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WO2024251991A1 - Dispositif de production de cristaux de carbonate de lithium - Google Patents

Dispositif de production de cristaux de carbonate de lithium Download PDF

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Publication number
WO2024251991A1
WO2024251991A1 PCT/EP2024/065811 EP2024065811W WO2024251991A1 WO 2024251991 A1 WO2024251991 A1 WO 2024251991A1 EP 2024065811 W EP2024065811 W EP 2024065811W WO 2024251991 A1 WO2024251991 A1 WO 2024251991A1
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WO
WIPO (PCT)
Prior art keywords
reactor
lithium
medium
thermally insulated
lithium carbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/065811
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German (de)
English (en)
Inventor
Bernd Schultheis
Christoph Ney
Markus Pfänder
Jenny Hess
Georg Katzmann
Jing Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
K Utec AG Salt Technologies
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K Utec AG Salt Technologies
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Filing date
Publication date
Application filed by K Utec AG Salt Technologies filed Critical K Utec AG Salt Technologies
Publication of WO2024251991A1 publication Critical patent/WO2024251991A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0018—Evaporation of components of the mixture to be separated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
    • B01D9/0054—Use of anti-solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/81—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis the stirrers having central axial inflow and substantially radial outflow
    • B01F27/813—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis the stirrers having central axial inflow and substantially radial outflow the stirrers co-operating with stationary guiding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D2009/0086—Processes or apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the invention particularly relates to a device for the continuous and controlled crystallization of lithium carbonate, but can also be used for comparable, preferably inorganic crystals.
  • the device according to the invention is suitable for producing crystals with defined grain size, particle distribution and grain structure, especially of lithium carbonate, but also in particular of other metal hydroxides, metal carbonates, metal sulfates, metal nitrates, amino and carboxylic acids as well as their salts by precipitation from their aqueous solutions.
  • the basic principle of crystallization or precipitation of solids from an aqueous solution is to cause supersaturation of the dissolved solid in the aqueous solution in order to carry out the crystallization or precipitation process in a controlled manner by reducing the supersaturation.
  • This can be done in various ways.
  • a precipitation reaction in which the solution of a reactant is placed in a stirred vessel and an associated precipitant is added dropwise or otherwise dosed while stirring.
  • the precipitated particles should have a homogeneous particle size and uniform particle structure. Even in continuous processes in which reactant and precipitant are continuously added, it is important to ensure homogeneous reaction conditions in the stirred vessel and to avoid uncontrolled crystal formation.
  • lithium carbonate (U2CO3) can be produced by adding alkali carbonates (precipitant) to a lithium salt solution (reactant).
  • the precipitation of lithium carbonate (U2CO3) is also possible by adding lithium salts (precipitant) to alkali carbonates (reactant).
  • lithium salt solutions and alkali carbonate salt solutions can be continuously added to a solution and/or suspension in the reaction vessel or reactor. The reaction can be controlled by increasing or decreasing the temperature and optionally by the dosing ratios.
  • lithium carbonate (U2CO3) is produced by carbonating a lithium hydroxide (LiOH) solution, ie, by introducing CO2 (g) or CO2 dissolved in water into a lithium hydroxide solution.
  • LiOH solution and CO2 (g) or CO2 dissolved in water can be continuously fed into a solution and/or suspension in the reaction vessel or reactor.
  • the reaction can be controlled by increasing or decreasing the temperature and the rate of addition of the reactants.
  • Another precipitation process is based on the thermally induced decomposition of lithium hydrogen carbonate (UHCO3) dissolved in water.
  • a purified lithium hydrogen carbonate solution is decomposed by thermal exposure into CO2 (gaseous) and lithium carbonate (U2CO3) as a precipitate.
  • U2CO3 lithium carbonate solution
  • U2CO3 aq
  • the lithium hydrogen carbonate (aq) purified in this way can be used to crystallize high-purity lithium carbonate by thermal decomposition with release of CCh.
  • the reactor or crystallizer essentially consists of a cylindrical container, possibly with a flat, curved or conical bottom, an axial stirrer with guide tube and a clarification ring for separating an annular clarification chamber from the remaining suspension-filled crystallizer contents, as well as supply and discharge elements for the solid and liquid substances.
  • the crystallizer from DD 227615 makes it possible to continuously mix the solid and liquid starting materials, ensure the reaction process, achieve a high crystal density in the reaction chamber and thus a coarse crystallizate, which can be withdrawn from the reactor in a thickened, highly concentrated form, while the liquid reaction phases in the reactor leave clarified via an overflow.
  • the axial stirrer leads to mixing through the suction effect of the stirrer, which starts at the upper end of the guide tube and is generated by the suction-in inclined blades of the stirrer.
  • the stirrer conveys the suctioned suspension to the bottom of the tank and sucks it back in again after it rises up the cylindrical tank walls at the upper end of the guide tube.
  • a specific flow deflection is provided by an annular installation in the form of a deflection ring with a roof-shaped cover and, if necessary, a transfer of solids separated in the clarification chamber to a central part of the reactor.
  • this apparatus has only limited use for the crystallization of mineral salts such as lithium carbonate on a large scale.
  • it is not suitable for the homogeneous production of crystals in reactions in which crystallization is induced or supported by increasing the temperature.
