WO2017096495A1 - Système et procédé séquentiel électrolytique pour augmenter la concentration de lithium présent dans des saumures - Google Patents

Système et procédé séquentiel électrolytique pour augmenter la concentration de lithium présent dans des saumures Download PDF

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Publication number
WO2017096495A1
WO2017096495A1 PCT/CL2016/050068 CL2016050068W WO2017096495A1 WO 2017096495 A1 WO2017096495 A1 WO 2017096495A1 CL 2016050068 W CL2016050068 W CL 2016050068W WO 2017096495 A1 WO2017096495 A1 WO 2017096495A1
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Prior art keywords
pools
solution
dilute
stage
concentrate
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PCT/CL2016/050068
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English (en)
Spanish (es)
Inventor
Jaime Roberto SIMPSON ALVAREZ
Victor ARAYA BORQUEZ
Marco CORTES PANTOJA
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Propipe Maquinarias Ltda.
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Publication of WO2017096495A1 publication Critical patent/WO2017096495A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium

Definitions

  • the invention discloses a sequential system and process to increase the concentration of lithium present in natural brines that replaces the evaporation / precipitation pool stages currently used.
  • the system and process allows to avoid the loss of water by evaporation because once the natural brine is processed, it considers recovering the water using a fraction as industrial water and incorporating the rest of the water evacuated to a Salar.
  • the system allows a lithium concentration process to be carried out more quickly, effectively and efficiently compared to existing systems and procedures.
  • the sequential system and process dispenses with stages of transfer and deposition of brines in the natural state in large pools or evaporation pools that occupy large areas of land, where in these cases, the loss of water is considerably high since it evaporates without being reused or reincorporated to natural salt.
  • the system and process of the invention for not using said evaporation stages allows recovering a large part of the water naturally contained in the brine solution and incorporating it back into the soil from which it was extracted, so that the environmental impact is significantly less.
  • the sequential system and process comprises one or more replicable phases (FR) comprising stages composed of a set of electrolytic devices, followed by a forced precipitation stage and a solid-liquid separation stage of salts that can also be reinstated into the salt in partial or total form.
  • FR replicable phases
  • the sequential system and process of the invention comprises at least one replicable phase (FR), wherein said replicable phase is a sequential set of mechanisms and activities comprising three sequential stages (ES); wherein said stages comprise at least one concentration stage via electro dialysis as Stage I, followed by at least one precipitation stage such as Stage II and then by at least one solid-liquid separation stage such as Stage III.
  • FR replicable phase
  • ES sequential set of mechanisms and activities comprising three sequential stages (ES)
  • said stages comprise at least one concentration stage via electro dialysis as Stage I, followed by at least one precipitation stage such as Stage II and then by at least one solid-liquid separation stage such as Stage III.
  • the main lithium deposits that are in operation are classified as pegmatites or as paleo brines-lacustrine salt deposits, where the vast majority of prospecting factors only verify the presence of abnormal lithium concentrations, without economic performance in the market current.
  • lithium is found in the salt deposit areas of the High Cordillera and, to a lesser extent, in the nitrate fields and associated salt deposits.
  • the sequential system and process of the invention dispenses with stages of transfer and deposition of brines in the natural state in large pools or evaporation pools, where the loss of water is considerably high since it evaporates without being reused or re-incorporated into natural salt flats.
  • the system and process of the invention for not using said evaporation stages allows to reduce the times considerably and allows to recover a large part of the water naturally contained in the brine solution and incorporate it again to the soil from which it was extracted, with very low environmental impact.
  • lithium can be obtained from a double lithium aluminum silicate deposit (L ⁇ AIS ⁇ 2O6 or L ⁇ 2O-Al2O3-4SiO2), where the percentage contents are
  • the first stage is the concentration of the solutions, by means of solar evaporation pools:
  • the initial contents of the brines of the Salar de Atacama are around 0.17% of Li, reaching concentration up to values of the order of 4.3% to 5 , 8%.
  • the system of the invention is oriented in this first stage, where the incorporated process allows to dispense said pools or solar evaporation pools.
  • the second stage is the treatment of the concentrated brine in a chemical plant:
  • LI2CO3 99.5% purity
  • the concentrated brines are purified and crystallized, then a carbonation process is carried out, a subsequent precipitation and finally The drying of the crystals.
