EP3638624A1 - Procédé de production de composés de lithium et éventuellement d'autres métaux alcalins - Google Patents

Procédé de production de composés de lithium et éventuellement d'autres métaux alcalins

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Publication number
EP3638624A1
EP3638624A1 EP18750313.1A EP18750313A EP3638624A1 EP 3638624 A1 EP3638624 A1 EP 3638624A1 EP 18750313 A EP18750313 A EP 18750313A EP 3638624 A1 EP3638624 A1 EP 3638624A1
Authority
EP
European Patent Office
Prior art keywords
furnace
alkali metals
reagent
mineral
mixture
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
EP18750313.1A
Other languages
German (de)
English (en)
Inventor
Milos Faltus
Hong VU
Petr Dvorak
Eva KRISTIANOVA
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.)
Vysoka Skola Chemicko Technologicka V Praze
Original Assignee
Vysoka Skola Chemicko Technologicka V Praze
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Vysoka Skola Chemicko Technologicka V Praze filed Critical Vysoka Skola Chemicko Technologicka V Praze
Priority to DE18750313.1T priority Critical patent/DE18750313T1/de
Publication of EP3638624A1 publication Critical patent/EP3638624A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/364—Avoiding environmental pollution during cement-manufacturing
    • C04B7/365—Avoiding environmental pollution during cement-manufacturing by extracting part of the material from the process flow and returning it into the process after a separate treatment, e.g. in a separate retention unit under specific conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a method for recovering compounds of lithium and optionally of further alkali metals from silicate raw materials.
  • Alkali metals especially rare ones such as Li, Rb and Cs, and also K and Na as minor components, can be obtained from silicates, aluminosilicates, phosphates and other minerals, such as lepidolite, zinnwaldite, spodumene, petalite, pollucite and amblygonite, by several methods.
  • a first method is autoclave leaching at high temperatures and pressures in acidic medium, often using mineral acids, such as sulfuric acid, hydrochloric acid or other acids.
  • mineral acids such as sulfuric acid, hydrochloric acid or other acids.
  • sulfuric acid is used because it is the cheapest and most accessible leaching agent.
  • Typical leaching agents for autoclave leaching in alkaline medium are solutions of NaOH or Na 2 C0 3 .
  • neutral medium for example in solutions of NaCl, Na 2 S0 4 , CaCl 2 and other salts.
  • anion parts are dissociated from the structure of minerals and alkali metals are dissolved.
  • a silicate or aluminosilicate residue, respectively, is precipitated on the bottom of the autoclave.
  • a second, probably the most common, method for recovering alkali metals is sintering minerals containing alkali metals with different sintering agents, mainly CaC0 3 , CaO, (Ca,Mg)C0 3 , MgC0 3 , MgO, CaS0 4 , CaCl 2 , Na 2 S0 4 , NaCl, NaOH, Na 2 C0 3 , K 2 S0 4 , or with other chemicals or their mixtures at different ratios.
  • Sintering takes place in a furnace at a temperature within the range of from 700 to 1150 °C.
  • sintering decomposition of the structure of silicates, aluminosilicates or phosphates occurs, and that leads to formation of insoluble compounds of alkali metals, separation of anion parts into an insoluble form or binding of the anion parts of alkali metal compounds on insoluble silicates, aluminosilicates or phosphates.
  • the resulting sinters are water leached. Some sinters disintegrate when getting into contact with water when they are still hot. Some sinters disintegrate before leaching when exposed to air. For some sinters, milling is needed before leaching.
  • the patent document CN103979809 describes a method of utilizing leaching residues after Li recovery from lepidolite sinters as a constituent in production of white Portland cement, by milling the leaching residues together with white Portland clinker, gypsum and lime. This method provides utilization of otherwise hardly utilizable waste products after recovery of Li and other alkali metals from silicate minerals. This way to utilize waste is not feasible under current legislation in force in the EU.
  • the patent US2627452 describes a process of sintering a mixture of spodumene, calcium carbonate, and eventually sand and calcium chloride at an unspecified ratio, at temperature from 1100 °C to 1200 °C, which leads to volatilization of lithium chloride and its separation from the Portland clinker.
  • This patent has several major disadvantages.
  • the first disadvantage is that at temperatures in the described interval, a good Portland clinker with required properties according to current standards is not formed, but a mixture of quicklime and clinker minerals with dominantly dicalcium silicates without glassy phase and additional common minerals of Portland clinker is formed instead.
  • the invention also does not take into account the possibility of feeding chlorine into the furnace in other form than CaCl 2 , especially as chlorine gas or chlorine from fuels, which contain chlorinated organic compounds, such as PVC, chloroprene rubber and others.
  • this patent does not deal with the possibility of utilization of calcareous rocks with low content of CaC0 3 , for example clay limestone and marl. This aspect is very important, because lithium rich sources are not always located close to sources of sufficiently pure limestone.
  • Another patent US 1202327 describes a possibility of recovering alkali metal compounds during production of Portland clinker, using fuels containing sulfur in the presence of water steam in the calcination zone of the furnace.
