The invention is in the field of inorganic chemistry, integrating electrochemical processes with steps of hydrometallurgical value extraction and carbon dioxide capture.
Technologies for efficient sequestration of gaseous carbon dioxide are potentially an important tool for addressing anthropogenic climate change. Various approaches have been suggested for sequestering carbon as mineral carbonates, including techniques that accelerate weathering reactions of minerals in ultramafic and mafic source rocks. These enhanced weathering (on land) or ocean alkalinity enhancement (at sea) approaches consume CO2 but are necessarily accompanied by a release of mineral dissolution products such as alkaline species and metal compounds, for example Si, Ca, Mg, Fe, Ni, and Co species. The ecological effect of these processes are uncertain (see Bach et al., CO2 Removal With Enhanced Weathering and Ocean Alkalinity Enhancement: Potential Risks and Co-benefits for Marine Pelagic Ecosystems, Frontiers in Climate, vol. 1, 2019, pg 7). There is a need for processes that integrate carbon capture with the recovery of metal values from mineral feedstocks.
Processes are provided in which successive steps of hydrometallurgical value extraction are carried out on a mineral feedstock, such as an olivine, mafic, saprolite or ultramafic feedstock. In select embodiments, the products of carbon capture reactions and an electrolytic reagent-generating process are utilized as inputs to hydrometallurgical value recovery steps. The electrolytic process provides the acid leachant (HCl or H2SO4) and an alkali hydroxide (NaOH or KOH), with the alkali hydroxide then available for use either directly as a precipitant in the hydrometallurgical steps, or available for conversion to an alkali metal carbonate or bicarbonate that can in turn be used as the precipitant in the hydrometallurgical steps. In an alternative embodiment, the alkali hydroxide from the chloralkali process may be used to precipitate a calcium hydroxide product, with the calcium hydroxide product then available for use directly in carbon dioxide gas scrubbing, or for use to accept a carbonate that is provided by a CO2 scrubbing process.
Processes are accordingly provided for the coproduction from mineral feedstocks such as basaltic rocks of less carbon intensive, or carbon negative, nickel, iron, calcium and magnesium hydroxides or carbonates. Basaltic sand materials that include amorphous silicates may also be produced. These processes may involve (1) magnetic separation, (2) hydrochloric or sulfuric acid leaching, (3) selective precipitation of metal hydroxides or carbonates in successive steps, which may involve pH modulation (in select embodiments, nickel may for example be separated using a resin in leach step) (4) electrolysis of a resulting barren solution, for example a chloralkali process for treating NaCl(aq), or an electrolytic salt splitting anion exchange process for treating Na2SO4(aq), and (5) acid and alkali reagent recycling, for example in the case of a chloralkali process, hydrochloric acid production from the hydrogen and chlorine gas products of the electrolysis.
Process of the invention accordingly provide for the use of less carbon intensive nickel, iron, calcium and magnesium hydroxides or carbonates, as well as olivine and basaltic sand material, including amorphous silicates, in marketable products. These may for example include feedstocks for battery, steel, cement, tyre, glass, aggregate, or concrete industries. Products of the present processes, such as the solid siliceous residue or iron precipitate products, may for example be subject to washing and/or alkalization. The adjustment of pH by way of alkalization (alkali addition) may improve the suitability of the final product, for example to produce a siliceous residue suitable for use as a supplementary cementitious material (SCM) in cements with improved cementitious properties.
The present processes provide avenues for the coproduction of less carbon intensive nickel and iron hydroxides, and this in turn may provide avenues to decarbonate sectors associated with the transition to a low carbon economy—such as electric vehicles and batteries. The invention also facilitates low carbon steelmaking, by compensating carbon heavy pyrometallurgy with a carbon negative magnetic, hydrometallurgical and electrochemical process.
The present processes provide for the coproduction of less carbon intensive amorphous silicates, marketable as a supplementary cementitious material (SCM) for cements, or in the tyre manufacturing industry. Basaltic sand materials may be produced by the present processes, with an inert surface, for example for use as aggregate in concrete mixes. The invention accordingly facilitates the construction of less carbon intensive concrete buildings.
Processes are accordingly provided for processing a comminuted mineral feedstock, comprising:
Processes may further include scrubbing carbon dioxide from a CO2 containing gas, including ambient air, by treating the CO2 containing gas with a scrubbing solution comprising the alkali hydroxide precipitant, to produce one or more of the alkali metal carbonate or bicarbonate precipitants.