  • the evaporation rate of water naturally contained in the brine is of the order of 10 liters per day per square meter of pool area.
  • Lithium carbonate is the most important base compound among Li salts, its demand represents 60% of Li products. Its importance mainly lies in the fact that it is easy to purify and serves for the conversion of other inorganic and organic lithium salts such as LiCI, LiBr and ÜOH-H2O and other compounds.
  • the process currently used for the extraction of salt brines is carried out by means of pumps that suck the brine about thirty meters deep, discharging them through pipes to a system of solar evaporation pools, where Li is concentrated from 0, 17% to 4.3%.
  • the construction of the pools inside the salt flat is done by breaking the salt crust and leaving a flat surface on which a layer of clay lies. Both the dikes and the bottom of the first evaporation pools are coated with a resistant plastic 0.5 mm thick.
  • the protection of polyurethane is achieved with a layer of NaCI salts approximately thirty centimeters thick.
  • halite NaCI
  • silvinite NaCI + KCI
  • carnalite KCI x MgC x 6H2O
  • bischophyte MgC x 6H2O
  • LiCI-MgC x 7H2O in order to recover the lithium it contains, it is then repulped and washed with a solution saturated in magnesium chloride, but not saturated in lithium chloride.
  • the concentrated brine reaches 5.8% of Lithium, 20% of Magnesium and 0.7% of Boron expressed as boric acid (H3BO3), being ready to be transported to a chemical plant.
  • the chemical treatment in the Plant consists in eliminating the remaining magnesium, in two stages of purification, such as carbonate and magnesium hydroxide, respectively.
  • the concentrated brine is diluted to a content of 0.6% of Lithium, with the mother water from the final stage of precipitation of lithium carbonate.
  • This product is obtained by hot reaction (about 85 Q C), between the purified brine free of magnesium (1ppm) and a solution of Na2CO3, precipitating the L2CO3.
  • the final product is dried and marketed in crystals (70%), or it is compacted to be sold in the form of granules (30%).
  • the purity of the product is close to 99.5% of L2CO3.
  • its boron content 400-600 ppm
  • Application AR-1996033648 refers to a process for extracting boron from natural brines using solvent extraction and, for its part, application CL-19840000615, which refers to a process for regeneration of lithium aluminate using aqueous solution washing, notes that in the state of the art processes that range from extraction from natural brines to obtaining a final product such as lithium aluminate or carbonate predominate
  • the sequential system and process of the invention differs from what exists because it considers intervening and replacing a part of the processes currently used, to avoid the use of evaporation pools or pools and obtain a higher concentration of lithium from natural brines.
  • This system allows to considerably reduce the environmental impact caused at present because it does not use the stages of pools for evaporation concentration.
  • the system of the invention returns part of the water contained in the natural brine to the soil from which it was extracted, reduces the times and reduces the affected land surfaces, so it considerably reduces the pollution that currently impacts the environment and affects the flora and fauna of the intervened areas or regions.
  • Fig. 1 shows a scheme of the system and process that comprises a phase with its respective stages.
  • Fig. 2 shows in side section a device as a minimum unit of electrolytic cell for the system and its process
  • Fig. 3 shows a scheme of the process system comprising four phases and their respective stages.
  • Fig. 4 shows a schematic example of a complete phase of the system and process. Detailed description of the invention:
  • the present invention is a sequential system and process for increasing the concentration of lithium present in natural brines and replacing stages of evaporation / precipitation pools and allowing to avoid the loss of water by evaporation, because once the natural brine is processed, two aqueous flows are generated: one of them results with characteristics of industrial water with low lithium contents, called DILUTE, and the other resulting flow is an aqueous solution of high concentration of lithium, called CONCENTRATE. A fraction of the DILUID can be reused as process water and the rest is reincorporated into a salt area.
  • the CONCENTRATE is the final product of the system and process disclosed, and in its entirety continues its treatment for the production of lithium chloride or lithium carbonate or metallic lithium in plants designed specifically for each of the aforementioned products.
  • salts are generated by precipitation that can be arranged in the same salt or sold, as is done in the current processes.
  • the system allows the lithium concentration process to be carried out more quickly, efficiently and efficiently compared to existing systems and procedures and allows the recovery of a large part of the water naturally contained in the brine solution and incorporating it back into the soil from which it was extracted, with a considerably lower environmental impact.
