonate salt or a bicarbonate salt of a monovalent cation or a divalent cation component of said strong acid; and a complex of a strong acid and said OWB (OWB*strong acid) in a reaction mixture;

(b) adding CO ₂ to said reaction mixture in (a) and promoting precipitation of said carbonate salt and increased formation of said OWB*strong acid;

(c) from a portion of the mixture of (b), isolating the carbonate salt or bicarbonate salt formed and the liquid filtrate comprising said OWB*strong acid;

(d) contacting said OWB* strong acid in said filtrate in (c) with solids comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof, wherein the metal is a mono or divalent cation to produce salts of said strong acid; and

(e) applying said salts of said strong acid obtained in (d) to the reaction mixture of step (a).

[00049] According to this aspect and in some embodiments, such processes further comprise the steps of: (f) in said combining in step (a), said reaction mixture further comprises a hydrophilic solvent and water;

(g) separating out said hydrophilic solvent in step (c) when isolating the carbonate salt or bicarbonate salt formed and the liquid filtrate comprising said OWB*strong acid and recycling said hydrophilic solvent to step (a);

(h) Separation of the strong acid from said OWB*strong acid to obtain free strong acid and contacting said free strong acid with said solid comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof in (d) such that at least a portion of said solids react with said strong acid to form a salt of strong acid; and

(i) Recycling said OWB and salt of strong acid to step (a).

[00050] According to this aspect and in some embodiments, such processes further comprise the steps of:

(f). Prior to step (a) contacting a solution comprising OWB*HCl with a solid comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof, wherein said metal is a monovalent cation or a divalent cation and wherein at least a portion of said solid reacts with said strong acid to form a salt of a strong acid;

(g). Preparing a reaction mixture comprising at least one salt of a strong acid produced in step (f); at least one organic weak base (OWB); and a hydrophilic solvent as part of step (a); and

(h) Recycling the OWB* strong acid, hydrophilic solvent and the salt of said strong acid obtained in step (e) to step (a).

[00051] In other aspects, the processes may further be directed to a process yielding the production of sodium carbonate or sodium bicarbonate, and further comprising the steps of:

[00052] (i) Preparing said reaction mixture as a solution comprising at least one organic weak base (OWB), sodium chloride and water;

(j) Adding CO ₂ in step (b) to yield a precipitate comprising sodium carbonate or sodium bicarbonate or a combination thereof and a liquid phase comprising OWB*HCl; (k) from the portion of the mixture removed in step (c), isolating Na2CO ₃ or NaHCO ₃ , NaCl or a combination thereof and a mother liquor liquid phase;

(1) Mixing the liquid phase comprising of OWB*HCl, obtained in step (j) with metal carbonate produced in the process described in Claims 1, 6, 7 or 10 or a with a fresh divalent cation carbonate salt, or a combination thereof to yield an organic phase comprising OWB, and an aqueous phase comprising a strong acid salt and CO ₂ ;

(m) Feeding the aqueous phase comprising the salt of strong acid to step (a) as described herein; and

(n) Feeding CO ₂ from step (1) to step (b).

[00053] In still other aspects, the solid for use in the processes as described herein is Fly ash and the processes further comprise the steps of:

(i) Contacting a solution comprising OWB* strong acid with Fly ash solids to produce at least one salt of a strong acid;

(j) Removing at least part of said salt of strong acid;

(k) Preparing a reaction mixture comprising of said salt of strong acid and organic weak base (OWB);

(l) Adding CO ₂ into said reaction mixture and precipitation of a carbonate salt or a bicarbonate salt or the combination thereof and production of a solution comprising OWB*strong acid; and

(m) Separating at least a portion of the resulting solution comprising OWB*strong acid obtained in (1) and adding the strong acid produced thereby to step (a).

[00054] In still further embodiments of the invention the processes as described herein extend to processing ore comprising Cu sulfides and Cu pyrites comprising also carbonates of divalent carbonate or divalent weak acid salts, said process comprising the steps of: (a) Contacting a solution comprising OWB* strong acid with solids selected form the raw material of the product or a waste obtained from processing said ore comprising Cu sulfides and Cu pyrites, to produce at least one salt of a strong acid;

(b) Removing at least a portion of said salt of a strong acid produced in (a) and preparing a reaction mixture comprising said salt of strong acid and an organic weak base (OWB);

(c) Adding CO ₂ to said reaction mixture in (b), precipitating a carbonate salt or a bicarbonate salt or a combination thereof to yield a liquid phase solution comprising OWB*strong acid;

(d) Removing at least a portion of the suspension obtained in (c) and separating out at least a portion of the solution comprising OWB* strong acid; and

(e) adding the strong acid produced in (d) to step (a) in processes as described herein, as will be understood to be appropriate by the skilled artisan and conducting a loop reaction with such described processes.

[00055] In still other embodiments, the solid comprises a phosphate ore or a carbonate ore or a combination thereof, and the processes of the invention further comprise the steps of:

(i) Contacting a solution comprising OWB* strong acid with said ore to produce at least one salt of a strong acid and residual solids;

(j) Removing at least a portion of said at least one salt of a strong acid and preparing a reaction mixture comprising said at least one salt of a strong acid and an organic weak base (OWB);

(k) Adding CO ₂ to said reaction mixture and precipitating a carbonate salt or a bicarbonate salt or a combination thereof to yield a suspension further comprising an OWB* strong acid solution;

(l) Removing at least a portion of the suspension obtained in (k) and separating out at least a portion of the OWB*strong acid solution; and

(n) adding the OWB* strong acid produced in (1) to step (a) of processes as herein described, as will be understood to be appropriate by the skilled artisan. [00056] In other embodiments, the processes of this invention may be extended to relate to methods for the separation of CO ₂ from flue gas, comprising the steps of:

(i) Contacting a solid comprising a carbonate or a bicarbonate salt with a solution comprising an organic base in the presence of a strong acid (OB*Strong acid) to yield concentrated CO ₂ gas, OWB and a salt of a strong acid;

(j) Removing at least a portion of the resulting solution obtained in (a) and adding compressed Flue gas comprising CO ₂ to said resulting solution;

(k) precipitating a carbonate salt or a bicarbonate salt or a combination thereof, to yield a liquid phase comprising a solution of OWB*strong acid and providing for the release of residual gases; and

(l) Removing at least a portion of said solution and recycling said solution to step (a).

[00057] In further embodiments, the processes as herein described are further extended to provide for the fixation of CO ₂ as a monovalent carbonate or monovalent bicarbonate or combination thereof, and such process further comprise the steps of: m) In a loop reaction, further adding the resulting salt of said strong acid obtained back to step (a) to produce OWB*Strong amine and a carbonate or a bicarbonate salt; n) In said loop reaction, further adding said carbonate or bicarbonate salt back to Step (a); o) Adding the organic base obtained in step (a) to a reaction mixture comprising NaCl, water, NaHCO3; p) Adding CO ₂ to the reaction mixture obtained in step (c) to produce NaHCO3 crystals and OB*Strong acid; and q) Adding the OB*strong acid obtained in (p) back to step (a).