Processes are according provided for processing a comminuted mineral feedstock, comprising:
Processes may further involve reacting the alkali hydroxide product of the electrolysis process directly or indirectly with a carbon source to produce one or more of the alkali metal carbonate or bicarbonate precipitants. The step of reacting the alkali hydroxide product with a carbon source may involve scrubbing carbon dioxide from a CO2 containing gas by treating the CO2 containing gas with a scrubbing solution comprising the alkali hydroxide product, to produce one or more of the alkali metal carbonate or bicarbonate precipitants.
In select embodiments, calcium may be precipitated from the Mg-depleted solution with a fifth alkali hydroxide precipitant, to produce a calcium hydroxide product, and generating one or more of the alkali metal carbonate or bicarbonate precipitants by treating the calcium hydroxide product with a carbon source, such as a CO2 containing gas or a metal carbonate, and the CO2 containing gas may for example be air. When the alkali hydroxide product comprises NaOH, scrubbing carbon dioxide from the CO2 containing gas may accordingly involve precipitating Na2CO3 hydrates from the scrubbing solution in a crystallisation process to produce a solid Na2CO3 crystallizer product, and one or more of the alkali metal carbonate or bicarbonate precipitants comprises the solid Na2CO3 crystallizer product.
In alternative embodiments, the alkali metal carbonate or bicarbonate precipitant may be one or more of NaHCO3, Na2CO3 or K2CO3, or a mixture thereof. The alkali hydroxide precipitant may be one or both of NaOH or KOH, or a mixture thereof. The acid leachant may for example be a mineral acid, such as HCl or H2SO4, or a mixture thereof.
The electrolysis process may involve a chloralkali process, producing the alkali hydroxide precipitant and/or the alkali hydroxide product, a Cl2(g) product and a H2(g) product. The Cl2(g) product and the H2(g) product may then be reacted to produce HCl as the acid leachant.
When the Mg-depleted solution includes Na2SO4, the electrolysis process may involve a salt splitting process that includes electrolytic generation of: the alkali hydroxide product and/or the alkali hydroxide precipitant; and, H2SO4 as the acid leachant.
Precipitating magnesium from the Fe/Al/Mn depleted solution with the alkali hydroxide precipitant, may involve addition of a CO2(g) precipitant to produce the Mg-depleted solution and the magnesium carbonate precipitate product. The CO2(g) precipitant may for example include, or be made entirely from, the carbon dioxide off gas from the step of precipitating iron and/or aluminum from the loaded leach solution.
In select embodiments, an initial step of magnetically separating material from the comminuted mineral feedstock may be implements, for example so as to enrich the feedstock in select materials.
In select embodiments, the loaded leach solution may be subjected to a resin in leach process so as to selectively remove nickel values from the loaded leach solution, to obtain a purified nickel product.
The products of the process may be further treated for example by washing and/or alkalization of the solid siliceous residue, washing and/or alkalization of the iron and/or aluminum hydroxide or oxide precipitate product.
A hematite seed material may be added to the step of precipitating iron and/or aluminum so as to seed the precipitation of a hematite product. When the iron and/or aluminum hydroxide or oxide precipitate product comprises a hematite seed material, the hematite seed material may be recirculated to the step of precipitating iron and/or aluminum so as to seed the precipitation of a hematite product.
A brine that includes some or all of the Fe/Al/Mn depleted solution may be recirculated to the comminuting step, to provide the comminuted mineral feedstock.
The mineral feedstock may for example be, or include, one or more of a nickel saprolite ore or tailing, an olivine ore or tailing, an asbestos ore or tailing, a mafic mineral, a saprolite material, an ultramafic rock, olivine, wollastonite or combinations thereof.
Processes are provided in which successive steps of hydrometallurgical value extraction are carried out using the products of carbon capture and an electrolytic reactant regeneration process, such as a chloralkali process or an electrolytic salt splitting anion exchange process. The electrolytic reactant regeneration process provides an acid leachant and an alkali hydroxide, with the alkali hydroxide (e.g. NaOH) then available for use either directly as a precipitant in the hydrometallurgical steps, or available for conversion to an alkali metal carbonate (e.g. Na2CO3) or bicarbonate (e.g. NaHCO3) that can in turn be used as the precipitant in the hydrometallurgical steps.
In an alternative embodiment, the alkali hydroxide from the chloralkali process may be used to precipitate a calcium hydroxide product, with the calcium hydroxide product then available for use directly in carbon dioxide gas scrubbing, or for use to accept a carbonate that is provided by a CO2 scrubbing process.
In some embodiments, a crystalliser step may be introduced to precipitate Na2CO3 or Na2CO3 hydrates from a CO2 enriched solution that is being treated with the alkali hydroxide (NaOH) product of the chloralkali process. In such processes, a crystalliser may be used to reduce water content in the hydrates by modulating temperature, pressure and NaOH concentration. The solid Na2CO3 product may then be used as a carbonate precipitant.