  • the System and sequential process of the invention comprises at least three sequentially linked mechanisms that make up a replicable phase (FR), where a replicable phase comprises at least three sequential stages (ES); a concentration stage via electro dialysis such as Stage I (EI), followed by a precipitation stage such as Stage II (E-ll) and followed by a solid-liquid separation stage such as Stage III (E-lll).
  • the System and sequential process of the invention comprises one or more replicable sequential PHASES, which are repeated successively as many times as necessary, to achieve the concentration and quality of the lithium-rich solution required.
  • Each PHASE as a set of devices and activities within the process system, comprises at least the three stages mentioned.
  • the concentration stage via electro dialysis comprises a conveniently arranged mechanism of electro dialysis cells (MOED) (4), whose devices can be electro dialysis cells (ED), reverse electro dialysis cells (EDR) , electro-dialysis with ion exchange (EDI), Electro-Electrodialysis or Reactive Electrodialysis (EED or E2D), which may or may not be assisted with magnetic fields or ultrasound, where it is understood as a conveniently arranged mechanism (MOED) (4) arrangement of one or more electro dialysis cells grouped and connected for example in series or in parallel, so as to form an internal circuit for the incoming solution or fluid.
  • MOED conveniently arranged mechanism
  • Electro dialysis cells comprise a plurality of ion exchange membranes, which are polymers that in their interior pores functional groups with a specific electrical charge have been fixed on their walls, so that if these fixed functional groups have a positive electrical charge they will allow the passage of anions through said membranes. On the contrary, if the fixed charges are negative, they will allow cations to pass through said membranes.
  • the former are called anionic ion exchange membranes (MUTA) and the latter are referred to as cationic ion exchange membranes (MIITC).
  • Fig. 1 shows in schematic the system and process comprising a replicable sequential phase (1), with its three respective stages, where said replicable sequential phase begins with the entry of the solution from a brine source (2) to a stage I (E-I), wherein said stage comprises a mechanism that is formed by an ordered mechanism of one or more electrolytic or electro-dialysis cells (4), then the solution is conducted to a stage II (E-ll ) comprising a precipitation mechanism (17) and subsequently the solution is conducted to a stage III comprising a solid / liquid separation mechanism (21).
  • E-I stage II
  • the solution is conducted to a stage III comprising a solid / liquid separation mechanism (21).
  • the solution can enter a new phase (23) that includes, like the first phase, the three stages mentioned.
  • Figure 1 also shows the recirculation and return ducts of the solution.
  • Figure 1 shows a phase (1) that begins with the conduction of a brine flow (3) from a brine source (2) to stage I (EI) comprising said ordered mechanism of electro-dialysis cells (4 ), where through a clean water flow (6) conducts clean water from a source of clean water (5) to said mechanism (4).
  • EI stage I
  • diluted fluid is conducted through a dilute flow (7) to a dilute storage tank (8) where through a dilute recirculation flow (9), said dilute is leads to a brine recovery zone (10) with low lithium content.
  • a flow of concentrate (11) exiting the ordered mechanism of electro-dialysis cells (4) of this stage I (EI) is conducted towards a produced concentrated flow distribution valve (12), in which said valve distributes a concentrate recirculation flow (13) back to the ordered mechanism of electro-dialysis cells (4) and distributes an outgoing flow of concentrate produced (14) from the first stage I (EI).
  • the outgoing flow of concentrate produced (14) from the first stage I (EI) enters stage II (E-ll), in which said stage comprises a precipitation mechanism (17) where from a reagent supply source and Precipitation inputs (15) a flow of precipitation reagents (16) is conducted entering this stage II (E-ll).
  • stage III E-
  • stage III E-lll
  • a flow of precipitated salts (24) comes out corresponding to a solution purified and concentrated in lithium, where said flow (24) enters a storage tank for precipitated salts (25)
  • a stream of purified solution (22) leaving this stage III is led to a new phase (23) where said flow enters stage I (EI) of the next phase, by a flow of recirculant (26).
  • Fig. 2 shows a sectional diagram of the minimum unit of a device corresponding to an electro dialysis cell (ED), which is connected to a positive pole (29) and a negative pole (30 ); the inner channels or compartments of said cell are separated by a MIITC (31) and a MUTA (32).
  • an electrode wash channel (26) is incorporated where an electrode wash solution circulates.