  • the inventors of the present invention were faced with the problem that a local increase in temperature, e.g. with at least one additional pipe that introduces a reactant and/or precipitant at high temperatures (so-called "steam lance"), leads to uncontrolled crystal growth in the vicinity of and in particular on the surface of the steam lance.
  • Heat input via the outer walls of the crystallizer or by pumping the reaction medium through an external heat exchanger leads to comparable problems.
  • product losses occur because the resulting crystal particles are not sufficiently homogenized.
  • problems arise with cleaning and with the limited execution time of a continuous process. Maintenance intervals become shorter, the reactor becomes dirty, and the crystallization process becomes low-yielding.
  • the object underlying the present invention is therefore to provide an improved process or an improved apparatus for producing homogeneous metal salt crystals with a defined, as homogeneous as possible grain distribution and grain structure.
  • the problems identified by the inventors which arise from an inhomogeneous temperature distribution, must be avoided.
  • a reactor comprising at least one reactor element which enables the supply of liquid or gaseous starting substances (e.g. medium, reactant and/or precipitant) into the reactor chamber at an elevated temperature without creating an inner surface in the reactor chamber at which a temperature gradient to the reactor solution or reactor suspension is created.
  • liquid or gaseous starting substances e.g. medium, reactant and/or precipitant
  • a thermally insulated steam lance which is a thermally insulated feed pipe, is introduced into the reactor of the present invention.
  • the steam lance is suitable for introducing starting substances in the form of gases, such as steam or gaseous CO2, or aqueous solutions at high temperature into the reactor, so that thermally induced or promoted crystallization can be initiated there.
  • the thermal insulation prevents unwanted deposits from forming on the surface of the feed pipe in process media containing dissolved salts or solids, the solubility of which increases greatly as the temperature drops.
  • the steam lance comprises an insulation jacket which thermally insulates a substance-carrying inner tube in the steam lance from the reaction space in the reactor.
  • the insulation jacket can be insulated by air or a thermally inert liquid, for example by a circulating liquid that is supplied and discharged.
  • the insulation jacket comprises at least one insulation layer with a cooling medium, a conventional insulation medium or a vacuum layer.
  • the insulation layer of the insulation jacket has a thermal conductivity of 0.05 W/(mK), e.g. with a layer thickness of 2 cm or more.
  • Thermally insulated means that there is a maximum of a small, limited heat flow from the inside of the reactor to the steam lance or to the inside of the steam lance or in the opposite direction.
  • the insulation layer serves as a measure to limit this heat flow.
  • an inlet pipe or a steam lance is referred to as “thermally insulated” if the quotient of the thermal conductivity of the reactor medium AR and the boundary layer thickness dR on the surface of the insulation layer around which the flow takes place on the reactor side is at least a factor x greater than the quotient of the thermal conductivity of the insulation layer Ai and its layer thickness di.
  • the factor x is equal to the value of the temperature difference between the inside of the steam lance and the medium temperature in the reactor. In a preferred embodiment, x is at least 5, more preferably at least 10.
  • the boundary layer thickness dR is a value that depends on the geometry and conditions in the reactor and is determined by the quotient of the Nusselt number and the given length of the steam lance.
  • the insulation layer of the insulation jacket will have a thermal conductivity of 0.05 W/(mK) or less, preferably 0.01 W/(mK) or less, more preferably 0.005 W/(mK) or less.
  • the layer thickness of the insulation layer is 0.1 cm or more, 0.2 cm or more, 0.5 cm or more, 1.0 cm or more, 1.5 cm or more, 2.0 cm or more; or 3.0 cm or more.
  • layer thicknesses of 1.0 cm or more are common, preferably 1.5 cm or more, more preferably 2.0 cm or more; or most preferably 3.0 cm or more.
  • thermal conductivity of a thermal conductivity of 0.01 W/(mK) or less layer thicknesses of 0.2 cm or more, 0.5 cm or more, or 1.0 cm or more are preferred; however, larger layer thicknesses - as mentioned above - are possible.
  • layer thicknesses of 0.1 cm or more, 0.2 cm or more, or 0.5 cm or more are preferred; however, larger layer thicknesses are possible.
  • thermal insulation is achieved by introducing at least one insulating layer on the surface of the feed pipe, which contains vacuum or a coolant.
  • the insulation jacket is particularly preferably made up of several layers.
  • the outer layer serves to prevent heat losses that are transferred to the cooling medium.
  • An inner layer prevents the cooling of the medium that flows through the steam lance.
  • this embodiment is also suitable for introducing cold process media into a hot environment within the reactor without a relevant temperature gradient occurring to the surface of the steam lance. In this case, unwanted deposit formation on the surface of the feed pipe in the case of process media with dissolved salts or solids, the solubility of which increases significantly with increasing temperature, can be avoided.
  • the temperature gradient between the surface of the steam lance and the interior of the reactor should be less than 1 K, preferably less than 0.1 K, and ideally not measurably small. In this way, temperature-induced deposit formation of crystals, e.g. Li2CO3 crystals, on the surface of the steam lance can be reduced or preferably completely avoided.
  • the heat loss is in principle of minor importance as long as no crystal formation is induced.