  • the patent US4285194 describes a solution for recovering Li adsorbed on a clay mineral, also a type of phyllosilicate, by sintering the mineral with CaO or CaC0 3 in the presence of H 2 0-HC1 vapours at temperature range of from 450 °C to 950 °C.
  • the patent has an additional disadvantage that the obtained sinter is not utilizable in building industry, because at the given temperature range and with the given chemical composition a full-value material, such as Portland clinker or hydraulic or air lime, cannot be formed.
  • the conventional chloride by-pass systems do not have a sufficient capacity for efficiently processing larger quantities of raw materials containing alkali metals, including lithium, and allow processing only relatively small quantities of those raw materials. Adding larger quantities of the raw material as a corrector leads to high losses of alkali metals into cement clinkers and at the same time to degradation of clinkers due to disproportionately high contents of alkali metals in the clinker.
  • There is a number of known documents which address the production of low alkali clinkers with simultaneous recovery of alkali metals or deal with Li recovery from silicate ores by the volatilization method CN 101607796 A; CN 201530782 U; GB 891784A; GB 804962 A).
  • None of the above listed documents addresses directly the issues related to processing of phyllosilicate ores with low Li content and low content of other alkali metals, and to highly effective recovery of rare alkali metals when processing larger quantities of low-grade lithium silicate ores at a low ratio between calcium and silicon/aluminum.
  • the documents do not address the influence of fluorine on sintering or melting temperature as well as the phase composition of clinkers.
  • None of the above listed patents or patent applications address issues related to selectively recovering individual alkali metals contained in fractions of gas phases from the kiln space. At the same time, the listed documents do not address the loss of thermal heat, which can be essential for the process economics.
  • the alkali metals pass into glass phase to a large extent, because the mixture does not contain the necessary minimal quantities of Ca or other alkaline earth metals.
  • an energetically and environmentally friendly solution for the recovery of alkali metals from low grade phyllosilicate ores was developed as described below.
  • the object of the invention is a method for recovering lithium compounds and optionally further alkali metal compounds, wherein a mineral from the group of phyllosilicates containing lithium and optionally further alkali metals as well as at least 0.2 wt. %, preferably at least 0.9 wt.
  • %, of fluorine undergoes a thermal treatment in a furnace at a temperature within the range of from 1100 °C to 1700 °C, preferably at a temperature within the range of from 1220 °C to 1700 °C, at a pressure within the range of from 20 KPa to 150 kPa for a period of 15 to 360 minutes, in the presence of a reagent which contains a) at least one substance from a group comprising carbonates, oxides, hydroxides, sulfates, sulfites and chlorides of alkaline earth metals, preferably of calcium; and b) at least one substance capable of releasing chlorine and/or hydrogen chloride and/or sulfur trioxide and/or sulfur dioxide during the thermal treatment, wherein the molar ratio of the total amount of sulfur trioxide and/or sulfur dioxide expressed as S0 3 and/or of chlorine and/or hydrogen chloride expressed as Cl 2 to the total amount of alkali metals including lithium , released from the silicate mineral in the reaction space of
  • the fluorine content in the mixture of the phyllosilicate mineral with the reagent is from 0.1 to 2 wt. %, preferably from 0.2 to 2 wt. %, for decomposition of the structure of the phyllosilicate mineral and volatilization of lithium compounds and optionally of further alkali metal compounds from the thermally treated phyllosilicate mineral; the compounds of lithium and optionally of further alkali metals are subsequently recovered by condensation by drawing off from one or more different places with different temperatures within the internal space of the furnace from 50 to 100 vol. % of flue gases formed in the furnace , wherein the rate and volume of the drawn-off flue gases from different places can be different for the selective recovery of compounds of individual alkali metals or their groups.
  • the weight ratio of the total amount of alkaline earth metal oxides, in particular calcium oxide, to Si0 2 in the mixture of the silicate mineral with the reagent is at least 1.
  • the weight ratio of the total amount of alkaline earth metal oxides, in particular calcium oxide, to the total amount of Si0 2 , A1 2 0 3 and Fe 2 0 3 in the mixture of the silicate mineral with the reagent is equal to at least 1.7.
  • the mineral from the group of phyllosilicates containing Li and optionally further alkali metals, alone or with the reagent or with at least one substance contained in the reagent, is subjected before the thermal treatment to a mechanochemical activation in a high-speed countercurrent two- rotor mill at a rotating circumferential rotor speed of at least 180 m.s ⁇
  • the mineral from the group of phyllosilicates containing Li and optionally further alkali metals is continuously or periodically stirred during the thermal treatment in the presence of the reagent.
  • the mineral from the group of phyllosilicates containing Li and optionally further alkali metals alone or with the reagent or with at least one substance from the group containing carbonates, oxides, hydroxides, sulfates and sulfites is subjected to a thermal pretreatment at a temperature within the range of from 700 °C to 1000 °C, leading to dehydroxylation of the phyllosilicate mineral and to dehydration and/or decarbonization of substances in the reagent.
  • a raw materials mixture containing at least the phyllosilicate and a component a) of the reagent, optionally also a component b) of the reagent is subjected to milling in a high-speed countercurrent mill before the thermal treatment.