  • the wash channel (26) is separated from a concentrate channel (27), by a MIITC (31).
  • the opposite wall of the Concentrate channel (27) corresponds to a MUTA (32) that separates physically the concentrate channel of a Dilute channel (28).
  • the opposite wall of the Dilute channel (28) is a MIITC (31) that physically separates the Dilute channel (28) from the next concentrate channel (27).
  • the opposite side of said concentrate channel (27) consists of a wall formed by a MUTA (32), adjacent to the washing channel of the sector that is negatively polarized.
  • the concentrate channel assembly (27) - Dilute channel (28) can be repeated many times inside the electrolyte device, which will always have an electrode wash channel (26) in the positively polarized electrode and another wash channel electrode (26) in which it is negatively polarized.
  • the Electrode Wash solution (26) may be an acidic aqueous solution, an alkaline aqueous solution or fresh solution identical to that used in the dilution channels; The choice depends on technical and economic analysis.
  • the ions contained in the aqueous solutions (27) and (28) are arranged according to the electric field, resulting in the anions approaching the positively polarized electrode and the Cations approach the polarized sector negatively.
  • the wall closest to the positive electrode is a MUTA (32), an area where there is a high concentration of anions that will pass through the MUTA ( 32), leaving the dilute channel (28) and integrating it into the solution contained in the concentrate channel (27).
  • MUTA 32
  • MIITC MIITC
  • the zone of high concentration of anions is flanked by a MIITC (31) that prevents the passage through it and the opposite wall, of high concentration of cations is flanked by a MUTA (32 ) that prevents the passage of cations through it.
  • MIITC MIITC
  • MUTA MUTA
  • An orderly arrangement of electrodialysis cell devices will allow to obtain a Diluted solution (28) of low concentration of ionic species with respect to the initial solution and a concentrated solution (27) in ionic species in relation to the initial solution.
  • the efficiency in ionic separation depends largely on the exposed area of the MUTA (32) and MIITC (31) membranes and the electric field imposed between the electrodes.
  • the dilute (28) and concentrate (27) channels can be fed in series or in parallel, but, the mass transferred depends on the transfer rate of the chemical system (moles / sxm 2 ), of the Membrane and electric field area.
  • the cell voltages required for ion transfer from natural lithium brines depend on the amount of dilute (28) and concentrate (27) channels that contain the ED cells, depending on the ionic charge of the system and the rates Mole transfer Li / sxm 2 .
  • ED cells contain many dilute (28) and concentrate (27) channels, usually on the order of 250, however, cells with more channels could be used; the limit is imposed by the electrical supply that is composed of a transfo-rectifier or a transformed-rectified system that supplies regulated direct current with a potentiometer.
  • the electrical connections for the ED cells can be in series, parallel or series-parallel, and a rectifier can feed the entire set of cells, a group of cells or even, each cell can be considered to have its own rectifier.
  • the concentrate feed can be considered
  • a group of ED cells must be properly sorted, forming a solution circuit that optimizes resources and achieves production and quality objectives, and can be hydraulically connected to each other in series, in parallel or in circuits that mix systems in series and parallel. .
  • STAGE II (E-ll) comprises at least one chemical precipitation mechanism that receives all the concentrated solutions produced in the concentration system or systems corresponding to STAGE I (EI), whose concentrations are very close to the saturation concentration of some of the impurities contained in the concentrate.
  • STAGE II can be formed by an accelerated evaporation with thermal sources, adding pH / potential modifiers in a stirred, static pond or in sedimentation pools. Precipitating reagents must be carefully determined for each chemical system in which they will be applied and which could be soda ash and caustic soda as is the case in most cases where solutions from natural brines are treated.
  • STAGE II produces a pulp, which corresponds to a mixture between solids (crystals or amorphous precipitates) produced by precipitation and the aqueous solution after precipitation. The pulp is the feeding of STAGE III.
  • STAGE III comprises a solid / liquid separation mechanism that may be composed of a Thickening-Filtration assembly, only filtration or only pools of sedimentation.
  • the thickening can include any equipment that allows to obtain a liquid on swimming pool with very low presence of solids (less than 10 ppm) and a pulp with a percentage of solids between 55% and 60%; Thickening can operate with flocculants, but the type, dosage and concentration of flocculant required must be experimentally defined.