  • no deposits of crystals, e.g. of U2CO3, occur on the surface of the steam lance, i.e. the deposit formation of crystals, e.g. of U2CO3, on the surface of the steam lance is limited to a deposit formation rate of maximum T10' 5 m/h, preferably to a maximum of T10' 6 m/h.
  • a temperature gradient between the surface of the steam lance and the interior of the reactor of less than 1 K, preferably less than 0.1 K, a maximum of T10 -5 m/h, preferably a maximum of T10' 6 m/h, is achieved.
  • the reactor comprises one or more steam lances for the supply of liquid or dissolved starting substances (medium, reactant and/or precipitant), which are introduced at certain defined positions in the reaction vessel, particularly preferably within the guide tube, in the area between the guide tube and the clarification ring at the height of the upper edge of the guide tube or in the inner area of the clarification ring on or below the process medium surface. Solids are fed into the latter area directly onto the process medium surface.
  • the reactor comprises at least one external circulation line.
  • the circulation line has an inlet at the upper end of the reactor and an outlet at the lower end of the reactor, where the inlet and outlet can optionally be provided with heatable and/or coolable sleeves.
  • the circulation line comprises a heating element at the inlet, which heats the supplied starting substance (such as medium, reactant, precipitant) before it enters the reactor.
  • the inlet in this aspect of the invention is a steam lance as described above.
  • the heating element consists of a T-shaped tube in which steam or another heating medium such as hot water is mixed with the circulation stream.
  • the present invention offers a number of advantages over conventional methods and devices.
  • the reactor according to the invention and the associated method according to the invention have few incrustations, which means that little maintenance is required.
  • the reactor-related homogenization during the crystallization process results in a regular and narrow grain size distribution and thus improved filterability and washability.
  • the resulting crystallizate contains smaller amounts of water-insoluble, non-washable impurities.
  • the production output per apparatus is increased, the reactor service life is increased, and the maintenance intervals are longer.
  • lithium carbonate can be provided as spherical crystallizate that is particularly easy to wash out and process further.
  • Lithium carbonate as a spherical crystallizate preferably has a diameter of 0.15 mm to 0.75 mm as a median value and a narrow particle size distribution of 0.09 to 0.65 mm as a limit value for the lower and 0.20 mm to 0.80 mm for the upper 10-of-100 mass percentile and particularly preferably a particle diameter of 0.20 with an even narrower distribution of 0.169 mm as a limit value for the lower and 0.255 mm for the upper 10-of-100 mass percentile.
  • Figure 1 describes a device (“reactor”) for crystallizing mineral salts, in particular lithium carbonate, comprising a cylindrical container, preferably with a straight, curved or slightly conical bottom, with a centrally arranged axial stirrer (6) in a guide tube (3) which generates a flow directed towards the bottom of the container, as well as a clarification ring (1) for clarifying the reactor overflow, as well as an overflow channel (2) for collecting and draining the reactor overflow and an optional deflection ring (4) to support the clarification.
  • the reactor optionally comprises a wall flow breaker (5) to interrupt a possible tangential flow.
  • An underflow (10) is provided for the suspension discharge.
  • Such a reactor is known in the prior art.
  • the device of the present invention is characterized by at least one thermally insulated feed pipe (7) (i.e. a thermally insulated steam lance (7)) for media, reactants and/or precipitants, which projects into the reactor interior, preferably into the medium inside the reactor.
  • a thermally insulated feed pipe (7) i.e. a thermally insulated steam lance (7)
  • media, reactants and/or precipitants which projects into the reactor interior, preferably into the medium inside the reactor.
  • the ratio of the height of the container to the diameter of the container is between 0.8 and 1.3, more preferably 0.9 to 1.2.
  • the volume of the reactor is between 20 liters and 300 m 3 .
  • the continuous tests required for this are preferably carried out in volumes between 20 and 400 liters.
  • Scale-up is carried out using the factors for the component dimensions specified for this reactor type, related to the reactor diameter.
  • U2CO3 is usually produced with a specific crystallization rate of 5 - 40 kg of product per 1 m 3 of reactor volume and hour. Ideally, a low crystallization rate promotes better quality lithium carbonate.
  • the reactor volume and thus the dimensions of all components are determined by the specific crystallization rate for a given production rate for U2CO3.
  • the reactor can be built with a volume larger than 300 m3 , but there is currently no practical operating experience.
  • the bottom of the container is straight.
  • the bottom of the container comprises a straight bottom inclined at an angle of up to 5° to the bottom outlet.
  • the bottom is domed with a curvature that preferably extends to the wall flow breakers.
  • the clarification ring (1) according to the reactor of the present invention which serves to clarify the reactor overflow, preferably comprises a diameter of 50% of the vessel diameter, with a preferred clarification height of 0.15 to 0.28 in relation to the vessel height.
  • the clarification ring comprises a horizontal slit near the clarification lower edge.
  • the overflow channel (2) (here also "overflow") of the reactor of the present invention serves to collect and drain the reactor overflow. It is preferably inclined at an angle of 1 to 5 degrees to the outlet.
  • the width of the overflow channel depends on the overflow volume. It is preferably provided with maintenance hatches in the reactor cover so that any fine material that has sedimented in the overflow channel can be flushed out.