  • Milling in the high-speed countercurrent mill has several advantages over other milling methods, such as acceleration of the reactions due to prevention of formation of aggregates. Aggregates can be formed in other milling methods for example due to hygroscopicity of some components (e.g. CaCl 2 ), and the countercurrent mill usually also helps to remove water from the milled mixture.
  • the substance capable of releasing chlorine and/or hydrogen chloride during the thermal treatment may be chlorinated organic compounds, such as chlorinated polymers (for example polyvinylchloride, polychloroprene), polychlorinated biphenyls, or halogenated oils. These compounds can be burnt as alternative fuels and their emissions contain chlorine and/or hydrogen chloride. Utilization of these flue gasses, which would otherwise need to be removed, in an industrial process and chlorine fixation are very desirable from the economic and environmental point of view.
  • the flue gasses are drawn off to a separate air-cooled condenser/heat exchanger system, in which the flue gasses are cooled to a temperature within the range of 100 °C to 900 °C, leading to condensation of volatile alkali metal compounds contained in the flue gasses.
  • the condensed alkali metals compounds are removed from the condenser mechanically and/or pneumatically and/or hydraulically, wherein the air heated in the condenserheat exchanger is used as a heating air for the thermal pre -treatment of the phyllosilicate mineral containing lithium and optionally further alkali metals, alone or together with the reagent or together with at least one substance from the group containing carbonates, oxides, hydroxides, sulfates and sulfites at a temperature within the range of from 700 °C to 1000 °C; and/or the preheated air is used as a heating air for the thermal treatment of the phyllosilicate mineral together with the reagent in the furnace at a temperature within the range of from 1100 °C to 1700 °C, preferably at a temperature within the range of from 1220 °C to 1700 °C and/or for other technological operations.
  • These technological operations may include solution concentration, evaporation, drying and heating.
  • a solution of at least one substance from the group of chlorides, sulfates and sulfites of alkaline earth metals, in particular of Ca is added to the mixture of the phyllosilicate mineral with at least one substance from the group containing carbonates, oxides and hydroxides of alkaline earth metals, in particular of Ca, before the thermal treatment; or the said mixture is treated with at least one inorganic acid, in particular selected from a group comprising hydrochloric acid, sulfuric acid and sulfurous acid, or with a solution thereof; and subsequently the mixture is homogenized, dried, deagglomerated and/or milled to the particle size smaller than 50 ⁇ for increasing the quality of homogenization of the mixture of the phyllosilicate mineral with substances of the reagent and for increasing the effectiveness of the subsequent thermal treatment.
  • Alkali metals including lithium are recovered in particular in the form of halides, for example chlorides, fluorides, or in the form of sulfates or double salts, such as sulfate/aluminates, halide/aluminates (for examples chloride/aluminates).
  • halides for example chlorides, fluorides
  • sulfates or double salts such as sulfate/aluminates, halide/aluminates (for examples chloride/aluminates).
  • Alkali metals shall be understood as including in particular lithium, rubidium, cesium, sodium, potassium.
  • Alkaline earth metals shall be understood as including in particular magnesium, calcium.
  • Phyllosilicates or layered silicates are a group of silicate minerals composed of flat layers of shared three-atom or four-atom molecules of Si0 4 of tetrahedral form. Most phyllosilicates have a platelet or leaf-like habitus (according to the direction of cleavage they are mostly thin scales or leaves) with perfect fragmentation, due to the presence of endless networks in the structure, including Si tetrahedra. The individual nets are then bound into layers by relatively weak forces.
  • interconnection between network layered complexes may be different - either weak electrostatic forces connected by the presence of (OH) groups, or so-called interlayer cations (usually Na, K, Ca, Mg, Rb, Li) may be located between network complexes.
  • the phyllosilicates form the Class VIII / H.
  • the phyllosilicates suitable for use in the method of the present invention belong in particular to mineral groups:
  • the main mineral with industrial content of Li is hectorite Na 0j3 (Mg, Li) 3 Si 4 O 10 (OH) 2 ; however other minerals such as illite contain a high amount of K and
  • Rb, or montmorillonite may adsorb lithium
  • - mica group which includes a variety of minerals with Li content of from about 0.4 wt. %, for example up to about 4 wt. % Li, such as lepidolite, zinnwaldite, polylithionite, trilithionite, protolithionite, Li-muskovite, Li-biotite;
  • the invention is based on the finding that during thermal treatment in an oxidative medium in the presence of a reagent containing alkaline earth metals, especially calcium, and also substances capable of releasing volatile gasses such as Cl 2 , S0 3 and others, which may include certain types of alternative fuels, the structure of phyllosilicate minerals containing the groups (F,OH), for example zinnwaldite (KLiFe ⁇ + Al(AlSi3)Oio(F,OH)2), decomposes.
  • the decomposition of the phyllosilicate mineral takes place so that at first F and OH bound in the group (F,OH) are released, meanwhile oxidation of Fe 2+ to Fe 3+ and a release of one molecule of H 2 0 occurs, and subsequently a molecule of HF is formed.