  • the solid / liquid separation mechanism as stage III (E-lll) incorporates any filtration system that includes disk filters, ceramic filters, drum filters, band filters, tubular filters, plate filters, hyperbaric filters; may or may not include washing stages.
  • STAGE III can also operate with a settling pool system, in which the precipitates are stored in one of them, while the excess overflows a wall that allows a clear solution to accumulate in an adjacent pool; In this case, at least two sedimentation pools are recommended to ensure the operational continuity of the Process.
  • the Fl G.3 presents an example of a flow chart of the system and process that consists of four replicable sequential phases, to treat natural brines extracted from a Salar with high lithium contents, in this case it is shown how the process starts with the supply of natural brine (SN) to STAGE lA, in which said stage consists of a conveniently arranged system of electro-dialysis cells (SOED) that normally operate at room temperature, but could operate at a temperature higher than the ambient incorporating heating systems or heat exchangers prior to entering the STAGE lA.
  • SOED electro-dialysis cells
  • the (SOED) of STAGE lA additionally considers the feed of a concentrated solution recirculation 1 (RC1) that corresponds to a fraction of the Concentrated solution 1 (C1) produced in STAGE lA and is also fed with a Recirculation solution of Industrial Water 1 (RA11) that corresponds to a fraction of the dilute generated by the ordered system of electro dialysis cells (D1) and by the recirculation of industrial water 2 (RAI2) that corresponds to a fraction of the dilute (D2) generated in Stage lB.
  • RC1 concentrated solution recirculation 1
  • RA11 Recirculation solution of Industrial Water 1
  • D1 ordered system of electro dialysis cells
  • RAI2 recirculation of industrial water 2
  • RA11 and (RAI2) can be used as part of the anolyte and catholyte wash solution required in electro dialysis cells or can be mixed with natural brine (SN) to feed the (SOED) of STAGE lA or You can prevent entry to STAGE lA.
  • the solution (RC1) is mixed with a fraction of (SN) and constitutes the solution that will feed the Concentrate channels of the electro-dialysis cells arranged in (SOED) of STAGE lA.
  • the remaining fraction of (SN) which can be mixed with (RAM) and (RAI2), constitutes the supply of the Dilute channels of the electro-dialysis cells that make up the (SOED) of STAGE lA.
  • the products of STAGE 1A correspond to a concentrated solution (C1) and the diluted solution (D1); a fraction of the concentrated solution (C1) is recirculated to the feed of the concentrate channels, called concentrate recirculation 1 (RC1) and the remaining fraction of (C1) is conducted as feed (AP1) to a precipitation stage, called STAGE ll-A.
  • C1 concentrated solution
  • D1 diluted solution
  • RC1 concentrate recirculation 1
  • AP1 a precipitation stage
  • STAGE ll-A the solution (AP1), which feeds the precipitation system, has been concentrated to a concentration very close to saturation, therefore in this STAGE ll-A, composed of a precipitation system, It can force accelerated evaporation with thermal sources, adding pH / potential modifiers in a stirred, static pond or in sedimentation pools. Precipitating reagents must be carefully determined for each chemical system in which they will be applied and which could be soda ash and caustic soda as in most cases.
  • the product resulting from STAGE ll-A is a pulp, mixture of precipitated particles and aqueous solution (PP1), it must be subjected to a solid-liquid separation system (STAGE II lA) that allows obtaining a concentrated solution of the species of interest (CP1), but, with less impurity than the solution (AP1) and, obtaining particles and crystals of precipitated salts (P1) which, depending on their chemical composition, can be marketed or re-integrated into the Salar in areas discussed above.
  • STAGE II lA solid-liquid separation system
  • the system of STAGE II may be composed of a Thickening-Filtration set, only filtration or only settling pools.
  • the thickening can include any equipment that allows to obtain a liquid on swimming pool with very low presence of solids (less than 10 ppm) and a pulp with a percentage of solids between 55% and 60%; Thickening can operate with flocculants, but the type, dosage and concentration of flocculant required must be experimentally defined.
  • Filtration can contemplate any filtration system that includes disk filters, ceramic filters, drum filters, band filters, tubular filters, plate filters, hyperbaric filters; may or may not include washing stages. The requirement is that the filtered solution must contain less than 10 ppm of suspended particles and the filtrate has a humidity of less than 15%.