[00058] In further embodiments, the processes as herein described are further extended to provide for the fixation of CO ₂ as a monovalent carbonate or monovalent bicarbonate or combination thereof, said process further comprising the steps of: m) Adding the OWB obtained in (a) to a reaction mixture comprising an aqueous phase comprising a monovalent salt of strong acid and a monovalent bicarbonate and a second phase comprising an OWB and OWB*Strong acid, to produce a bicarbonate salt of mono- valent cation crystals; n) Removing at least a portion of the bicarbonate salt crystals of the monovalent cation produced in Step (m) and at least a portion of the strong acid salt produced in Step (m); o) In a loop reaction, adding said second phase of step (n) to step (e); p) Adding OWB of step (m) to a reaction mixture comprising NaCl, water and NaHCO3; q) Adding CO ₂ to the reaction mixture in step (p) to produce NaHCO3 crystals and OB*Strong acid; and r) Adding the OWB*strong acid to step (m).

[00059] According to these aspects and in some embodiments, the processes further comprise the steps of: s) Reacting a metal oxide-containing solid with the strong acid obtained in step (d); t) Separating the liquid phase of (s) from any undissolved solids; and u) Applying the liquid phase obtained in step (t) to step (a) to function as the salt of a strong acid.

[00060] According to these aspects and in some embodiments, the processes further comprise the steps of: v) Reacting a strong acid with ores comprising Ca or Mg oxides or silicates; and w) .Feeding the resulting liquid phase to step (b).

[00061] The embodied processes according to these aspects further comprise the steps of: s) Preparing a reaction mixture comprising at least one organic weak base extractant (OWB), NaCl and water; t) Adding CO ₂ to said solution inducing the precipitation of sodium bicarbonate; u) Removing at least a portion of the resulting aqueous suspension and separating the precipitated sodium bicarbonate.

[00062] All publications, patents, and patent applications mentioned herein are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of a conflict between the specification and an incorporated reference, the specification shall control. Where number ranges are given in this document, endpoints are included within the range. Furthermore, it is to be understood that unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges, optionally including or excluding either or both endpoints, in different embodiments of the invention, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise. Where a percentage is recited in reference to a value that intrinsically has units that are whole numbers, any resulting fraction may be rounded to the nearest whole number.

DETAILED DESCRIPTION OF THE INVENTION

[00063] As described herein, it has surprisingly been found that strong acid can be separated from its strong acid salts by performing the reaction in an organic phase comprising of OWB* strong acid, with or without a hydrophilic solvent, between the strong acid salt, and CO ₂ .

[00064] This invention provides a general method for the beneficiation of solids wherein the solids comprise of salts or oxides selected from metal oxides, metal hydroxides, metal carbonate, metal salt of weak acid or the combination thereof, wherein the metal is selected from a mono or divalent cation.

[00065] The beneficiation process of this invention may comprise the following steps:

(a) Adding a salt of strong acid to a reaction mixture comprising of OWB and OWB* strong acid (b). Adding CO ₂ into said reaction mixture to produce a strong acid, in the form of OWB*strong acid and precipitation of a carbonate salt or a bicarbonate salt of a monovalent cation or a divalent cation, or the combination thereof

(c). Removing at least part the suspension comprising the carbonate salt or the bicarbonate salt or the combination thereof and the solution comprising OWB*strong acid.

(d). contacting at least part of the strong acid produced in (a) to solids comprising salts or oxides selected from metal oxides, metal hydroxides, metal carbonate, metal salt of weak acid or the combination thereof, wherein the metal is selected from a mono or divalent cation, and leaching at least part of said solids to produce salt of strong acid that is added in step (a).

[00066] In some embodiments, this invention provides process for the beneficiation of solids comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof, wherein the metal is a mono or divalent cation, the process comprising the steps of:

(a) combining at least one organic weak base (OWB), at least one salt of a strong acid wherein said salt is a carbonate salt or a bicarbonate salt of a monovalent cation or a divalent cation component of said strong acid; and a complex of a strong acid and said OWB (OWB*strong acid) in a reaction mixture;

(b) adding CO ₂ to said reaction mixture in (a) and promoting precipitation of said carbonate salt and increased formation of said OWB*strong acid;

(c) from a portion of the mixture of (b), isolating the carbonate salt or bicarbonate salt formed and the liquid filtrate comprising said OWB*strong acid;

(d) contacting said OWB*strong acid in said filtrate in (c) with solids comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof, wherein the metal is a mono or divalent cation to produce salts of said strong acid; and

(e) applying said salts of said strong acid obtained in (d) to the reaction mixture of step (a). [00067] In some embodiments the reaction mixture comprises a solvent such as water, and in some embodiments, the solvent includes at least one hydrophilic solvent or a combination thereof.

[00068] In some embodiments, the bicarbonate or a carbonate salt, present in the suspension is removed from the suspension, to give a clear suspension.

[00069] In some embodimentsat least part of the hydrophilic solvent present in the clear solution, is separated from said reaction mixture before it is used in step (d).

[00070] In some embodiments, at least part of the carbonate salt is separated from the suspension of step (c) to produce a resulting solution.

[00071] In some embodiments, the hydrophilic solvent is not separated from the reaction mixture before it is used in step (d). In a preferred embodiment, the strong acid is not separated from the OWB* strong acid. In this preferred embodiment, in step (d), the solids are contacted with OWB* strong acid.

[00072] In some embodiments, the strong acid is removed from OWB*strong acid after the separation of the hydrophilic solvent and before it is used in step (d). In this preferred embodiment, in step (d), the solids are contacted with the free strong acid.

[00073] In some embodiments, the hydrophilic solvent present in steps (a) and (b) is separated from said reaction mixture prior to use in step (c). According to this aspect and in some embodiments, the strong acid is removed from said OWB*strong acid following separation of said hydrophilic solvent and prior to its use in step (d).

[00074] In some embodiments, the strong acid in said mixture of step (c) is contacted with said solids, in the form of a free strong acid or OWB*strong acid or a combination thereof.

[00075] According to this aspect and in some embodiments, such processes further comprise the steps of:

(f) in said combining in step (a), said reaction mixture further comprises a hydrophilic solvent and water;

(g) separating out said hydrophilic solvent in step (c) when isolating the carbonate salt or bicarbonate salt formed and the liquid filtrate comprising said OWB*strong acid and recycling said hydrophilic solvent to step (a); (h) Separation of the strong acid from said OWB*strong acid to obtain free strong acid and contacting said free strong acid with said solid comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof in (d) such that at least a portion of said solids react with said strong acid to form a salt of strong acid; and

(i) Recycling said OWB and salt of strong acid to step (a).

[00076] According to this aspect and in some embodiments, such processes further comprise the steps of:

(f). Prior to step (a) contacting a solution comprising OWB*HCl with a solid comprising salts or oxides selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts of weak acids or any combination thereof, wherein said metal is a monovalent cation or a divalent cation and wherein at least a portion of said solid reacts with said strong acid to form a salt of a strong acid;

(g). Preparing a reaction mixture comprising at least one salt of a strong acid produced in step (f); at least one organic weak base (OWB); and a hydrophilic solvent as part of step (a); and

(h) Recycling the OWB* strong acid, hydrophilic solvent and the salt of said strong acid obtained in step (e) to step (a).

[00077] In some embodiments, the strong acid is removed from the OWB*HCl by using a method selected from washing it, using a mixer-settler unit/s by water or by aqueous solution or by thermal decomposition or by contact of the OWB*HCl with a compound comprising of metal oxide or hydroxide of carbonate or bicarbonate or a salt of weak acid.