  • F,OH fluoride-containing group
  • oxidation of Fe 2+ to Fe 3+ and a release of one molecule of H 2 0 occurs, and subsequently a molecule of HF is formed.
  • alkaline earth metal compounds especially calcium compounds
  • oxides of lithium and of further alkali metals are formed. The oxides alone are not capable of being volatilized at temperatures below 1700 °C.
  • the oxides react with chlorine or S0 3 to form salts that are capable of being volatilized within the temperature range of from 1100 °C to 1670 °C.
  • the method of the present invention has several fundamental differences and it is based on a thermal treatment by a complete or a partial melting of the silicate mineral, during which the formation of chlorides and/or sulfates of lithium and further alkali metals and subsequent complete volatilization occur, depending on pressure/temperature conditions, the residence time of the phyllosilicate mineral containing lithium and optionally further alkali metals inside the furnace, and also on the heating rate of the raw materials mixture entering the furnace.
  • the residue after the recovery of Li and optionally further alkali metals has a form of acidic, basic or ultrabasic glassy phase, optionally with varying percentages of crystalline phases of clinker minerals, especially belite, sulfobelite, alite and others.
  • the fluorine present in the system enters at the temperature range of from 1100 °C to 1300 °C several reactions, during which the formation of CaF 2 , fluorosilicate and fluoroaluminate minerals takes place at varying degrees.
  • the method of recovering lithium according to this invention is energetically and environmentally very efficient, because it requires only a small volume of raw materials, or raw materials of lower quality with lower CaO content and it also produces a smaller volume of C0 2 emissions, compared to the previously known methods.
  • An additional fundamental difference is that unlike the conventional cement technology, 50 to 100% of flue gases are drawn off from the furnace space into an apparatusfor condensation of alkali metals.
  • the traditional cement technology uses the so-called cement chlorine or alkaline by-pass to reduce the content of alkalis, CI, S and other substances in production of Portland clinker.
  • This system 10 wt.% exceptionally 25 wt. % of flue gases are drawn off from the furnace in places with the highest concentration of alkalis, CI and S.
  • fine and very fine milled they can be used as an analog of granular blast furnace slag and must also meet all the requirements for granular blast furnace slag, especially a minimum glassy content of at least 2/3 and a minimum CaO: Si0 2 weight ratio of at least 1.
  • This material also has to meet a number of other requirements given by the standard for granular blast furnace slag.
  • the formation of the analogue of granular blast furnace slag takes place at temperatures usually above 1500 °C, but at lower pressures and with a suitable composition of the raw material mixture, in particular with an increased content of fluorine, the transition to viscous state may occur at temperatures several hundred degrees lower.
  • this composition In addition to the advantages of low energy costs associated with a small amount of dissociated CaC0 3 and low carbon footprint, this composition generates a very low hydration heat and has a very low alkali content.
  • CaO:Si0 2 below 1, so-called acidic slags are formed. They have an advantage in that they crystallize slowly and can be cooled off only by air in order to maintain the absolute dominance of the glass phase. After fine grinding, they can be used as high quality pozzolans for the preparation of pozzolanic or mixed cements. Accordingly, the solid products of this treatment are suitable for use as binders or binder components for significantly limiting the risk of alkaline reaction of the aggregate. For the preparation of hydraulic binders based on solid residual products after obtaining the Li and further alkali metals according to the invention, the use of mechanochemical activation is suitable.
  • Another major advantage of the solution according to the present invention is the possibility of selectively drawing off the gaseous products from different locations in the furnace at different temperatures which allows to a large extent a selective recovery of individual alkali metals or their compounds, or individual fractions of volatile compounds enriched always with one compounds of a certain alkali metal, respectively.
  • the solution according to the present invention also envisages the possibility of heat recovery/recuperation during the condensation of the volatile alkali metal compounds which can be condensed in an air-cooled heatexchanger recuperation systems.
  • the cooling air is heated and the heat that has been removed from the furnace together with the flue gases may enter the pre-heating treatment process of the raw material mixture in the precalciner independently or as the combustion air for the precalciner or furnace in which sintering or melting is carried out.
  • this heat can be used for other technological operations, but unlike other solutions, it is utilized, and that positively contributes to the economy of the process of recovering Li and other alkali metals.
  • the invention is further explained in the examples which should not be construed as limiting the scope of the invention.
  • a raw material mixture in the ratio shown in Table 1 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, zinnwaldite concentrate from the deposit Cinovec and CaCl 2 .
  • the mixture is ground in a high-speed counter mill at a circumferential speed of 210 ms 1 to the medium grain size of less than 50 ⁇ . It is then subjected to a particle size enlargement to 7 mm and melting in an internally heated shaft furnace at 1350 °C for 30 minutes. During the melting in the furnace, chlorides and other compounds of alkali metals are released.
  • the furnace pressure is maintained at ⁇ 90 kPa.
  • All hot flue gas carrying volatile compounds is drawn off from the furnace into a regenerative condenser in which the extracted alkali metal salts are obtained from the hot gas.
  • the resulting mixture contains 75% of Li, 90% of K and 95% of Rb from the original batch.
