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EP-4133219-B1 - SYSTEM AND PROCESS FOR DIRECT LITHIUM EXTRACTION AND PRODUCTION OF LOW CARBON INTENSITY LITHIUM CHEMICALS FROM GEOTHERMAL BRINES

EP4133219B1EP 4133219 B1EP4133219 B1EP 4133219B1EP-4133219-B1

Inventors

  • WEDIN, Francis
  • GRANT, ALEXANDER

Dates

Publication Date
20260513
Application Date
20200408

Claims (15)

  1. System for production of battery-quality lithium hydroxide monohydrate, lithium carbonate or both from a geothermal brine, said system comprising: a binary cycle geothermal plant (200); a direct lithium extraction circuit (400) positioned downstream of said binary cycle geothermal plant; said direct lithium extraction circuit configured to selectively recover lithium or lithium chloride from said geothermal brine to produce a lithium concentrate stream; said direct lithium extraction circuit powered by electricity generated from said binary cycle geothermal plant with no carbon-based fuel consumption; a lithium chloride concentration and purification circuit (600) positioned downstream of said direct lithium extraction circuit; said lithium chloride concentration and purification circuit configured to remove water from said lithium concentrate stream and purify said lithium concentrate stream simultaneously to form an upgraded lithium chloride concentrate stream; said lithium chloride concentration and purification circuit powered by electricity and/or steam generated from said binary cycle geothermal plant with no carbon-based fuel consumption; and a lithium battery chemical processing circuit (800) positioned downstream of said lithium chloride concentration and purification circuit; said lithium battery chemical processing circuit configured to produce battery-quality lithium hydroxide monohydrate, lithium carbonate or both from said upgraded lithium chloride concentrate stream; said lithium battery chemical processing circuit powered by electricity and/or steam generated from said binary cycle geothermal plant with no carbon-based fuel consumption.
  2. System as claimed in Claim 1 further comprising a chemical inhibitor circuit (100), wherein the binary cycle geothermal plant (200) is positioned downstream from said chemical inhibitor circuit.
  3. System as claimed in any one of the preceding Claims further comprising a brine pre-conditioning circuit (300) that is configured to remove deleterious components from said geothermal brine as oxides, hydroxides and/or oxyhydroxides; said brine pre-conditioning circuit being positioned intermediate of said binary cycle geothermal plant (200) and said direct lithium extraction circuit (400), wherein said brine pre-conditioning circuit is preferably configured to oxidize said geothermal brine and/or modify a pH of said geothermal brine to selectively precipitate said deleterious components from said geothermal brine.
  4. System as claimed in any one of the preceding Claims wherein said direct lithium extraction circuit (400) is further configured to selectively recover lithium or lithium chloride from said geothermal brine using adsorption, ion exchange, ionic liquids, and/or solvent extraction to selectively remove lithium from said geothermal brine to form said lithium chloride concentrate stream.
  5. System as claimed in Claim 4 wherein said adsorption uses a manufactured resin-based alumina imbibed adsorbent, a lithium alumina intercalates adsorbent, an alumina imbibed ion exchange resin, or an alumina-based adsorbent, wherein said ion exchange uses a metal oxide ion exchange material, said metal oxide ion exchange material preferably comprising Li a Ti b Mn c Fe d Sb e Cu f V g O h , wherein [a-f] are numbers between 0 and 1 and h is a number between 1 and 10, or Li a Ti b Mn c Fe d Sb e Cu f V g O h , wherein [a-f] are numbers between 0 and 1 and h is a number between 1 and 10, and/or wherein said solvent extraction uses perfluoroethers (PFE), hydrofluoroethers (HFE), perfluoropolyethers (PFPE), hydrofluoropolyethers (HFPE), amines perfluorinated (PFA), preferably ternary (PFTA), hydrofluorinated amines (HFA), preference ternary (HFTA), perfluorinated polyamines (PFPA), polyamines hydrofluorées (HFPA), perfluorothioethers (PFTE), hydrofluorothioethers (HFTE), perfluoropolythioethers (PFPTE), hydrofluoropolythioethers (HFPTEs), hydrofluorothioethersamines (HFTEA), perfluoroazacyclohexanes, perfluoroetheramines, hydrofluoroetheramines (HFEA), perfluorothioetheramines, perfluoroethylenes alcohols, perfluorocyclohexanes, hydrofluorocyclohexanes, perfluorodecalins, perfluorocycloethers, hydrofluorocycloethers, perfluorocyclothioethers, hydrofluorocyclothioethers, liquids ionic hydrophobic which can be based on bis (trifluoromethylsulfonyl) imide (TF2N-) ions.
  6. System as claimed in any one of the preceding Claims wherein said lithium battery chemical processing circuit (800) further comprises an electrolysis circuit (700) configured to form a lithium hydroxide concentrate stream from said upgraded lithium chloride concentrate stream of said lithium chloride concentration and purification circuit (600).