[00078] In some embodiments, the strong acid is not separated from OWB*strong acid before it is used in in step (d).

[00079] In some embodiments, the solids comprise metal oxides or metal hydroxides or metal carbonate or salt of weak acid or the combination thereof. In a preferred embodiment the strong acid is separated, as a free acid into said solids to produce salt of strong acid. In another preferred embodiment, the salt of strong acid is added to a reaction mixture comprising of OWB and OWB*strong acid, an hydrophilic solvent and water. In some embodiments, CO ₂ is added into said reaction mixture to produce OWB*Strong acid and a metal carbonate or a metal bicarbonate or a combination thereof. In a preferred embodiment, at least part of the suspension comprising the metal carbonate and/or the metal bicarbonate is removed and the metal carbonate and/or metal bicarbonate are separated from the suspension to form a clear solution. In some embodimentsthe hydrophilic solvent is separated from said clear solution and recycled to said reaction mixture. In a preferred embodiment, the strong acid is released from OWB*Strong acid. In a preferred embodiment, the released strong acid reacts is contacted with a solid comprising a metal oxide or a metal hydroxide or a metal carbonate or metal bicarbonate or the combination thereof.

[00080] In some embodimentsthe reaction mixture comprises at least one enhancer, wherein an enhancer is a solvent that increase the basicity of the OWB. In a preferred embodiment the enhancer is selected from one of a long chain alkanol or a long chain carboxylic acid, a long chain phosphate comprising compound and wherein said enhancer is more hydrophobic than butanol, or the combination thereof.

[00081] In some embodiments, the reaction mixture comprises at least one enhancer, wherein an enhancer is a solvent that increase the basicity of the OWB.

[00082] In some embodimentsthe reaction mixture comprises water.

[00083] In some embodimentswherein the reaction mixture comprises at least an aqueous phase comprising a salt of a strong acid and an organic phase comprising OWB and OWB* strong acid.

[00084] In some embodiments, said solid is selected from an ore, fraction or fractions of solid separated from ore and the combination thereof.

[00085] In some embodiments the solid is Fly-ash wherein Fly ash comprises solids obtained as a result of incineration of organic materials. In some embodiments, the incinerated organic material comprises waste. In some embodiments the solid selected from municipal waste stream, sewage, waste from farms, industrial, biochemical and the combination thereof.

[00086] In some embodiments said solid comprises mono valent cations or divalent cations. [00087] In some embodiments said solid comprises also tri valent cations or higher valent cations and the combination thereof.

[00088] In some embodiments said solids comprising anions of weak acids selected from phosphate, silicate, sulfur comprising anions, carbonate, and the combination thereof. [00089] In some embodiments the solid comprise divalent cations. In some embodiments, the solids comprise cations selected from Calcium, magnesium, Zinc, Manganese, Copper

[00090] In some embodiments the solid is an ore comprising a rare earth element (REE), or rare element (RE) along with the metal oxides or metal hydroxides, metal carbonate or salt of weak acid.

[00091] In some embodiments the solid is an ore comprising phosphate and solids comprising a metal oxide or a metal hydroxide or a metal carbonate or a salt of a weak acid or the combination thereof

[00092] In some embodiments the solid is an ore comprising CaCO3 or CaMgCO3 or a combination thereof.

[00093] In some embodiments the OWB is tertiary amine having a pK1/2 of 0 to 5.

[00094] In some embodiments the OWB is tertiary amine with pK1/2 of 3-5.

[00095] In some embodiments the OWB is tertiary amine with pK1/2 of 0-3.

[00096] In some embodiments the OWB is tertiary amine with pK1/2 of 0-1.

[00097] In some embodiments the OWB is alkyl tertiary amine comprises from side chains selected of, methyl alkyl amine, ethyl alkyl amine, propyl alkyl amine, butyl alkyl amine, pentyl alkyl amine or hexyl alkyl amine, cyclic and/or aromatic group and the combination thereof.

[00098] In some embodiments the OWB has lower molecular weight then Tris 2- ethyl hexyl amine. In another preferred embodiment, the OWB comprises atoms selected from N, S, P, C, O and the combination thereof.

[00099] In some embodiments the strong acid has a pK1/2 lower than 4. In another preferred embodiment the strong acid has a pK1/2 lower than 3.

[000100] In some embodiments the strong acid is selected from HCl, halogenic acids, H2SO4, HNO3 or the combination thereof.

[000101] In some embodiments the salt of a weak acid is a salt of acid with a pK1/2 of higher than 2.

[000102] In some embodiments the salt of a weak a salt selected of the anions silicate or a phosphate or of S ⁼ or of SO ₃ ^3- or the combination thereof. [000103] In some embodiments the hydrophilic solvent is selected from the group of alkanol, alkanol ester, alkanol ether, polyols, polyol ether, polyol ester, hydrophilic polar solvents or the combination thereof.

[000104] In some embodiments the hydrophilic solvent is selected from ethanol, 1- propanol, iso butanol or third butanol, esters, ethers, amides and polar solvents or the combination thereof.

[000105] In some embodiments the pK1/2 of the OWB is higher than 2 and lower than 7.

[000106] In some embodiments, the reaction mixture comprises a hydrophobic diluent.

[000107] In some embodiments, the cation of salt of strong acid is selected from the group comprising of monovalent cations or divalent cations and in some embodiments, the cation of salt of strong acid is sodium, ammonium or calcium or magnesium or a combination thereof.

[000108] Separation of the hydrophilic solvent

[000109] One of the effects of the inclusion of a hydrophilic solvent is the increase in the basicity of the OWB in the reaction mixture. In order to enable efficient release of the strong acid from the OWB*strong acid, the hydrophilic solvent is removed prior to strong acid release.

[000110] In some embodiments, the mother liquor does not contain a hydrophilic solvent.

[000111] In another preferred embodiment, the hydrophilic solvent present in the mother liquor is not separated from the mother liquor or from the clear solution obtained after the separation of the metal carbonate salt. In this embodiment, the acid reacts with the solids while present in the form of OWB* strong acid.

[000112] In another embodiment, according to this aspect, the mother liquor comprises a hydrophilic solvent and the strong acid should be released from OWB* strong acid and the released strong acid, called also the free strong acid, is contacted with the solids to form a salt of the strong acid.

[000113] In some embodiments, the hydrophilic solvent is removed by washing with water or with aqueous solution. In some embodiments back extraction is conducted then at temperatures higher than 40°C and in another embodiment, according to this aspect, back extraction is conducted at a temperature higher than 80°C. [000114] In some embodiments, the hydrophilic solvent is removed by evaporation. The vapors are cooled to form a liquid that might be recycled to the wash of reacted solids or a wash of the produced metal carbonate or metal bicarbonate or added to the reaction mixture.

[000115] In another embodiment according to this aspect, at least part of the hydrophilic solvent is removed by splitting the phase comprising mainly the OWB*HCl and the solvent into 2 liquid phases, the one comprises of most of the OWB*HX while the second comprises of part of the hydrophilic solvent, the salt of strong acid and water.

[000116] The split of a hydrophilic solvent split is, in some embodiments, a means of providing for savings in production costs.

[000117] In some aspects, a small change in conditions causes a major separation effect. It was very surprisingly found that such an effect can be achieved in solutions comprising a hydrophilic solvent, OWB, strong acid, salt of strong acid and water for some hydrophilic solvents having a narrow range of LogP(octanol/water).