  • a basic melt is formed, almost free of chlorine, sulfur and alkali metals, which is fast-cooled by an air flow to a temperature below 400 °C, followed by additional cooling down to a temperature below 100° C, to form a basic granular slag with a CaO: Si0 2 ratio of 1.02 and a (CaO + Si0 2 ) /(A1 2 0 3 + Fe 2 0 3 ) ratio of 3.46.
  • the slag can be used to produce hydraulic binders as a granular blast furnace slag analogue.
  • the heated air from the melt cooling and from the regenerative condenser is used as combustion air for heating the shaft furnace.
  • Table 1 Composition of the raw material mixture for preparation of basic granular slag in a shaft furnace
  • a raw material mixture in the ratio shown in Table 2 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC and zinnwaldite concentrate from the deposit Cinovec.
  • the mixture is ground in a high-speed counter mill at a circumferential rotor speed of 210 m.s 1 to the average grain size of less than 30 ⁇ , then the ground mixture is at first calcined in a cyclone pre-calciner for about 12 seconds at a temperature of 920 °C. Due to the high content of F, this prepared mixture is melted in a rotary kiln (furnace) at a temperature of 1350 °C for 40 min to form a melt virtually free of CI, S and alkali metals.
  • the fuel used in the rotary kiln contains 114 kg of CI per 1 tone of zinnwaldite concentrate.
  • the heated air from the melt cooling is used as combustion air for heating the rotary kiln.
  • the furnace pressure is maintained at -110 kPa.
  • All hot flue gas is drawn off from the furnace into a condenser/heatexchanger in which volatile alkali metal chlorides are obtained from the hot gas.
  • the obtained mixture contains 85% of Li, 92% of K and 97% of Rb from the original batch.
  • the air heated in the condenser/heat exchanger is used as calcination and combustion air in the calciner.
  • a portion of the flue gases is drawn off at approximately 25% of their total volume at a distance of 7 m from the start of the rotary kiln. The rest of the flue gases are drawn off above the input ports for the raw material mixture at the start of the rotary kiln.
  • Table 2 Composition of the raw material mixture for preparation of basic granular slag in a rotary furnace
  • a raw material mixture in the ratio shown in Table 3 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, zinnwaldite concentrate from the deposit Cinovec and CaCl 2 .
  • the mixture is ground in a high-speed two-rotor counter mill at a circumferential speed of 210 m.s 1 to an average grain size of less than 50 ⁇ and then subjected to a heat treatment consisting of calcination in a pre-calcination cyclone apparatus for approx. 10 seconds at temperature of about 950 °C and subsequently melted in a shaft furnace at 1420 °C for 30 minutes. During melting in the furnace volatilization of alkali metal salts occurs.
  • the product After rapid cooling of the melt in an air flow to a temperature below 400 °C and subsequent cooling by a water spray to a temperature below 100 °C, the product is usable for the production of mineral fibers or hydraulic binders as an analogue of granular blast furnace slag.
  • the obtained mixture contains 90% of Li, 95% of K and 95% of Rb from the original batch.
  • the heated air from the melt cooling is used as the primary combustion air for heating the shaft furnace.
  • the heated air from the condenser/heat exchanger is used as secondary combustion air.
  • Table 3 Composition of the raw material mixture for preparation of basic granular slag in a shaft furnace with internal heating
  • a raw material mixture in the ratio shown in Table 4 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC and zinnwaldite concentrate from the deposit Cinovec.
  • the mixture is milled in a high speed two-rotor counter-rotating mill at a rate of 220 m.s 1 to an average particle size of less than 50 microns.
  • the milled product is further subjected to preheating and calcination in a cyclone-type precalciner for 10 s and subsequently melted in a rotary furnace (kiln) with a diameter to length ratio 1 : 15.
  • the product After rapid cooling of the melt in an air flow to a temperature below 400 °C and subsequent cooling by a water spray to a temperature below 100 °C, the product is usable for the production of hydraulic binders as an analogue of granular blast furnace slag.
  • the heated air from the melt cooling is used as the primary combustion air for heating the shaft furnace.
  • the heated air from the condenser/heat exchanger is used as combustion and calcination air for the pre-calciner.
  • the condensed mixture obtained contains 91% of Li, 94% of K and 96% of Rb from the original batch.
  • a raw material mixture in the ratio shown in Table 5 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, zinnwaldite concentrate from the deposit Cinovec and CaCl 2 .
  • the mixture is milled in a high-speed mill at a rotation speed of 200 m.s 1 to an average grain size of less than 70 ⁇ and melted at 1500 °C for 20 minutes in a continuous bathtub furnace with four parallel series of passes.
  • compounds, mainly alkali metal chlorides are formed, volatilized from the sintering mixture and drawn off from the furnace through the passes.
  • the furnace pressure is maintained at 90 kPa.
  • Flue gases removed from the furnace by the passes are discharged to a condenser/heat exchanger where condensation of volatile alkali metal compounds occurs.
  • the flue gases removed from the furnace through the third and fourth series of passes do not contain lithium chlorides.
  • the melt which is rapidly cooled by air in a fluid cooler to a temperature below 200 °C, is usable for the production of hydraulic binders as an analogue of granular blast furnace slag.