By using a carbonate precipitant to precipitate iron and aluminum from the leach solution, at a suitably low pH, the carbonate will decompose to release a concentrated stream of CO2, and the concentrated CO2 stream may in turn be sequestered or fixed.
As illustrated in
Conditions for leaching may include a leaching temperature of from 80° C. to boiling point, to 115° C. or higher. Acid addition during HCl leaching may for example range from 500 to 1000 kg HCl per dry tonne of solid feed, varying with the chemical composition of the feed. Leaching times may for example be for effective residence times of from 1 hour to 8 hours. Leaching may for example be carried out in a single stage or two or more countercurrent stages. In a single stage process, the acid and ore are added together and allowed to react at a leaching temperature to completion. In a multistage leach, fresh ore is contacted with partly reacted solution so as to maximize the use of the acid (low terminal acidity) and in the second or subsequent stage, the partly leached ore (from the first stage) is contacted with high acid to maximize extraction of Mg/Ni/Co/Fe, etc. The multistage process may involve additional solid/liquid separation steps to ensure countercurrent movement of solids and liquids.
The raw materials for the present processes may contain a variety of silicate minerals including magnesium, iron, nickel and cobalt and minor impurity elements. The chemistry of acid leaching, with HCl, may therefore be represented the following reactions:
Mg2SiO4+4HCl=2MgCl2+SiO2+2H2O
Ni2SiO4+4HCl=2NiCl2+SiO2+2H2O
Fe2SiO4+4HCl=2FeCl2+SiO2+2H2O
Other minerals present in source materials such as iron oxides or aluminum oxides may also react with HCl to form additional salts in solution:
FeO(OH)+3HCl=FeCl3+2H2O
AlO(OH)+3HCl=AlCl3+2H2O
Natural mineral source materials are of course not pure compounds, so that the source minerals my contain a variety of elements (eg. Mg, Ni, Co, Fe in one silicate mineral) and may be hydrated or weathered. Geological descriptions of suitable feed materials include: nickel saprolite ores, olivine ores, and asbestos ores and tailings.
The product of HCl leaching is a weakly acidic solution containing various chloride salts. A silica rich residue is recovered as a solid product. This residue may for example be washed to remove salts and excess acid with fresh water, and/or alkalized (alkali conditioning) with a base to adjust pH, and then directed to cement manufacture where the silica may be used as a replacement for other materials (thus lowering the carbon intensity of cement manufacture) and as a strengthener to improve the yield strength of concrete, with the silica acting as a supplementary cementitious material (SCM) in a high performance concrete.
Iron and/or aluminum are precipitated (“Iron and Aluminum Precipitation”) from the loaded leach solution with an alkali hydroxide (NaOH) or alkali metal carbonate or bicarbonate precipitant (Na2CO3 as illustrated in
HCl+NaOH=NaCl+H2O
FeCl3+3NaOH═FeO(OH)+3NaCl+H2O
2FeCl3+6NaOH═Fe2O3(hematite)+6NaCl+3H2O
AlCl3+3NaOH═AlO(OH)+3NaCl+H2O
2AlCl3+6NaOH=Al2O3+6NaCl+3H2O
CrCl3+3NaOH═CrO(OH)+3NaCl+H2O
2CrCl3+6NaOH=Cr2O3+6NaCl+3H2O
The pH adjustment may for example be conducted with stoichiometric amounts of alkali hydroxide. Over-addition of NaOH may result in precipitation of Ni/Co (undesirable) so control of base addition must be maintained. The Fe/Al precipitation temperature may for example be 75° C. to boiling point. Seed (precipitate) may be recycled, for example in the form of hematite, to ensure growth of suitably sized particles, and materials, for enhanced solid/liquid separation. An initial mineral seed, such as hematite, may be used to initiate the process of precipitating a select material, such as hematite. Fe/Al precipitation time may for example be 1 to 8 hours. NaOH may for example be added progressively through precipitation tanks (continuous) so as to enhance precipitation of coarser/separable precipitates. The Fe/Al precipitation product may be separated by S/L separation and washed.
The Fe/Al precipitation residue may for example be treated to form commercial products, such as hematite. For example, drying and partial reduction may be used to form magnetite and a mixed Al/Cr oxide. The magnetite can be separated using magnetic separation and the Al/Cr oxide can be sold as a product for the refractory market.