[000118] For other hydrophilic solvents, out of this range, such phenomena of a small change in conditions causes a major separation effect does not in fact, occur.

[000119] In some embodiments the separation of the hydrophilic Solvent Split is done by using a method comprising a change in temperature, heating of the solution, addition of CO ₂ , addition of liquid CO ₂ , addition of a salt of the strong acid, addition of a hydrophobic solvent, addition of OWB, addition of a hydrophilic solvent, addition of water, addition of aqueous solution, removing of at least part of the hydrophilic solvent or any combination thereof.

[000120] In some embodiments the residual hydrophilic solvent is removed from the phase comprising OWB and acid by washing with water or an aqueous solution. In some embodiments the residual hydrophilic solvent is washed by the strong acid salt solution.

[000121] Separation of the strong acid from OWB*HX

[000122] In some embodiments the strong acid is not separated from OWB*strong acid. In this embodiment, OWB*strong acid is contacted with the solids to form the salt of strong acid.

[000123] In another embodiment, the strong acid is separated from OWB*strong acid. [000124] In some embodiments the strong acid is removed from the phase comprising OWB* strong acid by its thermal decomposition at a temperature higher than 100°C. In another preferred embodiments, the acid is removed from the phase comprising OWB by thermal decomposition at a temperature higher than 100°C.

[000125] In some embodiments, the strong acid is removed from the phase comprising OWB*strong acid by contact with a base or a carbonate salt or a bicarbonate salt or a salt of weak acid or the combination thereof.

[000126] In some embodiments, the acid is removed from the phase comprising OWB by contact water or aqueous solution comprises the strong acid salt.

[000127] Any method known in the field for the separation of the strong acid from the OWB*strong acid can be used here even if not mentioned above.

[000128] The method of the invention is preferably carried out continuously.

[000129] In another embodiment, the solvent is a polar solvent with high solubility in water. In some embodiments, the hydrophilic solvent is DMSO, DMSO, methyl formamide or other hydrophilic polar solvents. It will be appreciated that other solvents with similar properties may be used in accordance with this aspect, such as will be known to the skilled artisan and the listed examples serves for illustrative purposes alone and are not meant to be limiting.

[000130] The present invention also provides a method for production of HCl from a CaCl ₂ waste stream obtained from the mining industry or other solids, while producing CaCO ₃ and HCl that can be recycled to the ore-leaching step of the embodied processes or sold as HCl solution./used in other unrelated commercial applications, for example. In a similar way, the present invention can be used for separation of strong acids other than HCl from mining industry thus recycling the strong acid to previous steps and producing carbonate, or bicarbonate salts or oxides.

[000131] In some embodiments, the cation in the strong acid salt is a divalent cation or a monovalent cation.

[000132] In some embodiments the cation is a divalent cation and in some embodiments the cation is one of Ca or Mg or the combination thereof. In some embodiments the cation is a monovalent cation and some embodiments the cation is ammonium or sodium.

[000133] In some embodiments the strong acid is selected from HCl, halogenic acids, H ₂ SO ₄ ,

HNO ₃ , H ₃ PO ₄ . [000134] Type and origin of the solid

[000135] The core process can be implied for any solid comprising of metal oxide, metal hydroxide, metal carbonate or metal bicarbonate, a salt of a weak acid or the combination thereof. In the following, it is described some groups of processes from various fields. It will be evident to those skilled in the art that the applications mentioned here are only a part of optional applications and the invention is not limited to those applications.

[000136] Applications in the chemical industry

[000137] In some embodiments the strong acid salt is CaCl ₂ derived from the process for the production of NaCO ₃ or NaHCO ₃ or the combination thereof and the invention therefore also includes a method for the production of sodium bicarbonate and/or sodium carbonate.

[000138] The Solvay process involves heating of CaCO ₃ to release CO ₂ and produce CaO. CO ₂ is released from at least a portion of the CaCO ₃ and reacts with NaCl in the presence of CaO to give the product NaCO ₃ and CaCl ₂ . The waste solution comprises the divalent cation salt of HCl, can react in the present invention to give the products HCl and CaCO ₃

[000139] The chemical equations of the Solvay process:

Eq. 1. CaCO ₃ ====== CaO + CO ₂ + H ₂ O

Eq. 2. 2NaCl + CO ₂ + H ₂ O + CaO ==== 2NaHCO3 or Na ₂ CO ₃ + CaCl ₂

The next stage, in the present invention, in some embodiments, CaCl ₂ produced by the Solvay process reacts according to the following equations

Eq. 3. OWB + CaCl ₂ + CO ₂ + water ==== OWB*HCl + CaCO ₃ (goes to Eq.1)

Eq. 4. OWB*HCl ======= OWB + HCl. [000140] In still further embodiments, the invention provides a novel procedure for the production of NaHCO3 or Na ₂ CO ₃ . This procedure skips the reaction described in Eq. 1. And 2 and supplies an additional product, i.e. HCl.

[000141] The process reactions are :

Eq. 5. OWB(1) + NaCl + CO ₂ + H ₂ O ==== OWB*HCl + NaHCO ₃

Eq. 6. OWB(1)*HCl + MCO ₃ =====OWB + MCE

[000142] OWB(l) is an organic weak base having a pK 1/2 in the range of 0.5 to 5.

[000143] MCO3 is a divalent metal carbonate. In some embodiments, the metal carbonate is selected from CaCO3, MgCO3 or the combination thereof

[000144] In some embodiments the OWB released in Eq. 6 is recycled to Eq. 5.

[000145] In another embodiment, the produced CaCl ₂ is converted to CaCO3 as demonstrated in eq. 7.

[000146]

Eq. 7. OWB (2) + CaCl ₂ + CO ₂ + water ==== OWB*HCl + CaCO ₃

The CaCO ₃ in Eq. 7 goes to the reaction in Eq. 6.

Eq. 8. OWB (2)*HCl ======= OWB (2) + HCl

[000147] In some embodiments the OWB (1) phase may further comprise an enhancer. The term “enhancer” as used in connection with the processes as herein described refers to an organic compound having at least one hydrophilic function that is added into an extractant (such as the OWB ( 1 )) in order to increase its basicity. In some embodiments the enhancer is an alkanol selected from C4-C20 alkanols

[000148] The overall reaction is:

NaCl + CO ₂ + H ₂ O ==== NaHCO ₃ + HCl. [000149] Global warming solutions

[000150] The process as described above can serve also for global warming solution

[000151] In the first step :

[000152] 2 NaCl + 2OWB(1)+2CO ₂ + water === 2OWB(1)*HCl +2NaHCO ₃

[000153] The OWB here has a pK1/2 of 1.5-4

[000154] In Step 2:

[000155] 2*OWB(1)*HCl + CaCO3 ==== OWB(l) + CaCl ₂ + CO ₂

[000156] The CaCO3 might come as a waste from the mining industry. For each mole of CO ₂ produced in second step, 2 mole of CO ₂ are consumed in Step 1.

[000157] In this process NaHCO3 is a valuable product.

[000158] Another option is converting the CaCl ₂ in the process described before, i.e

[000159] Step 3. CaCl ₂ + OWB + CO ₂ + water ==== CaCO ₃ + OWB*HCl

[000160] Freeing the HCl from OWB (2) will give additional product meaning dilute HCl solution

[000161] The CaCO3 that is produced in Step 3 is to be consumed in Step 2.