  • the guide tube (3) of the reactor of the present invention serves to generate the desired flow conditions.
  • the guide tube diameter is preferably 0.23 to 0.36 in relation to the container diameter.
  • the guide tube length is preferably 0.49 to 0.82 in relation to the container height.
  • the installation height of the guide tube preferably ends at a height of 0.092 to 0.42 in relation to the container height above the floor.
  • the deflection ring (4) serves to support the clarification ring.
  • the width of the deflection ring is preferably 0.07 to 0.10 in relation to the vessel diameter.
  • the installation height is a maximum of 0.5 in relation to the vessel height (from the top to the middle of the reactor).
  • the inclination is preferably up to 30° to the vertical.
  • the wall flow breaker (5) serves to prevent tangential flow.
  • the width of the wall flow breaker is preferably up to 0.1 in relation to the container diameter.
  • the installation height is preferably in the range between 0.046 and 0.128 in relation to the container height, in the lower half of the container.
  • the agitator of the reactor of the present invention is preferably a 6-blade impeller.
  • the impeller diameter is preferably 0.21 to 0.33 in relation to the container diameter.
  • the installation height of the impeller is preferably 0.08 to 0.020 in relation to the container height with a stirring blade height of preferably between 0.042 and 0.066 in relation to the container diameter.
  • the inclination of the stirring blades is preferably between 30°C and 60°C.
  • the thermally insulated feed pipe (7) (ie the thermally insulated steam lance (7)) is suitable for introducing media, reactants and/or precipitants with a temperature of 0°C to the boiling temperature, ideally between 40°C and 100°C, more preferably between 50°C and 85°C for precipitation processes and between 40°C and 100°C, preferably between 80°C and 100°C for boiling solutions or for thermal decomposition or precipitation processes, for example the decomposition of dissolved lithium hydrogen carbonate by steam introduction.
  • the feed pipe can be operated at 0°C to 30°C, preferably at ambient temperature and pressure.
  • concentrations of 50 to 450 kg of solids per cubic meter are set at the reactor underflow for suspensions containing lithium carbonate by the amount removed at the reactor underflow.
  • the solids concentration at the reactor underflow is preferably between 150 kg and 300 kg/m 3 . It is particularly preferably between 180 and 250 kg/m 3 if lithium carbonate is produced from lithium chloride solutions.
  • the mass flow of dissolved lithium salt required for precipitation is introduced through the feed pipe.
  • Specific crystallization and dissolution rates for lithium carbonate are preferably set between 5 and 25 kg/(m 3 h). In the case of very high purity requirements or very narrow grain size distributions, a specific crystallization rate of less than 15 kg/(m 3 h) is particularly recommended in the case of crystallization.
  • Precipitation processes according to the invention comprise the precipitation of lithium carbonate by adding lithium salt solution as a precipitant to an alkali carbonate solution (starting material).
  • an alkali carbonate solution can be added as a precipitant to a lithium salt solution (starting material).
  • alkali carbonate solution and lithium salt solution are introduced into the reactor through two different feed pipes.
  • solid lithium carbonate is precipitated from a lithium carbonate solution (starting material) by adding a lithium salt or a lithium salt solution (as a precipitant).
  • the lithium salt or the lithium salt solution can be initially introduced into the reactor so that solid lithium carbonate is precipitated by adding lithium carbonate solution as a precipitant.
  • lithium salt solution and lithium carbonate solution are introduced into the reactor through two different feed pipes.
  • carbon dioxide (as a precipitant, gaseous or as an aqueous solution) is introduced into a lithium hydroxide solution.
  • a lithium hydroxide solution can also be introduced into an aqueous carbon dioxide solution.
  • lithium hydroxide solution and carbon dioxide are introduced into the reactor through two different feed pipes.
  • hot water or steam is introduced into a lithium hydrogen carbonate solution.
  • the precipitant hot water or steam causes the precipitation of lithium carbonate from the lithium hydrogen carbonate solution with the formation of carbon dioxide.
  • This reaction can also be supported by pressurizing a lithium hydrogen carbonate solution in the reactor.
  • a lithium hydrogen carbonate solution can also be added to hot water in a reactor.
  • Lithium hydrogen carbonate solution and hot water or steam are preferably introduced into the reactor through two different feed pipes.
  • carbon dioxide gaseous
  • aqueous solution mixed with carbon dioxide can be made to form solid lithium carbonate by adding a lithium carbonate suspension. This produces a lithium hydrogen carbonate solution.
  • FIGS 2 to 11 show preferred embodiments of the invention. Combinations of the various embodiments shown here are also possible.
  • Fig. 2 shows a reactor according to the invention with one, optionally two feed pipes (steam lances) (7a), (7b). If there are two feed pipes, these can be installed symmetrically to the axis of the stirrer in the guide pipe (3) as shown here. The opening at the tip of the feed pipe protrudes into the interior of the guide pipe.
  • asymmetrically mounted thermally insulated feed pipes (7a), (7b) are provided, whereby one thermally insulated feed pipe (7a) protrudes into the interior of the guide pipe (3), the other does not, i.e. the thermally insulated feed pipe (7b) with opening at the tip of the feed pipe is introduced into another area of the reactor.