Nickel and cobalt may be selectively recovered in a variety of ways. In an HCl based leaching process, Ni and Co will be present in solution as NiCl2 and CoCl2 salts, and these salts can be recovered by ion exchange, for example using a Dow M4195 resin to extract Ni and Co in a Na-form resin. The resin can then be stripped with HCl solution to form a strong, purified solution of Ni/Co chloride salts. The resin may then be treated with NaOH solution after acid stripping to return to the resin “loading” step.
In select embodiments, the recovery of Ni/Co is by way of a mixed hydroxide precipitate (MHP). This can be done directly from the solution coming from the iron precipitation step, or can be effected starting with the ion exchange eluant containing nickel and cobalt chloride. In these processes, a solution of sodium hydroxide is added to from the precipitates:
NiCl2+2NaOH═Ni(OH)2+2NaCl
CoCl2+2NaOH═Co(OH)2+2NaCl
Other metals may also precipitate with the Ni/Co in minor amounts. For example Mn, Fe (remaining iron in solution).
The selectivity of Ni/Co MHP precipitation can be enhanced by using two stage MHP precipitation, in which a second stage precipitate is recovered and recycled to the first stage or to the discharge from the main leaching step (where acid is present to redissolve the Ni/Co and other metals from the second stage leach).
The mixed hydroxide precipitate may be recovered by S/L separation and washing. A pressure filter may be used with a “squeeze” cycle to minimize the entrained moisture in the washed Ni/Co MHP cake prior to shipping.
The Ni/Co MHP precipitation may be carried out between 25-90° C. with a terminal pH in the range of 5-8. The addition of base can also be controlled by stoichiometry rather than, or in addition to, pH. The Ni/Co MHP precipitation time may for example be 1-8 hours. Seed recycling may be used to maximize particle size and minimize contamination. The Ni/Co MHP process (as in all steps) may be conducted continuously.
As illustrated in
Most of the iron and aluminum are removed from solution in the first iron removal step. Manganese is generally not removed from solution in either the initial iron control or the Ni/Co MHP precipitation steps. Accordingly, a second stage of iron precipitation may be implemented with increased pH so as to maximize the removal of iron with an oxidant added to oxidize Mn and Fe to facilitate more complete removal and purification of all species. Suitable oxidants include gaseous chlorine or sodium hypochlorite (NaOCl). Example reactions include:
2FeCl2+NaOCl+4NaOH═2FeO(OH)+5NaCl+H2O
MnCl2+NaOCl+2NaOH=MnO2+3NaCl+H2O
AlCl3+3NaOH═AlO(OH)+3NaCl+H2O
Conditions for iron and/or aluminum and/or manganese scrubbing may be designed to maximize precipitation of the impurity elements while minimizing formation of magnesium hydroxide. The oxidant (eg. NaOCl) may be added so as to achieve a suitably high oxidation/reduction potential (ORP) to maximize the oxidative removal of Fe/Mn. Scrubbing temperature may for example be 25° C. to the boiling point. As in other precipitation steps, seed recycle can be used to improve performance. Scrubbing time may for example be 1 to 8 hours.
Alternatively, as illustrated in
Magnesium remaining in solution may be precipitated from the Fe/Al/Mn depleted solution with an alkali hydroxide precipitant (NaOH as illustrated), to produce a Mg-depleted solution and a magnesium hydroxide precipitate product (“Mg Hydroxide Precipitate”):
MgCl2+2NaOH═Mg(OH)2+2NaCl
This may for example be carried out by adding NaOH to MgCl2 solution, or by reversing the order of addition. In either case, the process may be carried out so as to provide a near complete removal of Mg as Mg(OH)2 from solution. This generally requires a near stoichiometric addition of NaOH.
The Mg-depleted solution may then be subjected to further purification, for example in an ion exchange resin separation step, or sent directly to an electrolysis to produce the alkali hydroxide precipitant and the acid leachant (in
As illustrated in
In the foregoing process, the step of scrubbing carbon dioxide from the CO2 containing gas may include a crystallisation step to precipitate Na2CO3 hydrates from the scrubbing solution, the alkali hydroxide precipitant being NaOH. The solid Na2CO3 crystallizer product may then be directed to provide one or more of the alkali metal carbonate or bicarbonate precipitants.
The alkali hydroxide precipitant may accordingly be NaOH (
MgCl2+Na2CO3=MgCO3+2NaCl
In select embodiments, essentially the full amount of NaOH produced by the chloralkali process is directed to the DAC system to produce Na2CO3 from CO2 captured directly from the atmosphere. In such a process, sufficient Na2CO3 is produced to provide the alkali metal precipitant for all aspects of the process, including recovery of MgCO3. In this way, sorbent regeneration for DAC, i.e. NaOH, is combined with long term mineralisation of the CO2. MgCO3 mineralisation thereby creates carbon negative products in the form of carbonates, that may for example be used as filler or construction aggregate.