[000162] A process for the separation of CO ₂ from flue gas or other gas streams comprising CO ₂

[000163] In some embodiments, the present invention is used for the production of concentrated CO ₂ gas from dilute CO ₂ streams. In some embodiments, the dilute CO ₂ stream is a flue gas originated by burning fuel in various plants, such as power plants for the production of electricity, motors, or any other source.

[000164] A process for the production of concentrated CO ₂ streams comprising the steps: [000165]

(a) Preparing a reaction mixture comprising of (a) at least one OWB (b) OWB* strong acid (c) a salt of a strong acid (d) water, in Vessel 1.

(b) Adding a stream comprising dilute CO ₂ at elevated pressure and getting a suspension comprising a precipitate comprising of metal carbonate and OWB*strong acid, and a gaseous stream poor in CO ₂ . (c) Removing at least part of the suspension into another vessel (Vessel 2), wherein the OWB*strong acid reacts with the metal carbonate to produce a solution comprising salt of strong acid and concentrated CO ₂ stream at pressure lower than that in Vessel 1.

(d) Removing at least a part of said solution comprising a salt of strong acid into the reaction mixture in step (a).

[000166] In some embodiments, the CO ₂ pressure in vessel (1) is higher than the CO ₂ pressure in Vessel 2. In some embodiments, the concentrated CO ₂ stream in vessel 2 is removed from Vessel 2 and pressurized. In some embodiments, the boiling point of the OWB is higher than 250°C. In some embodiments, the gaseous CO ₂ poor stream exiting Vessel 1 is cooled to condense the content of OWB. In some embodiments, the cooled gas is contacted with adsorbent to remove residual organic material.

[000167] In some embodiments, the reaction mixture comprises of an enhancer. In some embodiments the enhancer is selected from organic materials selected from alkanol or poly alcohol.

[000168] A process for processing of Fly Ash

[000169] Fly-ash is the solid particles obtained by burning of organic material. The 2 largest sources of fly ash are from burning of fuel and from burning of garbage. Fly-ash comprises a mix of inorganic materials, a significant part is in the form of oxides but they contain also other anions such chloride and Sulfur comprising solids and silicates. Due to the high temperature treatment, the fly ash comprises monovalent bases and divalent bases in the form of oxides/hydroxides.

[000170] Regulatory requirements impress the urgent need to reduce the volume of the fly ash to be buried and to remove dangerous soluble poisonous cations from same. One option to reduce the volume is to leach the solids in HCl, thus dissolving the mono-valent cations and the di- valent cations.

[000171] The cost of the consumed HCl is very high and therefore there is a need for a process to regenerate the acid.

[000172] Thus, in some embodiments, this invention provides a means to therefore provide a cost-effective source of the acid, fulfilling this need. [000173] In some embodiments, the fly ash is washed with water to dissolve the mono-valent basic oxides to form basic hydroxides and also part of the divalent oxides. In some embodiments, the washing procedure is done at 50°C-100°C.

[000174] The invention presented here provides processes, in some embodiments, by which a significant amount of fly-ash is converted into valuable products.

[000175] In some embodiments, Fly ash is contacted with a strong acid solution to produce salts of strong acid. In some embodiments, the leachate comprises mono-, di-, tri-, and/or 4- valent cations.

[000176] In some embodiments, the aqueous solution comprises concentrated CaCl ₂ solution, which is added into a reaction mixture comprising a suspension of metal carbonate, salt of strong acid, OWB, OWB*strong acid, and a hydrophilic solvent. CO ₂ is added into said reaction mixture to produce a metal carbonate and OWB* strong acid. At least part of the suspension is removed and filtered to yield metal carbonate and liquid stream comprising OWB*strong acid and a hydrophilic solvent. In some embodiments the hydrophilic solvent is removed and the strong acid is separated from the OWB* strong acid. The strong acid is reacted with the fly-ash to produce a salt of strong acid. In some embodiments, the solutions comprising the salt of a strong acid the OWB, the hydrophilic solvent are returned to the reaction mixture.

[000177] In each cycle, a divalent metal carbonate is produced. In some embodiments, the metal carbonate is CaCO3. The residual solution comprises various products such as KCl/NaCl which can be separated as products, various divalent salts, part of are at relatively high concentration and can be separated as salts of strong acid or metal carbonated.

[000178] In some embodiments, the residual aluminum salt that is obtained in the leaching step is precipitated from the solution to give aluminum hydroxide and a salt of strong acid. In some embodiments, the aluminum hydroxide is separated washed and dried to give a valuable product.

[000179] In some embodiments, valuable metal products are separated in a consecutive manner to produce the salts, hydroxides or oxides of the various metals.

[000180] Option 2, Leaching with OWB*Strong acid and consecutive separation of cations of higher valences. [000181] In another embodiment, Fly-ash is leached with OWB*strong acid without the separation of the strong acid from OWB* strong acid. It was found that in this method, the leaching becomes more selective.

[000182] In some embodiments, therefore, this invention provides a process for the production of products from fly- Ash comprising the steps:

(a). Adding a salt of strong acid to a reaction mixture comprising of OWB and OWB* strong acid

(b). Adding CO ₂ into said reaction mixture to produce a strong acid, in the form of OWB* strong acid and precipitation of metal carbonate.

(c). Removing at least part the suspension comprising the metal carbonate and the solution comprising OWB* strong acid.

(d). separation of the metal carbonate from the solution comprising OWB*strong base.

(e). contacting at least part of OWB*strong acid produced in (d) with Fly-Ash to produce a salt of strong acid and residual solids and OWB.

(f). Adding the OWB and the solution comprising the salt of strong acid to the reaction mixture in (a).

[000183] In some embodiments, the reaction mixture comprises waste and a hydrophilic solvent.

[000184] In some embodiments, the hydrophilic solvent is not separated prior to step (e).

[000185] In some embodiments, the Fly-Ash is washed with solution comprising water prior to step (e). In some embodiments, some divalent cations are separated by adding base. In some embodiments, the base solution is obtained by contacting aqueous solution with the Fly Ash.

[000186] In some embodiments, the washed solid is leached with a strong acid solution to dissolve the divalent cations and a small part of the tri and four valent cations.

[000187] In another preferred embodiment, the solids are leached with a strong acid, at higher temperature and concentration to dissolve also a larger part of the tri and four-valent cation.

[000188] In some embodiments, the suspension is filtered to get the un-leached solids and solution comprising the leached cations. [000189] In some embodiments, a base or a carbonate is added to precipitate the four-valent and tri-valent cations. In another preferred embodiment, the base or the carbonate salt are added gradually to precipitate gradually the cations thus getting fractions of solids comprising mainly the desired cation oxides.

[000190] In some embodiments, the residual solids obtained in Step (e) are contacted with a strong acid, to produce salts of multi-valent cations. In some embodiments, one of the salts is of titanyl chloride. In another preferred embodiment the salt is Aluminum Chloride. In another preferred embodiment, the salt comprises SiO3.

[000191] In some embodiments, the cations are precipitated by adding a base or a carbonate to said solution to precipitate first the highest valent cations, such as titanium oxide hydroxide. In some embodiments, the precipitated oxide is separated from the solution.

[000192] In some embodiments, an additional base or carbonate is added to the solution to precipitate the trivalent cation oxides. In some embodiments, the trivalent cation oxide is Al(0H)3.