  • the thermally insulated feed pipes (7) can be heated or cooled by a cooling or heating circuit in the insulation jacket of the respective thermally insulated Steam lance (7).
  • the cooling or heating circuit can contain a cooling or heating liquid, a cooling or heat transfer gas or a vacuum.
  • the cooling or heating circuit is preferably fed with an aqueous medium or with air.
  • the insulation jacket consists of three layers, which surrounds the thermally insulated feed pipe (7) for CO2 in a ring shape.
  • the inner and outer layers of the insulation jacket each consist of a chamber filled with material that has a low thermal conductivity.
  • This can be vacuum insulation panels, air or other solid or gaseous insulating materials with a thermal conductivity of less than 0.05 W/(mK), preferably less than 0.01 W/(mK), more preferably less than 0.005 W/(mK).
  • the middle layer consists of a chamber arranged spirally around the longitudinal axis of the thermally insulated feed pipe (7), through which a cooling medium flows (see Fig. 10 below). The outer layer serves to minimize heat losses. This embodiment can also be used to cool the process medium in the crystallizer.
  • the thermally insulated feed pipe is connected to a feed line that leads out of the reactor, so that a circulation line (12) is created.
  • the thermally insulated feed pipe (7) can also be fed by one or more further feed lines.
  • the circulation line is provided with cooling (or heating) sleeves (13), which are preferably attached directly to the entry points into the circulation line (12).
  • the T-shaped pipe used for mixing with the circulation flow can be thermally cooled or heated on the side where the heating or cooling medium is introduced against the rest of the pipe in a similar manner to that described for the steam lance.
  • a static mixer (8) is integrated into the circulation line.
  • the static mixer is a device for mixing liquids, or for mixing liquids with gases, whereby a homogeneous mixture of a mixture with a desired, adjustable mixing ratio is produced.
  • Static mixers are known in the prior art in various embodiments.
  • the reaction temperature in the feed pipe is also set in the static mixer.
  • the process parameters that are generated in the static mixer are as follows: A temperature in the range from 0°C to boiling temperature is set, preferably between 40°C and 85°C, for example between 80°C and 100°C.
  • For the dissolution of Lithium carbonate can be heated to a temperature between 10°C and 25°C. The flow rate and thus the speed of mixing can be adjusted by the circulating volume flow for a given dimension of the static mixer.
  • Fig. 8 shows preferred entry points, highlighted in hatching, at which the entry pipes (7) can introduce aqueous solutions and/or steam or CO2 into the reactor vessel.
  • the openings at the respective tips of the entry pipes here called "entry points”
  • Fig. 9 shows an embodiment of the invention for the crystallization of lithium carbonate with external clarification.
  • the reactor and a connected external clarifier (9) are connected to each other via the overflow (2).
  • the clarification overflow is collected in the external clarifier (9) and from there clarified crystals from the underflow of the external clarifier (9) are returned to the reactor via the thermally insulated feed pipe (7).
  • this embodiment it is possible to collect lithium carbonate particles entrained with the reactor overflow in the clarifier and return them to the reactor, which has a positive effect on grain growth.
  • this embodiment enables the production of larger particles than would be possible with the reactor alone.
  • the clarification area in the reactor is reduced and thus the speed of the solution flowing up to the overflow is increased.
  • Fig. 10 shows an embodiment of a thermally insulated feed pipe (7) (steam lance (7)) whose outer wall can be cooled with the ambient air.
  • the outer wall is insulated from the outside in such a way that the outside temperature of the steam lance does not exceed the reactor temperature in the reactor medium and preferably does not fall below it either. In this way, incrustations on the outer wall of the steam lance are avoided.
  • the feed pipe or steam lance can be fed with either a cooling or heating circuit.
  • the insulation jacket consists of three layers, which surrounds the feed lance for CO2 in a ring shape. The inner and outer layers of the insulation jacket can each be filled with air (see A1, A3).
  • the middle chamber arranged spirally around the longitudinal axis of the steam lance, can be flowed through with cold ambient air (A2).
  • This figure shows a comparatively cost-effective variant of the steam lance, for example for heating the lithium carbonate suspension, for example when dissolved lithium hydrogen carbonate is to be decomposed and crystallized as lithium carbonate.
  • Water vapor (D) or an aqueous solution can be passed through the central pipe.
  • Fig. 11 shows a combination of two apparatuses of the present invention, such as can be used for purifying lithium carbonate.
  • Contaminated lithium carbonate is dissolved in the unit reactor 1.
  • an aqueous suspension with the contaminated lithium carbonate and CO2 is continuously introduced into the reactor to form lithium hydrogen carbonate.
  • the reactor contains a sufficient amount of solid lithium carbonate, preferably with a concentration of 180-250 g/l. Coarse, insoluble contaminants also remain in the reactor, with suspension being discharged from the underflow (10) of the reactor after a specified operating time and filtered to prevent excessive accumulation of contaminants.
  • the solid lithium carbonate discharged with the solution overflow (2) is collected in a subsequent clarifier and returned to the unit reactor 1 with the clarifier underflow.
  • the clarifier overflow is fed to a fine filter so that even the finest particles are removed from the lithium hydrogen carbonate solution stream.