MgCl2+2NaOH+CO2(g)=MgCO3+2NaCl+H2O
As illustrated in
Reactions in various stages of the present process may be represented as follows:
In alternative embodiments, NaHCO3 may take the place of Na2CO3 in reactions in various stages of the present process.
Iron and/or aluminum are precipitated (“Iron and Aluminum Precipitation”) from the loaded leach solution with either an alkali hydroxide precipitant (
Nickel and/or cobalt are precipitated from the Fe/Al depleted solution with the alkali hydroxide precipitant (e.g. NaOH,
Iron and/or aluminum and/or manganese may be scrubbed from the Ni/Co depleted solution with the alkali hydroxide precipitant (
As illustrated, brine comprising the Fe/Al/Mn depleted solution may be recycled to the comminuting step to provide the comminuted mineral feedstock.
Magnesium may be precipitated from the Fe/Al/Mn depleted solution with the alkali hydroxide precipitant (NaOH as illustrated in
Carbon dioxide may be scrubbed from a CO2 containing gas (“Air” as illustrated) by treating the CO2 containing gas with a scrubbing solution comprising the alkali hydroxide precipitant (NaOH as illustrated), to produce one or more of the first, second, third and fourth alkali metal carbonate or bicarbonate precipitants (Na2CO3 as illustrated), for use respectively in i) iron and aluminum precipitation, ii) Ni/Co precipitation, iii) iron and aluminum precipitation with manganese removal, and iv) Mg precipitation.
In the foregoing process, the step of scrubbing carbon dioxide from the CO2 containing gas may include a crystallisation step to precipitate Na2CO3 hydrates from the scrubbing solution, the alkali hydroxide precipitant being NaOH. The solid Na2CO3 crystalizer product may then be directed to provide one or more of the alkali metal carbonate or bicarbonate precipitants.
The process acid leachant as illustrated is H2SO4. As such, processes are provided that use of a sulfate based system for treatment of magnesium silicates. In select embodiments, (
Steps in the sulfate process may be characterized by reactions therein, as follows:
Acid leaching (simplified);
In alternative embodiments, processes make use of NaOH, NaHCO2 or Na2CO3 precipitants, with some alternative chemistries shown below:
The present processes may be integrated with other carbon sequestration processes, such as ocean alkalinity enhancement. This present processes for the production of synthetic brucite and calcium hydroxide accordingly address environmental risks of direct ocean alkalinity enhancement with untreated mafic rocks. The present processes also create a less carbon intensive source of magnesium and calcium hydroxides to be used as feedstock in carbon capture and storage, including direct air capture technologies. The use of the brucite or calcium hydroxide products of the present processes in a direct air capture (DAC) process may be carried out so as to eliminate calcining and slacking steps that are otherwise required in these processes. The present processes provide for the use of basaltic sands in less carbon intensive industrial purposes, by producing low carbon sources of nickel and iron hydroxides as well as amorphous silicate (SiO2).
Although various embodiments of the invention are disclosed herein, many adaptations and modifications may be made within the scope of the invention in accordance with the common general knowledge of those skilled in this art. Such modifications include the substitution of known equivalents for any aspect of the invention in order to achieve the same result in substantially the same way. Terms such as “exemplary” or “exemplified” are used herein to mean “serving as an example, instance, or illustration.” Any implementation described herein as “exemplary” or “exemplified” is accordingly not to be construed as necessarily preferred or advantageous over other implementations, all such implementations being independent embodiments. Unless otherwise stated, numeric ranges are inclusive of the numbers defining the range, and numbers are necessarily approximations to the given decimal. The word “comprising” is used herein as an open-ended term, substantially equivalent to the phrase “including, but not limited to”, and the word “comprises” has a corresponding meaning. As used herein, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a thing” includes more than one such thing. Citation of references herein is not an admission that such references are prior art to the present invention. Any priority document(s) and all publications, including but not limited to patents and patent applications, cited in this specification, and all documents cited in such documents and publications, are hereby incorporated herein by reference as if each individual publication were specifically and individually indicated to be incorporated by reference herein and as though fully set forth herein. The invention includes all embodiments and variations substantially as hereinbefore described and with reference to the examples and drawings.
Filing Document | Filing Date | Country | Kind |
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PCT/IB2021/061024 | 11/26/2021 | WO |
Number | Date | Country | |
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63118677 | Nov 2020 | US |