[000193] In some embodiments, the strong acid is HCl. In some embodiments, the divalent cation is Calcium. In some embodiments the added base is Ca(OH)2.

[000194] In some embodiments, the solids obtained after washing the mono-valent cations are treated with an ammonium salt. In some embodiments the salt is ammonium chloride. In another preferred embodiment, the salt is ammonium salt of a weaker acid.

[000195] According to this aspect and in some embodiments, the ammonium salt reacts with the divalent cation oxides present in the solids to produce ammonia and the salt of the divalent cation.

[000196] In some embodiments, the ammonia released, by contacting the ammonium salt with the solids, as described, is used to back-extract, at least a part of acid from the OWB in step (e) of the embodied processes presented herein and claimed, for example in claim 1 hereinbelow. In some embodiments, the resulting ammonium salt is reacted, as described, with the divalent cation oxides present in the solids.

[000197] Biotechnology industry

[000198] In some embodiments, the strong acid salt is obtained by adding a strong acid to a fermentation broth comprising a salt of a divalent-cation salt of organic acid. In some embodiments the organic acid is produced using a fermentation process. In some embodiments the organic acid is Lactic acid and the salt is Ca-lactate. In some embodiments, the lactic acid is extracted from the resulting solution. In some embodiments, the resulting CaCl ₂ solution enters to the reaction described in Claim 1 step (b) to give free HCl and CaCO3. In some embodiments, The CaCO3 is added to the fermentation process to react with the produced organic acid.

[000199] In another preferred embodiment, the strong acid is citric acid. In some embodiments the citric acid is produced by fermentation. In some embodiments, citric acid is extracted from the fermentation broth and back-extracted to get citric acid solution. In some embodiments, citric acid is crystallized and recrystallized to get pure citric acid. In some embodiments a strong acid is added to the mother liquor from ae crystallization or re- crystallization stage, to precipitate citric acid. In some embodiments, the resulting CaCl ₂ solution is fed into the3 reaction mixture in step (b) of Claim 1. In additional preferred embodiment, the solution obtained after the crystallization of CaCO3 in Claim 1 separated from the hydrophilic solvent and the remaining citric acid solution is return to the citric acid crystallization steps.

[000200] In some embodiments the organic acid is selected from any organic acid that is produced in a fermentation process.

[000201 ] A process for the processing of phosphate rock comprising CaCO ₃ and/or CaMg(CO ₃ ) ₂ .

[000202] In some embodiments the solid is a phosphate rock. In some embodiments, the phosphate rock is contacted with a strong acid to produce one of di-calcium phosphate or mono-calcium phosphate. In some embodiments, the solids comprising the phosphate are filtered to give di-calcium phosphate or mono-calcium phosphate or the combination thereof and a solution comprising CaCl ₂ . In some embodiments the solution comprising CaCl ₂ is added to the reaction mixture of Step (a).

[000203] In another preferred embodiment, the phosphate rock comprises also significant level of metal carbonates.

[000204] The presence of metal carbonates (mainly CaCO3 or CaMg(CO3) ₂ ), in the ore leads to a significant increase in the production costs, due to the increase in acid consumption and the production of waste solution or solids. Using the method presented here, thus recycling the acid and minimizing of the production of waste, will reduce the production costs.

[000205] In some embodiments, OWB-Strong acid is added to the ore comprising phosphate and carbonate ores, to leach the carbonate ores. In some embodiments, solution comprising the salt of strong acid is filtered and added to the mother liquor in Step (a). In some embodiments, the salt of strong acid, is converted according the present invasion into metal carbonate and HCl. In some embodiments the residual solids comprising the phosphate are contacted with a strong acid or OWB*strong acid in temperature suited for leaching to produce phosphoric acid and a solution comprising a salt of strong acid. In some embodiments, the salt of strong acid is added into the reaction mixture of step (a).

[000206] Separation of Dolomite - CaMg(CO3) ₂ to produce CaCO3 and MgCO3

[000207] CaMg(CO3) ₂ is present as ore in mix in other ores. The present invention, gives a cost-effective process for the production of CaCO3 and various Mg products. Mg products are more expensive products then Calcium products. Among the products one may find Mg salts such as MgCl ₂ , MgCO3, MgO or Mg(OH) ₂ and Mg metal.

[000208] In some embodiments OWB*strong acid is added to a solid comprising CaMg(CO3) ₂ , to give a solution comprising Ca salt of strong acid and Mg salt of strong acid. In some embodiments, the resulting solution is added to the reaction mixture in Step (a). In some embodiments, CO ₂ is added to the reaction mixture to produce a suspension of CaCO3 and solution comprising OWB*strong acid. The suspension is filtered and the solution comprising OWB*strong acid is recycled to contact with solids.

[000209] The Crystallization of CaCO3 is selective and gives CaCO3 of high purity up to yields of around 30%. Water is added in this step to the reaction mixture in this step to give a concentrated MgCl ₂ solution, comprising also CaCl ₂ , at high MgCl ₂ /CaCl ₂ ratio. In some embodiments, the aqueous MgCl ₂ solution is crystallized to give MgCl ₂ crystals and mother liquor comprising CaCl ₂ and MgCl ₂ . In some embodiments, the MgCl ₂ crystals are separated from said mother liquor and the mother liquor is recycled to Step (a). In some embodiments, MgCl ₂ is converted to MgCO3 and OWB*HCl, according to the procedure of the present invention.

[000210] Beneficiation of Nussir’s ore [000211] Nussir’s ore is an ore comprising of CaCO3, CaMgCO3, Na-aluminum-silicates and K- Aluminum silicates and Cu-ores, mainly as Cu-sulfide ores or Cu-pyrite ore.

[000212] The ore is milled. Separation by flocculation gives 2 streams. The product streams comprising a product stream comprising the Copper ores. The waste stream comprises Aluminum silicate ores, carbonates such as CaCO3, CaMg(CO3) ₂ .

[000213] In some embodiments, the feed ore is leached by OWB* strong acid before the flocculation step. In another preferred embodiment, the feed ore is leached by a strong acid before the flocculation step. In some embodiments, the strong acid is HCl.

[000214] In another preferred embodiment, the product stream is leached to remove the residual carbonates left in the product stream, thus increasing its purity level. In some embodiments, the product stream is leached by OWB*strong acid. In some embodiments, the product stream is leached by a strong acid. In some embodiments, the strong acid is HCl.

[000215] In another preferred embodiment, the waste stream is leached to remove the residual carbonates. In some embodiments, the waste stream is leached by OWB*strong acid. In some embodiments, the waste stream is leached by a strong acid before the flocculation step. In some embodiments, the strong acid is HCl. In some embodiments, the waste stream is re-leached after the first leaching, done by, OWB*HCl by a new portion of OWB*HCl, at a temperature higher by at least 20°C than in previous leaching, to leach at least part of the residual copper ore present in the waste stream. In some embodiments, the re-leaching is performed by a strong acid. In another embodiment, the re-leaching is performed by HCl.

[000216] In some embodiments, the process as described herein provide for the production of metal carbonate from streams obtained from copper comprising ores, which in other embodiments, further comprise metal carbonates.