  7. System as claimed in Claim 6 wherein said electrolysis circuit (700) comprises an electrochemical or electrodialysis cell having an anode chamber with an anode electrode and a cathode chamber with a cathode electrode, wherein said electrochemical or electrodialysis cell preferably comprises a single compartment or multiple compartment electrochemical or electrolysis cell, and wherein said electrolysis circuit is preferably powered by electricity and heat generated from said binary cycle geothermal plant (200) with no carbon-based fuel input.
  8. System as claimed in any one of Claims 6 and 7 further comprising a lithium hydroxide processing circuit (1100) positioned downstream of said electrolysis circuit (700), said lithium hydroxide processing circuit configured to form lithium hydroxide monohydrate from said lithium hydroxide concentrate stream of said electrolysis circuit, wherein said lithium hydroxide processing circuit is preferably configured to produce battery-quality lithium hydroxide monohydrate from said lithium hydroxide concentrate stream, and wherein said lithium hydroxide processing circuit is preferably powered by electricity and heat generated from said binary cycle geothermal plant (200) with no carbon-based fuel input.
  9. System as claimed in any one of Claims 6 to 8 wherein said lithium battery chemical processing circuit (800) further comprises a CO 2 carbonation circuit (1000) positioned downstream of said electrolysis circuit (700), said CO 2 carbonation circuit configured to form lithium carbonate from said lithium hydroxide concentrate stream of said electrolysis circuit, and wherein said CO 2 carbonation circuit is preferably powered by electricity and heat generated from said binary cycle geothermal plant (200) with no carbon-based fuel input.
  10. System as claimed in any one of the preceding Claims wherein said lithium battery chemical processing circuit (800) further comprises a Na 2 CO 3 carbonation circuit (900) positioned downstream of said lithium chloride concentration and purification circuit (600), said Na 2 CO 3 carbonation circuit configured to form a lithium carbonate concentrate stream from said lithium chloride concentrate stream of said lithium chloride concentration and purification circuit, and wherein said Na 2 CO 3 carbonation circuit is preferably powered by electricity and heat generated from said binary cycle geothermal plant (200) with no carbon-based fuel input.
  11. System as claimed in Claim 10 further comprising a lithium carbonate processing circuit (1300) positioned downstream of said Na 2 CO 3 carbonation circuit (900), said lithium carbonate processing circuit configured to produce battery-quality lithium carbonate from said lithium carbonate concentrate stream.
  12. System as claimed in any one of Claims 10 and 11 wherein said Na 2 CO 3 carbonation circuit (900) further comprises a Na 2 CO 3 carbonation and liming circuit (1200) positioned downstream of said lithium chloride concentration and purification circuit (600), said Na 2 CO 3 carbonation and liming circuit configured to form said lithium carbonate concentrate stream from said upgraded lithium chloride concentrate stream of said lithium chloride concentration and purification circuit, wherein said Na 2 CO 3 carbonation and liming circuit is preferably powered by electricity and heat generated from said binary cycle geothermal plant (200) with no carbon-based fuel input.
  13. System as claimed in Claim 12 further comprising a lithium hydroxide processing circuit (1100) positioned downstream of said Na 2 CO 3 carbonation and liming circuit (1200), said lithium hydroxide processing circuit configured to form lithium hydroxide monohydrate from said lithium carbonate concentrate stream of said Na 2 CO 3 carbonation and liming circuit, wherein said lithium hydroxide processing circuit is preferably configured to produce battery-quality lithium hydroxide monohydrate from said lithium hydroxide concentrate, and wherein said lithium hydroxide processing circuit is preferably powered by electricity and heat generated from said binary cycle geothermal plant (200) with no carbon-based fuel input.
  14. System as claimed in any one of the preceding Claims further comprising a brine post-conditioning circuit (500) positioned downstream of said binary cycle geothermal plant (200), said direct lithium extraction circuit (400), said lithium chloride concentration and purification circuit (600), and said lithium battery chemical processing circuit (800), wherein said brine post-conditioning circuit (500) is preferably configured to combine wastes produced by said system prior to reinjection of said geothermal brine.
  15. Process for production of lithium hydroxide monohydrate, lithium carbonate or both from a geothermal brine using the system of any one of the preceding Claims.