  • the heated air from the melt cooling from the condenser/heat exchanger is used as the primary combustion air for heating the bath furnace.
  • the condensed mixture obtained contains 85% of Li, 90% of K and 92% of Rb from the original batch.
  • a raw material mixture in the ratio shown in Table 6 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, zinnwaldite concentrate from the deposit Cinovec and calcium chloride.
  • the mixture is milled in a high speed two-rotor counter-rotating mill to an average particle size of less than 30 ⁇ .
  • the milled product is further subjected to preheating and calcination in a precalciner at the temperature of 890 °C and subsequently melted in a rotary furnace with a diameter to length ratio 1 : 17. Due to the appropriate composition and the increased content of F, the melting occurs only at 1340 °C in the hottest furnace zone, at the furnace passage time of 45 min.
  • the furnace pressure is maintained at 110 kPa.
  • zinnwaldite and calcium chloride During sintering and subsequent melting, the decomposition of zinnwaldite and calcium chloride occurs, alkali metal chlorides are formed, volatilized and drawn off from the furnace space.
  • the drawing-off is carried out in such a way that first 10% of the volume of flue gas is drawn off from the space located 10 m from the beginning of the kiln, the other 15% is drawn off from the space located 5 m distant from the beginning of the rotary kiln and the rest of the gas is drawn off at the beginning of the rotary kiln. All gases are fed to condenser heat exchangers.
  • the condensed mixture obtained from the first drawing-off stage contains 70% of Li, 3% of K from the original batch.
  • the condensed mixture obtained from the second extraction stage contains 5% of Li, 80% of K and 88% of Rb from the original batch.
  • the condensed mixture obtained immediately from the beginning of the rotary kiln contains 1 % of Li, 3% of K and 4% of Rb from the original batch.
  • the melt is rapidly cooled in an air flow to a temperature below 100 °C.
  • the obtained product is usable for the production of glassy acid slag, which after milling can be used as pozzolanic additives to hydraulic binders for reducing the risk of alkaline reaction of aggregates.
  • the heated air from the melt cooling is used as the primary combustion air for heating the furnace.
  • the heated air of the feeder condenser is used as combustion and calcination air for the precalciner.
  • a raw material mixture in the ratio shown in Table 7 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, pure limestone from the deposit Certovy schody, zinnwaldite concentrate from the deposit Cinovec and calcium chloride.
  • the mixture is milled in a high speed two-rotor counter-rotating mill to an average particle size of less than 30 ⁇ .
  • the milled product is further subjected to preheating and calcination in a precalciner at temperature of 890°C and subsequently melted in a rotary kiln (furnace) with a diameter to length ratio 1: 17.
  • the condensed mixture obtained from the first drawing-off stage contains 75 % of Li, 5 % of K from the original batch.
  • the condensed mixture obtained from the second extraction stage contains 10 % of Li, 85 % of K and 90% of Rb from the original batch.
  • the condensed mixture obtained immediately from the beginning of the rotary kiln contains 1 % of Li, 5 % of K and 7 % of Rb from the original batch.
  • the clinker is rapidly cooled in an air flow to a temperature below 200 °C.
  • the obtained product is usable for the production of Portland cement and other hydraulic binders.
  • the heated air from the melt cooling is used as the primary combustion air for heating the shaft furnace.
  • the heated air of the feeder condenser is used as combustion and calcination air for the precalciner.
  • Table 7 Composition of the raw material mixture for sintering in a rotary kiln for the production of alithic Portland clinker
  • a raw material mixture in the ratio shown in Table 8 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, pure limestone from the deposit Certovy schody and zinnwaldite concentrate from the deposit Cinovec.
  • the mixture is milled in a high speed two-rotor counter-rotating mill at the at the circumferential speed of 210 m.s 1 to an average particle size of less than 30 ⁇ .
  • the milled product is further subjected to preheating and calcination in a precalciner at temperature of 890°C and subsequently melted in a rotary kiln (furnace) with a diameter to length ratio 1 :17.
  • the clinker is rapidly cooled in an air flow to a temperature below 200 °C.
  • the obtained product is usable for the production of Portland cements and other hydraulic binders.
  • the clinker together with the additives is ground in a shearing roller mill to achieve a grain size of less than 0.3 mm and subsequently in a high-speed, counter-rotating two-rotor mill to achieve the grain size below 50 ⁇ .
  • the heated air from the clinker cooling is used as the primary combustion air for heating the rotary kiln and partly for the precalciner.
  • the heated air from the condenser/heat exchanger is used as combustion and calcination air for the precalciner.
  • the obtained condensed mixture contains 85 % of Li, 90 % of K and 91 % of Rb from the original batch.
  • Table 8 Composition of the raw material mixture for sintering in a rotary kiln for the production of allitic - bellitic clinker
  • a raw material mixture in the ratio shown in Table 9 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, pure limestone from the deposit Certovy schody, zinnwaldite concentrate from the deposit Cinovec and gypsum from the semi-dry flue gas desulfurization method.