  • the Ill-A STAGE can also operate with a settling pool system, in which the precipitates are stored in one of them, while the overflowing overflows a wall that allows a clear solution to accumulate in an adjoining pool; In this case, at least two sedimentation pools are recommended to ensure the operational continuity of the Process.
  • the sequential system and process comprises one or more concentration-precipitation stages, in which the number of stages mentioned depends on the physical chemical characteristics of the natural solutions of the salt flat and must be determined experimentally with laboratory devices. It comprises one or more electrolytic devices (7) of ionic separation connected in series, in parallel or mixed connection, with at least one forced salt precipitation device and a solid-liquid separation device.
  • Each concentration-precipitation stage requires one or more electrolytic ion separation devices connected in series, in parallel or mixed connection, with at least one forced salt precipitation device and a solid-liquid separation device.
  • the electrolytic device is made up of a series of alternate compartments, called the Dilute channel and Concentrate channel, through which the aqueous solutions flow which will result in obtaining a diluted solution and a concentrated solution.
  • a Dilute channel always has two concentrate channels as a neighbor, separated by an MUTA anionic ion exchange membrane on one side and a MIITC cationic ion exchange membrane on the other.
  • the membrane constitutes a physical wall between both solutions, which prevents them from mixing, but, which maintains the electrical connectivity between both solutions by means of the selective transfer of anions from the diluted to the concentrate that pass through the MUTA and the transfer of cations that passes freely through the ITC from the dilute to the concentrate.
  • the driving force that produces the movement of ions in the solutions is achieved by the imposition of an electric potential difference between two conductive or semiconductor electrodes located at the two ends of the series of concentrates and diluted compartments.
  • One of the electrodes is positively polarized and immersed in a compartment called Anodic Wash Water, which aims to protect the electrode and prolong its life.
  • the electrode located at the opposite end is negatively polarized and is also immersed in an aqueous solution that meets the objective of protecting the electrode; This compartment is called Cathodic Wash Water.
  • the Anodic Wash Water compartment on one side has a solid wall and on the other hand, as an immediate neighbor, it has a Concentrate compartment in which they share a MUTA. Similarly at the opposite end, in the cationic Wash Water compartment it has a solid wall on one side and on the other side it has a MI ITC.
  • the materials of the electrodes that make up this conventional or modified electrolytic device are determined experimentally according to the chemical composition of the natural brine solution, which can be, for example, titanium, DSA (coated titanium mesh), lead dioxide, lead , stainless steel, graphite, platinized electrodes or any conductive or semi-conductive material resistant to the chemical aggressiveness of the brine.
  • electro dialysis cell The device consulted is conventionally known as "electro dialysis cell", and may consider a traditional electro dialysis (ED), reverse electro dialysis (EDR), electro dialysis-ionization (EDI), electro-dialysis assisted by electromagnetic fields or electro dialysis with separation of cations and anions, where in any of its forms the limit of the electro-dialysis stage in the process is defined by the critical concentrations of the species that precipitate by saturation in the concentrate. A fraction of the dilute can be used in the process, but, most of it can be recirculated to the salar.
  • ED electro dialysis
  • EDR reverse electro dialysis
  • EDI electro dialysis-ionization
  • the resulting solutions are driven to a stage of precipitation carried out in agitated or static ponds, in which the thermodynamic conditions are changed and precipitating agents can be added that promote the massive precipitation of contained salts
  • These salts can be returned to the natural salt or can be marketed after solid-liquid separation.
  • the solid-liquid separation can be carried out in filters of any type (plates, drum, ceramic, rotary or tubular) or in sedimentation pools in a way that allows obtaining a clear solution free of solids.
  • Each phase comprising the three stages of electro dialysis, agitation-precipitation and solid / liquid separation, must be repeated until reaching the required lithium concentration in the resulting solutions.
  • the feed to the following electro-dialysis-precipitation-solid-liquid separation sequence is the Concentrate produced, in which between 60 to 95% is conducted to the dilute of the next stage and the rest constitutes a new flow of concentrate, that is, The next stage is smaller than the previous stage.
  • Fig. 4 shows an exemplary scheme of a complete phase and its respective stages of the system and process of the invention, where the system and process comprises a phase (1) with its three respective stages.
  • the figure shows how the first phase begins with the entry to a stage I (El), of the solution from a brine source (2) and with the entry of clean water from a source of clean water (5), said stage it comprises a mechanism comprising one or more electrolytic cells (4), then the solution is conducted to a stage II (E-ll) comprising a precipitation mechanism (17) and subsequently the solution is conducted to a stage III comprising a solid / liquid separation mechanism (21).