  • the structure up to the fine filter ensures that a lithium hydrogen carbonate solution with a constant lithium hydrogen carbonate concentration is produced by controlling the temperature and pressure. Since a sufficient amount of lithium carbonate solid is always available, the solution is always concentrated to near the solubility limit of lithium hydrogen carbonate.
  • the dissolved amount of U2CO3 is replenished by the Li2CC>3 suspension so that the solid concentration in the unit reactor 1 and thus also the conversion rate, preferably 15 - 25 (kg/m 3 h), remains constant.
  • Ion exchangers following the fine filter serve to remove multivalent cations such as calcium, magnesium or aluminum and/or borates that have also been dissolved by the CO2 from the lithium hydrogen carbonate solution.
  • Lithium carbonate is then Supply of steam with the inventive structure in the unit reactor 2, the solid lithium carbonate is recrystallized, drained off at the lower reaches of the unit reactor 2 and the solid lithium carbonate is separated with a centrifuge and passed on for drying. The solution overflowing from the clarifier is collected and, depending on the permissible concentration of the other dissolved impurities such as sodium, potassium, chloride or sulfate, is used in whole or in part to suspend contaminated lithium carbonate.
  • the present invention provides an apparatus and a crystallization process.
  • a device for thermally controlled precipitation crystallization in the form of a reactor, consisting of a cylindrical container with a preferably flat, curved or slightly conical bottom, with a centrally arranged axial stirrer (6) with guide tube (3), which preferably generates a flow directed towards the container bottom, and an annular separating plate (1) (so-called "clarification ring” (1)) concentrically surrounding the axial stirrer (6) for separating a clarifying ring space from the stirred container contents and an overflow channel (2), characterized in that the reactor comprises a thermally insulated feed pipe (7) for introducing an aqueous phase or a gas phase, without having a surface in the reactor interior which has a temperature gradient to the temperature of the reactor medium.
  • the thermally insulated feed pipe (7) comprises an opening, preferably at the tip of the feed pipe, which projects into the interior of the reactor vessel, wherein the thermally insulated feed pipe (7) is thermally insulated, preferably by a casing which is fed with a cooling and/or heating medium.
  • the casing comprises a vacuum.
  • Another embodiment contains air as an insulating layer.
  • Yet another embodiment contains vacuum insulation or plastic foam.
  • the feed pipe is covered with three layers, wherein the inner and outer layers are thermally insulating in the manner described and the middle layer has a temperature-regulating effect by supplying a heating or cooling medium such that no measurable temperature gradient occurs between the surface of the feed pipe and the medium in which it is immersed.
  • the feed pipe is part of a circulation circuit (12) which is thermally adjustable and can preferably adjust the reaction temperature in gradual steps.
  • the above-mentioned embodiments comprise a reaction vessel which further comprises means for flow deflection (4) (e.g. a deflection ring (4)) and an underflow (10) suitable for product removal at the vessel bottom.
  • means for flow deflection (4) e.g. a deflection ring (4)
  • an underflow (10) suitable for product removal at the vessel bottom.
  • the reactor of the present invention comprises an integrated clarification zone (11).
  • the reactor of the invention comprises an additional external clarifier (9) (or “clarifier” (9)) located outside the reactor, into which the reactor overflow is introduced from the reactor overflow (2).
  • additional external clarifier (9) located outside the reactor, into which the reactor overflow is introduced from the reactor overflow (2).
  • clarifier (9) separated solid particles can be collected and returned to the reactor, thereby promoting crystal growth.
  • the external clarification device (9) is a clarification cone without a rake mechanism, a round thickener with a rake mechanism, a lamella clarifier, a centrifuge, or a decanter.
  • the reactor of the invention comprises two or more thermally insulated feed pipes (7).
  • the thermally insulated feed pipes (7a, 7b) are preferably arranged axially symmetrically to the axial stirrer (6).
  • two thermally insulated feed pipes (7) are arranged asymmetrically (7a), (7b) to the axial stirrer (6).
  • At least one thermally insulated feed tube (7) is mounted in the guide tube of the reactor (3), i.e. the feed tube opening at the tip of the thermally insulated feed tube (7) preferably projects into the guide tube.
  • the reactor of the present invention comprises a deflection ring (4).
  • the reactor of the present invention comprises a wall baffle (5).
  • the reactor of the present invention comprises an underflow (10).
  • the reactor of the present invention comprises a six-blade impeller (6a). The use of four-blade impellers or propeller impellers is also possible.
  • the reactor of the present invention comprises a static mixer (8).
  • the reactor of the present invention comprises a circulation line (12), preferably a heatable and/or coolable circulation line (12).
  • the thermally insulated feed pipe (7) is a thermally insulated steam lance (7), the outer wall of which can be cooled with ambient air, or the outer wall of which can be cooled or heated with a liquid medium.
  • the thermally insulated feed pipe (7) is preferably surrounded by a triple insulation layer.
  • a crystallization process in a cylindrical reactor vessel equipped with a stirrer comprising the following step: a) initiating a precipitation reaction by supplying at least one liquid or gaseous medium into a medium inside the reactor, the supplied medium having a different temperature, preferably a higher temperature, than the reactor medium, a temperature change occurring in the reaction medium inside the reactor which induces or promotes the precipitation reaction without a surface being introduced into the reactor which creates a temperature gradient to the reactor medium.