  • the mixture is milled in a high speed two-rotor counter-rotating mill at the at the circumferential speed of 240 m.s 1 to an average particle size less than 30 ⁇ .
  • the milled product is further subjected to preheating and calcination in a precalciner at temperature of 890°C and subsequently sintered in a rotary kiln (furnace) with a diameter to length ratio 1 : 17.
  • the clinker is rapidly cooled in an air flow to a temperature below 200 °C.
  • the obtained product is usable for the production of Portland cements and other hydraulic binders.
  • the clinker together with the additives is ground in a shearing cylindrical mill to achieve a grain size of less than 0.3 mm and subsequently in a high-speed, counter-rotating two-rotor mill at a circumferential speed of 230 m.s 1 to achieve a grain size below 10 ⁇ .
  • the heated air from the clinker cooling is used as the primary combustion air for heating the rotary kiln and partly for the precalciner.
  • the heated air from the condenser/heat exchanger is used as combustion and calcination air for the precalciner.
  • the obtained condensed mixture contains 89 % of Li, 92 % of K and 94 % of Rb from the original batch.
  • a raw material mixture in the ratio shown in Table 10 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, pure limestone from the deposit Certovy schody, a Li-Fe muscovite concentrate from the deposit Krasno and calcium fluoride.
  • the mixture is milled in a ball mill to achieve the average grain size of less than 30 ⁇ and further subjected to preheating and calcination in a cyclone pre-calciner at 900 °C for 10 seconds and then sintering in a rotary kiln (furnace)with the internal diameter to length ratio of 1 : 17.
  • the clinker is rapidly cooled in an air flow to a temperature below 200 °C.
  • the obtained product is usable as a base for the production of hydraulic binders.
  • the heated air from the clinker cooling is used as the primary combustion air for heating the rotary kiln and partly for the precalciner.
  • the heated air from the condenser/heat exchanger is used as combustion and calcination air for the precalciner.
  • the obtained condensed mixture contains 90 % of Li, 93 % of K and 95 % of Rb from the original batch.
  • a raw material mixture in the ratio shown in Table 11 is produced by mixing calcium marl from the deposit Upohlavy of Lafarge Cement JSC, Li-Fe muscovite concentrate from the deposit Krasno and calcium fluoride.
  • the mixture which is milled in a high-speed counter mill at a circumferential speed of 200 m.s 1 to achieve the mean grain size of less than 50 ⁇ .
  • the milled product is subjected to a thermal treatment consisting of calcination in a cyclone precalciner for about 10 seconds at temperature of about 950 0 C and subsequent melting in a rotary kiln (furnace) with a ratio of internal diameter to a length of 1 : 17 at 1420 0 C at the furnace passage time of 40 minutes.
  • the furnace pressure is maintained at 110 kPa.
  • a fuel with the content of 85.5 kg CI per 1 tone of the Li- Fe muscovite concentrate is used to heat the rotary kiln.
  • the Li-Fe muscovite decomposes, HCl and CI are released from the fuel, alkali metal chlorides are formed and volatilized. All hot flue gas is drawn off from the furnace into a condenser/heat exchanger in which volatilized alkali metal chlorides are obtained from the hot gas.
  • the melt is rapidly cooled in an air flow to a temperature below 100 °C.
  • the obtained product is usable as an analogue of granular blast furnace slag.
  • the heated air from the melt cooling is used as the primary combustion air for heating the rotary kiln.
  • the heated air from the condenser/heat exchanger is used as secondary combustion air.
  • the obtained condensed mixture contains 93 % of Li, 97 % of K and 99 % of Rb from the original batch.
  • Table 11 The composition of the feed mixture for sintering in a rotary kiln to produce a sulfobelic clinker
  • a raw material mixture in the ratio shown in Table 12 is produced by mixing pure limestone from the deposit Certovy schody and zinnwaldite concentrate from the deposit Cinovec.
  • the mixture is milled in a high-speed two-rotor counter mill at a circumferential speed of 200 m-s to achieve an average grain size of less than 50 ⁇ .
  • the milled product is subjected to pre-calcination in a cyclone calciner at 920 0 C for 12 s. Subsequently, the pre -calcined mixture is mixed with 30 % HC1 in the ratio shown in Table 12 in order to treat the mixture with HC1 .
  • the mixture is dried and subjected to deagglomeration in a two-rotor high-speed contralateral pin mill at a circumferential speed of 100 m.s ⁇ Furthermore, the mixture is subjected to sintering in a rotating kiln (furnace) with an internal diameter to length ratio of 1 : 17. Due to a suitable composition and an increased F content of 0.71, the sintering takes place only at 1380 °C in the hottest furnace zone at the furnace passage time of 40 min. The furnace pressure is maintained at 110 kPa. All gases from the rotary kiln are fed to a condenser/heat exchanger.
  • the obtained condensed mixture contains 92 % of Li, 93 % of Ka and 97 % of Rb from the original batch charge.
  • the mixture of alkali metal compounds and other compounds obtained from the furnace is processed further by known methods.
  • the clinker is rapidly cooled in an air flow to a temperature below 200 °C.