  • E-ll stage II
  • the solution is conducted to a stage III comprising a solid / liquid separation mechanism (21).
  • the solution can enter a second phase (23) that includes, like the first phase, the three stages mentioned.
  • the figure also shows the recirculation and the entry and return of solutions.
  • the process comprises one or more concentration-precipitation stages, where the number of stages mentioned depends on the physical chemical characteristics of the natural solutions of the salt flat and must be determined experimentally with laboratory devices.
  • Each process step comprises one or more electrolytic ion separation devices connected, comprises at least one mechanism of forced salt precipitation and comprises at least one solid-liquid separation mechanism.
  • Each electrolytic device is made up of a series of alternate compartments, called the Dilute channel and Concentrate channel, where aqueous solutions flow that will result in obtaining a diluted solution and a concentrated solution.
  • the sequential process comprises the following steps; a) conduct a brine from the natural salt (2) through a distributor pipeline to a concentrate pond;
  • a Dilute channel always has two Concentrate channels as a neighbor, separated by an MUTA anionic ion exchange membrane on one side and a MIITC cationic ion exchange membrane on the other.
  • the membrane constitutes a physical wall between both solutions, which prevents them from mixing, but, which maintains the electrical connectivity between both solutions by means of the selective transfer of anions from the diluted to the concentrate that pass through the MUTA and the transfer of cations that passes freely through the ITC from the dilute to the concentrate.
  • the driving force that produces the movement of ions in the solutions is achieved by the imposition of an electric potential difference between two conductive or semiconductor electrodes located at the two ends of the series of concentrates and diluted compartments.
  • One of the electrodes is positively polarized and immersed in a compartment called Anodic Wash Water, whose objective is Protect the electrode and prolong its life.
  • the electrode located at the opposite end is negatively polarized and is also immersed in an aqueous solution that meets the objective of protecting the electrode; This compartment is called Cathodic Wash Water.
  • the Anodic Wash Water compartment on one side has a solid wall and on the other hand, as an immediate neighbor, it has a Concentrate compartment in which they share a MUTA. Similarly at the opposite end, in the cationic Wash Water compartment it has a solid wall on one side and on the other side it has a MI ITC.
  • the materials of the electrodes that make up this conventional or modified electrolytic device are determined experimentally according to the chemical composition of the natural brine solution, which can be, for example, titanium, DSA (coated titanium mesh), lead dioxide, lead , stainless steel, graphite, platinized electrodes or any conductive or semi-conductive material resistant to the chemical aggressiveness of the brine.
  • the natural brine solution can be, for example, titanium, DSA (coated titanium mesh), lead dioxide, lead , stainless steel, graphite, platinized electrodes or any conductive or semi-conductive material resistant to the chemical aggressiveness of the brine.
  • electro dialysis cell The device consulted is conventionally known as "electro dialysis cell", and may consider a traditional electro dialysis (ED), reverse electro dialysis (EDR), electro dialysis-ionization (EDI), electro-dialysis assisted by electromagnetic fields or electro dialysis with separation of cations and anions, where in any of its forms the limit of the electro-dialysis stage in the process is defined by the critical concentrations of the species that precipitate by saturation in the concentrate. A fraction of the dilute can be used in the process, but, most of it can be recirculated to the salar.
  • ED electro dialysis
  • EDR reverse electro dialysis
  • EDI electro dialysis-ionization
  • the resulting solutions are driven to a stage of precipitation carried out in agitated or static ponds, in which the thermodynamic conditions are changed and precipitating agents can be added that promote the massive precipitation of contained salts
  • These salts can be returned to the natural salt or can be marketed after solid-liquid separation.
  • the solid-liquid separation can be carried out in filters of any type (plates, drum, ceramic, rotary or tubular) or in sedimentation pools in a way that allows obtaining a clear solution free of solids.
  • the electro-dialysis-precipitation-solid / liquid separation step must be repeated until the concentration of lithium required in the resulting solutions is reached.