  • a thermally insulated steam lance (7) is introduced into the reactor vessel.
  • the supplied medium is supplied by means of a circulation circuit (12).
  • a battery of two or more devices of the present invention is provided.
  • a battery of two devices (ie reactors) of the present invention is provided.
  • a reaction and a reverse reaction take place in these two devices.
  • a contaminated starting substance can be purified.
  • contaminated lithium carbonate is converted into Lithium hydrogen carbonate is converted, which is converted back into pure lithium carbonate in a second apparatus of the battery using added steam.
  • cleaning elements can be introduced between the two apparatuses, e.g. one or more ion exchangers and/or one or more filters.
  • a battery of three devices (here "apparatus") of the present invention is provided.
  • apparatus This is used, for example, to convert solid U2CO3 with a slightly overstoichiometric amount of solid Ca(OH)2 to dissolved LiOH and solid CaCOs.
  • the selected embodiment promotes the formation of a high concentration of dissolved LiOH with minimized lithium losses that arise from undissolved or recrystallized U2CO3 in the solid product CaCOs.
  • the conversion reaction preferably takes place predominantly in the first apparatus and the conversion reactions are quantitatively completed in the other two apparatuses.
  • the filtrate, the wash filtrate and the overflow from the third apparatus reach the second apparatus, which is additionally fed with the underflow of the first apparatus and the underflow of a clarifier downstream of the first apparatus.
  • the resulting dilution effect dissolves solid U2CO3 from the first apparatus, which reacts with the unreacted Ca(OH)2 to form LiOH and CaCOs and completes the reaction.
  • the overflow from the first apparatus is fed into a clarifier and clarified so that the clear solution flowing out of it can be further processed using known methods to form lithium hydroxide monohydrate or other products.
  • contaminated lithium carbonate is continuously dissolved in a unit reactor.
  • the dissolution rate of lithium carbonate which is preferably between 10 kg/m 3 h and 25 kg/m 3 h
  • fresh suspension with contaminated lithium carbonate is added so that a preferred solids concentration of between 180 kg/m3 and 250 kg/m 3 is maintained in the lower region of the reactor.
  • suspension is withdrawn continuously or at regular intervals from the underflow of the reactor so that preferably at least 95 out of 100 mass parts of lithium carbonate are dissolved in the contaminated feedstock.
  • the criterion for the volume flow of the suspension withdrawal at the reactor underflow is to ensure the specific dissolution rate, the achievement of which can be monitored by measuring the density, refractive index or other characteristic measured variables of the solution in the lithium hydrogen carbonate solution.
  • the lithium carbonate withdrawn from the underflow of the reactor is used for other purposes.
  • the solid lithium carbonate discharged with the solution overflow is collected in a subsequent clarifier and returned to the standard reactor 1 with the clarifier underflow.
  • the clarifier overflow goes to a fine filter so that even the finest particles are removed from the lithium hydrogen carbonate solution stream. These fine particles are usually contaminants and are also removed from the process.
  • the fine filter is followed by ion exchangers which serve to remove dissolved multivalent cations such as calcium, magnesium or aluminum and/or borates from the lithium hydrogen carbonate solution.
  • ion exchangers which serve to remove dissolved multivalent cations such as calcium, magnesium or aluminum and/or borates from the lithium hydrogen carbonate solution.
  • These are preferably regenerated with dilute hydrochloric or nitric acid. They are preferably conditioned with dilute lithium hydroxide solution. This avoids an enrichment of other alkali metals, which would be the case if potassium hydroxide or sodium hydroxide were used instead of lithium hydroxide.
  • the lithium hydrogen carbonate solution purified in this way is then used to produce lithium carbonate again.
  • the inventive structure For this purpose, it is crystallized with the inventive structure, with a specific crystallization rate of 10 - 25 kg/hm 3 , by supplying steam, separated with a centrifuge, washed if necessary and passed on for drying.
  • the solution overflowing from the clarifier is collected and, depending on the permissible concentration of the other dissolved impurities such as sodium, potassium, chloride or sulfate, used in whole or in part to suspend contaminated lithium carbonate.
  • the solution used to suspend the contaminated lithium carbonate is cooled by means of water evaporation and the evaporated water is compressed so that it is returned to the inventive structure as heating steam, thereby reducing thermal energy consumption.
  • lithium carbonate is crystallized in a reactor according to one of the described embodiments and either separated from the mother liquor or in this is enriched.
  • the lithium carbonate then passes into a second reactor corresponding to the embodiments described, which is equipped with at least two, preferably three steam lances that correspond to one of the embodiments according to the invention.
  • the previously produced lithium carbonate is preferably introduced in suspended form through one steam lance.
  • a solution with a further metal salt is introduced through another.
  • a medium is introduced through at least one further steam lance, which either leads to supersaturation of the further cation introduced in the reactor or, in a preferred variant, provides a further anion that forms a precipitate with the further cation, the precipitation of the product being driven by the lithium carbonate present.
  • the lithium carbonate particles provide a large amount of growth surfaces, so that the Ü2CO3 particles are evenly coated with a layer that contains the precipitate of the metal salt.