[000217] In some embodiments the leachate obtained, after leaching of the raw material or after leaching of product stream or the leachate obtained after leaching of the waste stream, is added to a reaction mixture comprising OWB and OWB*strong acid, which constitutes one embodied step of the process (step a). According to this aspect and in some embodiments, CO ₂ is added into said reaction mixture to produce a strong acid, in the form of OWB*strong acid and precipitation of a carbonate salt or a bicarbonate salt of a monovalent cation or a divalent cation, or the combination thereof. In some aspects, at least part the suspension comprising the carbonate salt or the bicarbonate salt or the combination thereof is removed and the solution comprising OWB* strong acid. In still other aspects, At least part of the strong acid produced in step (a) is contacted with a stream comprising metal carbonate that is at least partially leached at least to produce the salt of strong acid that is added in step (a).

[000218] According to this aspect, and in some embodiments, the ore comprises CaCO3 and MaCO3.

[000219] According to this aspect and in some embodiments, after preforming the reaction, the reaction mixture is enriched by MgCl ₂ . In some embodiments, a part of the MgCl ₂ enriched reaction mixture is crystallized to produce MgCl ₂ crystals. In some embodiments, the mother liquor obtained after the crystallization of MgCl ₂ is recycled to the CaCO3 production step.

[000220] It will be apparent to those skilled in the art that various modifications and variations can be made in the processes, methods and systems of the present invention without departing from the spirit or scope of the invention.

EXAMPLES

Global warming solutions

[000221] Example 1. Production of concentrated CO ₂ stream from dilute CO ₂ stream.

Procedure: A stream comprising 10% CO ₂ and 90% N2, is compressed into a tank at pressure of 20bar. The compressed gas is bubbled into a vessel comprising 10gr of 45wt% CaCl ₂ , 20gr Alamine336 and 20gr Alamine336*HCl, 10gr of 1 -propanol, 0.5gr of CaCO3 seed crystals and 3gr of water. The suspension was mixed for 1 hour. The outlet gas was compressed and collected.

[000222] Results

1. A sample of the solution is analyzed for HCl and amine content. Z = 0.90.

[000223] The CO ₂ /N ₂ stream was stopped and the pressure in the vessel is reduced.

[000224] The CO ₂ stream released from the vessel is collected. 1.8gr of CO ₂ were collected. [000225 ] Example 2: Separation of HCl from NaCl solution using TOA as the OWB.

[000226] Procedure

(A). A solution comprising 10gr 1 -propanol, 10gr of (Di-octyl,(mono-ethylhexyl) amine) and 50gr of 20 wt% NaCl aqueous solution is stirred at R.T in open vessel. CO ₂ is bubbled into the solution. After 1 hour, the crystals are filtered and the solution is titrated for acid content.

[000227] Results

[000228] The molar ratio between the acid and the amine is 0.85

(B). The amine phase obtained in (A) is added into a vial comprising CaCO3 crystal and water. The suspension is shaken. CO ₂ exits from the vial.

[000229] Results

[000230] The molar ratio between the acid and the amine is 0.1.

[000231 ] Example 3 : Production of HCl from a solution comprising CaCl ₂

[000232] Procedure

[000233] A solution comprising 3 gr 1 -propanol, 7gr TEHA (Tri ethyl hexyl amine) at

Z=0.51 (Z acid/OWB molar ratio) and 6 gr of 40wt% CaCl ₂ aqueous solution was stirred at RT in a closed vessel. CO ₂ at a pressure of 10 bar was introduced into the solution. After 4 hour, the crystals were filtered and the solution was titrated for acid content.

[000234] Results

Z = 0.94

Z = the molar ratio between HCl to the amine

[000235] Conclusion

[000236] In a case in which there is a solution comprising the TEHA (the OWB), solvent and the salt with no or with insignificant presence of a second phase, HCl was released from the salt and CaCO ₃ was produced. The reaction was efficient even when CO ₂ was bubbled to the solution in an open vessel.

In the case of octanol as the solvent, 2 liquid phases are formed and there is practically no CaCl ₂ in the solvent phase. In this case even at 7 bar of CO ₂ and high solvent content, HCl was not separated from its salt and no CaCO ₃ was formed.

[000237] Experiment 4. Separation of HCl from CaCl ₂ and release of HCl from the OWB .

[000238] Using TOA as the OWB,

[000239] Comparative Experiment 4.1. No solvent

[000240] Procedure

[000241] 5gr, 27% CaCl ₂ solution and 5 gr TOA (Tri octyl amine) were added into a vessel. No solvent was added and 2 liquid phases were present. The solution was stirred at RT in a closed vessel. CO ₂ at a pressure of 7 bar was introduced into the solution. After 1 hour, the crystals were filtered and the solution was titrated for acid content.

[000242] Result: Z = 0.36

[000243] Comparative Experiment 4.2.

[000244] TOA (Tri-octyl amine) as the Organic base ethanol as the solvent, P-CO ₂ = 2 bar.

[000245] Procedure: The procedure is similar to that in Experiment 6.1. but with ethanol as the solvent. A single liquid phase was present and CaCO ₃ crystals were formed.

[000246] Results: Z = 1

[000247] Step 2: Back extraction

[000248] 9gr of the upper phase was introduced into a vial. The solution was stripped at 60C, to remove all of the ethanol.

[000249] 10gr water is added into the vial and the solutions are stirred at RT for 30min. a sample from the aqueous phase was analyzed for acidity.

[000250] Result: The concentration of HCl in the aqueous phase is 0.18wt%.

[000251] Conclusions:

[000252] The acid could not be back extracted to give reasonable concentration. [000253] Experiment 4.2 TEHA as OWB, 1-propanol as the solvent.

[000254] Step 2 Back-Extraction

[000255] 9gr of the upper phase obtained in the solution of Experiment 4.1 was introduced into a vial. The solution was stripped at 60C, to remove all of the solvent.

[000256] 10gr water is added into the vial and the solutions are stirred at RT for 30min. a sample from the aqueous phase was analyzed for acidity.

[000257] Result: The concentration of HCl in the aqueous phase is 6wt%.

[000258] Conclusions: The HCl that was separated from CaCl ₂ , using TEHA in a single phase, could be back- washed to give an aqueous solution of 6wt%.

[000259] Experiment No 5 : Processing waste stream from Nussir Copper experimental plant

[000260] Nussir waste stream comprises CaCO3, CaMg(CO3) ₂ , Na or K aluminum silicates, silica and copper ore residue. The present experiment aimed to leach the metal carbonates, followed the production of CaCO3 and MgCl ₂ as products.

[000261] Experiment No.5.1: Leaching with OWB*HCl

[000262] Procedure: 1.00gr Nussir waste stream, 4.52gr Amine*HCl at Z=0.92, 2.56gr 1- propanol and 1.01gr water were added into a vial. The vial wash stirred (magnetic stirrer at RT for 7 hours. In parallel, a second vial comprises similar amount of ingredients, was shaken at 60°C for 7 hours. Vigorous release of CO ₂ was noted. After 7 hours, the suspensions were filtered and the resulting solutions were analyzed for Ca and Mg.

[000263] The results are presented in the following Table:

000264 Conclusions: The leaching with TEHA*HCl is efficient in leaching, mainly

CaCO3 and CaMg(CO3). At RT, and at 60°C about 100wt% of the dissolved solids are found in the leachate as CaCO3 and MgCO3. The leaching was efficient for both CaCO3 and CaMg(CO3) ₂ . If other components of the raw material are also leached, only a very small amount might be leached.

[000265 ] Experiment No 5.2: Reaction between leached solids and CO ₂ + water using TEHA as the OWB.