  • the feeding to the following sequence of electro-dialysis-precipitation-solid-liquid separation is the Concentrate produced, in which between 60 and 95% the dilute of the next stage is conducted and the remainder constitutes a new flow of concentrate, that is, the next stage is smaller than the previous stage.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un système séquentiel électrolytique pour augmenter la concentration de lithium présent dans des saumures naturelles qui remplace des mares ou piscines d'évaporation évitant la perte d'eau. Le système comprend au moins une phase séquentielle réplicable (1), ladite phase séquentielle réplicable comprenant à son tour au moins trois mécanismes reliés séquentiellement en trois étapes: une étape I (E-I) qui comprend un mécanisme ordonné composé d'une ou de plusieurs cellules électrolytiques ou électrodialyse (4), une étape II (E-II) qui comprend un mécanisme de précipitation (17) et une étape (III) (E-III) qui comprend un mécanisme de séparation solide/liquide (21); le système comprend en outre une source de saumure (2) et une source d'eau propre (5) reliées à l'E-I, au moins une cuve de stockage de produit dilué (8) qui est relié à l'E-I, une zone de récupération de saumure reliée à la cuve de stockage de produit dilué, une soupape de distribution de flux concentré produit (12) disposée entre l'E-I et l'E-II, une source d'alimentation en réactifs et intrants de précipitation (15) reliée à l'E-II, une source d'alimentation en réactifs et intrants de séparation (19) reliée à l'E-III et une cuve de stockage de sels précipités (25) qui reçoit le flux sortant de l'E-III.
PCT/CL2016/050068 2015-12-11 2016-12-12 Système et procédé séquentiel électrolytique pour augmenter la concentration de lithium présent dans des saumures WO2017096495A1 (fr)

Applications Claiming Priority (2)

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CL2015003609A CL2015003609A1 (es) 2015-12-11 2015-12-11 Sistema y proceso secuencial electrolitico para aumentar la concentración de litio presente en salmueras que reemplaza pozas o piscinas de evaporación y que evita la perdida de agua por evaporación, recupera una fracción como agua industrial y el resto la incorpora nuevamente a un salar
CL3609-2015 2015-12-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019000111A1 (fr) * 2017-06-30 2019-01-03 Protech Spa Système et procédé pour éliminer l'ion chlorure présent dans des solutions en circulation dans des processus industriels
CN117305584A (zh) * 2023-11-29 2023-12-29 中国科学院过程工程研究所 一种流动浆料电脱嵌提锂的系统和方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636295A (en) * 1985-11-19 1987-01-13 Cominco Ltd. Method for the recovery of lithium from solutions by electrodialysis
US20040074774A1 (en) * 2002-10-22 2004-04-22 Industrial Technology Research Institute Process for producing lithium concentrate from brine or seawater
WO2011133165A1 (fr) * 2010-04-23 2011-10-27 Simbol Mining Corp. Procédé de fabrication du carbonate de lithium à partir du chlorure de lithium
WO2015058287A1 (fr) * 2013-10-23 2015-04-30 Nemaska Lithium Inc. Procédés de préparation de carbonate de lithium
US20150197830A1 (en) * 2012-07-31 2015-07-16 Research Institute Of Industrial Science & Technology Method for Extracting Lithium from Solution Containing Lithium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636295A (en) * 1985-11-19 1987-01-13 Cominco Ltd. Method for the recovery of lithium from solutions by electrodialysis
US20040074774A1 (en) * 2002-10-22 2004-04-22 Industrial Technology Research Institute Process for producing lithium concentrate from brine or seawater
WO2011133165A1 (fr) * 2010-04-23 2011-10-27 Simbol Mining Corp. Procédé de fabrication du carbonate de lithium à partir du chlorure de lithium
US20150197830A1 (en) * 2012-07-31 2015-07-16 Research Institute Of Industrial Science & Technology Method for Extracting Lithium from Solution Containing Lithium
WO2015058287A1 (fr) * 2013-10-23 2015-04-30 Nemaska Lithium Inc. Procédés de préparation de carbonate de lithium

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019000111A1 (fr) * 2017-06-30 2019-01-03 Protech Spa Système et procédé pour éliminer l'ion chlorure présent dans des solutions en circulation dans des processus industriels
CN117305584A (zh) * 2023-11-29 2023-12-29 中国科学院过程工程研究所 一种流动浆料电脱嵌提锂的系统和方法
CN117305584B (zh) * 2023-11-29 2024-02-09 中国科学院过程工程研究所 一种流动浆料电脱嵌提锂的系统和方法

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