  • the order of precipitation can be reversed if necessary, so that lithium carbonate envelops the particles consisting of a different cation or anion.
  • lithium salt solutions are processed in a series of successive crystallization steps, which, in addition to lithium as a cation, can also contain other cations and anions that hinder the crystallization of a lithium carbonate suitable for batteries.
  • the embodiments and active principles described in the invention are used to first crystallize one or more cations and/or anions in at least two successive crystallization or precipitation steps without lithium being co-precipitated in relevant quantities.
  • Common cations that must be almost completely removed from the solution are calcium or magnesium.
  • Common anions that influence the crystallization and purity of lithium carbonate are sulfate and borate.
  • Low-sulfate solution The brine contains 0.9% lithium, 6.2% sodium, 13% chloride and 0.02% sulfate.
  • High potassium content The brine contains 0.9% lithium, 4.2% sodium, 3.0% potassium, 12.7% chloride and 0.12% sulfate.
  • the lithium solutions are divided.
  • the lithium solution is fed through an injection pipe at a rate of 19 liters per hour.
  • 8 liters of lithium solution per hour are introduced in a similar manner.
  • a solution with 30% sodium carbonate is used, which is introduced into the first stirred tank of the cascade through an injection pipe.
  • the third stirred tank of the cascade is used to extend the residence time.
  • the suspension leaving the stirred tank cascade is collected in a clarifier and the solid is thickened, filtered, washed to remove any caustic residues and analyzed.
  • Scenarios 2 and 4 are carried out in a setup corresponding to Figure 9. Heating and temperature regulation are carried out via a steam lance as shown in Figure 4, by feeding in approximately 1 liter per hour of a steam-water mixture. 8.7 liters per hour of lithium solution and 2.1 liters per hour of soda solution are simultaneously fed into the crystallization reactor according to the invention via a setup corresponding to Figure 2. From the tenth hour, 2 liters per hour of product suspension is removed from the reactor underflow and continued until test hour 32. The overflow from the reactor is fed into a clarifier in which the entrained solid particles are collected and returned to the reactor via the underflow of the clarifier. This return begins with the first test hour. The removed suspension is filtered, washed to remove any caustic soda and the product is analyzed. The following impurities are found in the product:
  • Example 3 Production of spherical lithium carbonate by precipitation from a lithium sulfate solution.
  • a mass flow of 10.5 kg per hour of a solution containing 7.3% U2SO4, 13.4% Na2SC>4, 6.3% K2SO4 and traces of calcium, magnesium, rubidium and cesium is introduced into the interior of the reactor's draft tube at a temperature of 22 °C via a steam lance according to the invention as shown in Figure 5. Simultaneously, 2 kg per hour of a 33% Nat- The lithium carbonate solution is introduced into the interior of the guide tube via a steam lance according to the invention as shown in Figure 4 in such a way that the amount of lithium ions introduced is in a molar ratio of 2.21:1 to the amount of carbonate ions introduced. In this way, 477 g of lithium carbonate are crystallized per hour.
  • the conditions mentioned correspond to a specific production rate of 23.9 kg/(m 3 h).
  • a product with a purity of 99% is obtained with sodium sulfate, potassium sulfate and lithium sulfate as the main impurities that cannot be washed out.
  • the product falls in a spherical shape with a median diameter of 0.208 mm and a narrow particle size distribution of 0.169 mm as the limit value for the lower and 0.255 mm for the upper 10-of-100 size percentile.
  • a cylindrical steam lance with an immersion depth of 5 m extends into a reactor with a volume of 300 m 3 , which circulates a suspension of U2CO3 and an 80 % saturated NaCl solution.
  • the steam lance is operated with steam saturated at a temperature of 160 °C.
  • the Ü2CO3 suspension boils at 105 °C.
  • the solution has a thermal conductivity of 6 W/(mK).
  • a Nusselt number of 3434 was determined for this arrangement and process configuration. In order to achieve a temperature difference of less than 0.1 K between the medium temperature and the surface temperature of the outside of the steam lance, insulation with a thermal conductivity of 0.05 W/(mK) with a layer thickness of approx. 2 cm is required.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un dispositif et un procédé de cristallisation continue contrôlée de cristaux de sels métalliques, en particulier de cristaux de carbonate de lithium. Ces cristaux peuvent être produits à grande échelle avec une grande homogénéité.
PCT/EP2024/065811 2023-06-07 2024-06-07 Dispositif de production de cristaux de carbonate de lithium Pending WO2024251991A1 (fr)

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EP2536663A2 (fr) 2010-02-17 2012-12-26 Simbol Mining Corp. Procédés pour la préparation de carbonate de lithium de haute pureté et d'autres composés lithiés de haute pureté
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DE10304314A1 (de) * 2003-02-04 2004-08-12 Kali-Umwelttechnik Gmbh Verfahren zur Herstellung von Magnesiumhydroxid mit definierter Partikelgröße und Partikelform
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EP2536663A2 (fr) 2010-02-17 2012-12-26 Simbol Mining Corp. Procédés pour la préparation de carbonate de lithium de haute pureté et d'autres composés lithiés de haute pureté
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