  • the obtained product is usable in the production of Portland clinkers and other hydraulic binders.
  • the clinker, together with additives, is milled in a shear roll mill to a particle size of less than 0.3 mm, and then in a high-speed countercurrent two-rotor mill at a circumferential velocity of 220 m.s 1 for the grain size below 40 ⁇ .
  • the heated air from the clinker cooling is used as the primary combustion air for heating the rotary kiln or partly for heating the precalciner.
  • the heated air from the condenser/heat exchanger is used as combustion and calcination air for the precalciner for drying the raw mixture after its reaction with HC1.
  • Table 12 The composition of the feed mixture for sintering in a rotary kiln to produce a sulfobelic clinker

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  • Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un procédé de récupération de lithium et éventuellement d'autres composés de métal alcalin, un minéral provenant du groupe des phyllosilicates contenant du lithium et éventuellement des métaux alcalins supplémentaires et également au moins 0,2 % en pds, préférablement au moins 0,9 % en pds, de fluor, étant soumis à un traitement thermique dans un four à une température comprise à l'intérieur de la plage de 1 100 °C à 1 700 °C, préférablement à une température située dans la plage de 1 220 °C à 1 700 °C, à une pression située à l'intérieur de la plage de 20 kPa à 150 kPa sur une durée de 15 à 360 minutes, en présence d'un réactif qui contient a) au moins une substance d'un groupe comprenant des carbonates, des oxydes, des hydroxydes, des sulfates, des sulfites et des chlorures de métaux alcalino-terreux, en particulier de calcium ; et b) au moins une substance capable de libérer du chlore et/ou du chlorure d'hydrogène et/ou du trioxyde de soufre et/ou du dioxyde de soufre durant le traitement thermique, où le rapport molaire de la quantité totale du trioxyde de soufre et/ou du dioxyde de soufre exprimé sous la forme de SO3 et/ou du chlore et/ou du chlorure d'hydrogène exprimé sous la forme de Cl2 par rapport à la quantité totale des métaux alcalins comprenant le lithium, libérés depuis le minéral silicate dans l'espace réactionnel dans le four, est d'au moins 0,5, la teneur des métaux alcalino-terreux, en particulier du calcium, recalculée sous la forme de leur teneur en oxyde, dans le mélange du minéral phyllosilicate avec le réactif étant d'au moins 20 % en pds, et la teneur en fluor dans le mélange du minéral phyllosilicate avec le réactif étant de 0,1 à 2 % en pds, préférablement de 0,2 à 2 % en pds, pour la décomposition de la structure du minéral phyllosilicate et pour la volatilisation des composés de lithium et éventuellement des composés de métal alcalin supplémentaires à partir du minéral phyllosilicate thermiquement traité, et les composés de lithium et éventuellement les métaux alcalins supplémentaires sont par la suite récupérés par condensation par soutirage du four de 50 à 100 % en volume du gaz de combustion formé dans le four depuis un ou plusieurs lieux différents présentant des températures différentes, où la vitesse et le volume d'extraction des gaz de combustion des différents lieux peuvent être différents pour la récupération sélective des composés de métaux alcalins individuels ou leurs groupes.
EP18750313.1A 2017-06-16 2018-06-15 Procédé de production de composés de lithium et éventuellement d'autres métaux alcalins Pending EP3638624A1 (fr)

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CZ2017-343A CZ2017343A3 (cs) 2017-06-16 2017-06-16 Způsob získávání sloučenin Li
PCT/CZ2018/050035 WO2018228618A1 (fr) 2017-06-16 2018-06-15 Procédé de production de composés de lithium et éventuellement d'autres métaux alcalins

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EP4039835A1 (fr) 2021-02-05 2022-08-10 Holcim Technology Ltd Procédé d'extraction de lithium à partir d'un mélange de matière première

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US2627452A (en) * 1949-07-06 1953-02-03 Scient Design Co Preparation of lithium chloride from spodumene
US2776202A (en) * 1955-08-18 1957-01-01 American Potash & Chem Corp Use of lepidolite as an additive in the lime-roasting of lithium-aluminosilicate ores
GB804962A (en) * 1956-10-09 1958-11-26 Chempatents Inc Preparation of high purity lithium carbonate from lithium ores
US3024082A (en) * 1957-06-27 1962-03-06 Scient Design Co Lithium chloride production
BE566808A (fr) * 1957-06-27
US3087782A (en) * 1959-12-23 1963-04-30 Texaco Development Corp Recovery of metal values from lithium ores
US7265254B2 (en) * 2001-07-30 2007-09-04 Taiheiyo Cement Corporation Waste processing method, waste processing system, integrated waste processing method, and integrated waste processing system
CN101607796B (zh) * 2009-07-30 2011-08-03 北京金隅红树林环保技术有限责任公司 一种利用高碱原料生产低碱水泥的方法

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AU2018285391A1 (en) 2020-02-06
CZ2017343A3 (cs) 2018-09-19
CA3066286C (fr) 2023-01-03
WO2018228618A1 (fr) 2018-12-20
CA3066286A1 (fr) 2018-12-20
DE18750313T1 (de) 2020-05-07

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