[000266] Procedure

[000267] 59.95gr of Nussir’s waste stream and 2wt% HCl solution, were added into a flask.

The flask was stirred using magnetic stirrer at RT. After leaching, the solution was filtered and concentrated under reduced pressure.

[000268] The concentrated solution, TEHA*HCl, 1 -propanol, CaCO3 seed crystal and water were added into a reactor. CO ₂ at lObar was continuously added to the reactor. , At the end of the experiment, water was used to wash the organic phase for 4 times and the aqueous solutions were collected. The solids formed in the reaction were washed 3 times with distilled water and dried. The water after wash was added into the collected water used to wash the organic phase. The resulting solution was concentrated. The concentrate was reacted to produce CaCO3 as in the previous cycle. The result crystals were washed with water and dried.

[000269] Results:

000270] Conclusions: Waste solids were leached efficiently and at high selectivity to other ores present in the waste stream. The product salts of HCl that were produced, were reacted with CO ₂ and water to produce CaCO3 at high selectivity (related to MgCO3), using TEHA*HCl. The resulting CaCl ₂ /MgCl ₂ solution was poor in CaCO ₃ and rich with MgCO3. [000271] Experiment 6. Production MgCl ₂ from the solution obtained in Experiment 5

[000272] Procedure: The mother liquor obtained in Experiment 4 is evaporated under reduced pressure at 60°C and using a magnetic stirrer. Crystals were formed. The crystals were filtered, washed with 1 -propanol dried and analyzed

[000273] Results: The crystals comprise MgCl ₂ with practically no CaCl ₂ .

[000274] Experiment No. 7. Crystallization of MgCO3 from solution comprising MgCl ₂

[000275] Procedure: 2.5gr MgCl ₂ , 3.2gr Amine*HCl at Z=0.5, 2.00gr 1-propanol, 0.1gr MgCO3 seed crystals and 0.75 water were added into a vial. CO ₂ at lObar was added continuously to the reactor. The vial wash stirred (magnetic stirrer at RT) for 12 hours.

[000276] The crystals were filtered under pressure of lObar CO ₂ , washed by 1-propanol and water dried and analyzed. The organic phase was analyzed for HCl content.

[000277] Results:

Z according to HCl/amine ratio = 0.92 Z according to produced MgCO ₃ = 0.93.

[000278] Experiment No. 8. Processing of dolomite (CaCO3*MgCO3) from Jerusalem mountains.

[000279] Procedure: Rock in Jerusalem Mountains was cut and processes to get its clean core. The core was crushed to get a fine white powder. The fine powder was used in the present experiment.

[000280] The fine powder, OWB*strong acid (or HCl solution), 1 -Propanol and water were added into 3 vials. The first tube was filled with amine*HCl, 1-propanol and H ₂ O. In each vial, 0.5mol of CaCO3 was added, (assuming all powder is CaCO3) 1.2 mol eq of HCl as free acid at 2% acid, or OWB*HCl, water at 10% of total solution and 1-Propanol at 1- propanol to OWB of 40:60. In one tube the temperature during leaching was 60°C. In the third tube the leaching was with 1.2 mol eq. of 10% HCl solution. [000281] Each tube was left over night. The solids were separated from the liquid. The organic phase was washed with water and all aqueous phase for each vial were combined for analysis.

[000282] Results:

[000283] Experiment No. 9 Processing fly ash [000284] Leaching of Fly ash with

TEHA*HCl at Z = 0.9

(a) Procedure: The leaching of Fly ash was done in 2 steps, simulating counter current leaching. First Fresh fly ash was leached with TEHA*HCl at Z = 0.7. 1- Propanol/TEHA = 0.4. Water = 12.6wt% of solution, Temperature = 50°C. In the second step, the residual solids from the first step were leached with TEHA*HCl at Z = 0.9.

[000285] Results

[000286] 42.4wt% of initial solids was leached in cycle 1.

[000287] 29.2wt% of the initial solid was leached in the second cycle.

[000288] Total solids leached in the process: 73.6wt% of initial solids.

[000289] Leaching with TEHA*HCl [000290] A similar experiment was done with 4wt% HCl solution at 60°C

[000291] Leaching with 4wt% HCl.\

[000292] Total solid leaching Yield: 73.6wt%

[000293] Leaching of trivalent cations and silicates (silicates are analyzed by Si content in the leachate solution.

[000294] Al = Aluminum, Ti - Titanium

[000295] Conclusions: Leaching with TEHA*HCl is highly selective. The two main types of non- divalent cations that are leached at high yield with 4wt% HCl solution are not leached with TEHA HCl.

[000296] These results demonstrated the simplification of the process while using TEHA*strong acid instead of using free acid.

[000297] In case in which one wants to produce both CaCO3 (and afterwards other divalent carbonates), he might leach first with OWB*strong base and produce from it the divalent cation carbonate, afterwards one might leach with free strong acid to leach the trivalent-four valent-cations at high purity and yield. From the pure solution, Al and/or Ti can be precipitated selectively by controlled increase in pH to precipitate first Ti and afterwards Al

[000298] A process for beneficiation of phosphate ores.

[000299 ] Experiment No 10: The experiments done with phosphate ore that comprise CaCO3.

[000300] Procedure Igr of phosphate ore comprising metal carbonate and 3gr of TEHA*HCl at Z=0.9, 1.5gr of 1 -Propanol and 1.5gr water are added into a vial. The vial is stirred for 8 hours at RT.

[000301] Results: The carbonate salts are leached to produce free CO ₂ and CaCl ₂ solution. [000302] It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being madteo the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

[000303] It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as set forth in the appended claims. Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed in the scope of the claims.

[000304] In some embodiments, the term "comprise" or grammatical forms thereof, refers to the inclusion of the indicated components of this invention, as well as inclusion of other active agents, and pharmaceutically acceptable carriers, excipients, emollients, stabilizers, etc., as are known in the pharmaceutical industry.

[000305] In the claims articles such as "a", "an" and "the" mean one or more than one unless indicated to the contrary or otherwise evident from the context. Claims or descriptions that include "or" or "and/or" between members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context.

[000306] The invention includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process.

[000307] The invention also includes embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.

[000308] Furthermore, it is to be understood that the invention provides, in various embodiments, all variations, combinations, and permutations in which one or more limitations, elements, clauses, descriptive terms, etc., from one or more of the listed claims is introduced into another claim dependent on the same base claim unless otherwise indicated or unless it would be evident to one of ordinary skill in the art that a contradiction or inconsistency would arise. Where elements are presented as lists, e.g. in Markush group format or the like, it is to be understood that each subgroup of the elements is also disclosed, and any element(s) can be removed from the group.

[000309] It should be understood that, in general, where the invention, or aspects of the invention, is/are referred to as comprising particular elements, features, etc., certain embodiments of the invention or aspects of the invention consist, or consist essentially of, such elements, features, etc.

[000310] For purposes of simplicity those embodiments have not in every case been specifically set forth in haec verba herein.

[000311] Certain claims are presented in dependent form for the sake of convenience, but Applicant reserves the right to rewrite any dependent claim in independent format to include the elements or limitations of the independent claim and any other claim(s) on which such claim depends, and such rewritten claim is to be considered equivalent in all respects to the dependent claim in whatever form it is in (either amended or unamended) prior to being rewritten in independent format.