Description

This invention relates generally to a system and process for direct lithium extraction (DLE) from geothermal brines, and more particularly to the sequential combination of a binary cycle geothermal plant, a DLE circuit, a lithium chloride concentration and purification circuit, and a lithium battery chemical processing circuit for the production of battery-quality lithium hydroxide monohydrate, lithium carbonate or both from geothermal brines. Lithium can be found in different kinds of natural resources including brines, sedimentary materials, and pegmatitic ores. Brines are aqueous resources which typically contain lithium, sodium, potassium, magnesium, and calcium chlorides in solution with other impurities both cationic and anionic. Lithium can be extracted from brines using two different classes of processing techniques: evaporative processes and DLE processes. Evaporative processes involve pumping brine to the surface to evaporate the water from the brine and crystallize impurity salts in large ponds before lithium is converted into a chemical product at the end of the system. DLE is a process which removes the lithium selectively from the brine while leaving the majority of the water and impurities for re-injection. There are three major classes of DLE: adsorption, ion exchange, and solvent extraction. Evaporative processes have been mainly deployed to process high lithium concentration, high purity brines in South America where evaporation rates are high. Many other brines exist around the world with lower lithium concentrations and higher impurity concentrations which cannot be processed economically using evaporative processes, but which could be developed in order to supply demand for lithium for lithium ion batteries in electric vehicles. Some of these brines include low grade South American salar brines, oilfield brines, and geothermal brines. Oilfield and geothermal brines exist in confined aquifers deeper than South American salar brine aquifers, typically greater than about 300 meters deep. This means that they are typically anoxic with oxidation reduction potential (ORP) of less than about 200 mV. Geothermal brines are a class of these brines that are heated to high temperatures and pressures by the Earth's interior, allowing for heat and electricity production from the energy in the brine. Some of these brines contain lithium and it may be economic to extract the lithium from these brines using DLE. However, brine chemistry may need to be modified before the brine enters DLE so that the DLE technology is not impaired by some constituents of the brine, and after the brine is processed in DLE so that it can be re-injected into the aquifer without scaling issues in the well or aquifer itself. This is especially challenging to do for binary cycle geothermal plants which typically are less permissive of changes in physical properties (pH, ORP, composition, temperature, pressure) of the brine before re-injection compared to flash steam geothermal plants. US 2019/0248667 A1 relates to a system and process for recovery of lithium from a geothermal brine. The system and process are configured for the sequential recovery of zinc, manganese, and lithium from a Salton Sea Known Geothermal Resource Area brine. The system and process includes: an impurity removal circuit; a continuous counter-current ion exchange circuit for selectively recovering lithium chloride from the brine flow and concentrating it; and a lithium chloride conversion circuit for converting lithium chloride to lithium carbonate or lithium hydroxide product. RU 2650447 C2 relates to geothermal power engineering. In particular, a method is disclosed that can be used to generate electricity by utilizing thermal and associated energy from geothermal resources and extracting dissolved chemical components from them. US 2014/0076734 A1 relates to a method and electrochemical device for low environmental impact lithium recovery from aqueous solutions. The method comprises the use of an electrochemical reactor with electrodes which are highly selective for lithium, where lithium ions are inserted in the crystal structure of manganese oxide in the cathode and extracted from the crystal structure of manganese oxide in the anode. It is therefore desirable to provide an improved system and process for DLE from geothermal brines, which produces energy using binary cycle geothermal plants. It is further desirable to provide a sequential combination of a binary cycle geothermal plant, a DLE circuit, a lithium chloride concentration and purification circuit, and a lithium battery chemical processing circuit for the production of battery-quality lithium hydroxide monohydrate, lithium carbonate or both from geothermal brines. It is still further desirable to provide a system and process for direct lithium extraction from geothermal brines where the DLE circuit utilizes adsorption, ion exchange, ionic liquids, and/or solvent extraction for the productio