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WO2019086511A1 - Procédé et installation pour le traitement thermique d'un minerai de lithium - Google Patents

Procédé et installation pour le traitement thermique d'un minerai de lithium Download PDF

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Publication number
WO2019086511A1
WO2019086511A1 PCT/EP2018/079818 EP2018079818W WO2019086511A1 WO 2019086511 A1 WO2019086511 A1 WO 2019086511A1 EP 2018079818 W EP2018079818 W EP 2018079818W WO 2019086511 A1 WO2019086511 A1 WO 2019086511A1
Authority
WO
WIPO (PCT)
Prior art keywords
air flow
flow treatment
lithium ore
treatment section
gas
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.)
Ceased
Application number
PCT/EP2018/079818
Other languages
German (de)
English (en)
Inventor
Meike Dietrich
Sven Hildebrandt
Andreas Hoppe
Jost Lemke
Tobias RISKEN
Karl Lampe
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.)
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
Original Assignee
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
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 ThyssenKrupp AG, ThyssenKrupp Industrial Solutions AG filed Critical ThyssenKrupp AG
Publication of WO2019086511A1 publication Critical patent/WO2019086511A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium

Definitions

  • the invention relates to a method for the thermal treatment of a lithium ore.
  • the invention further relates to a system designed for carrying out such a method.
  • Lithium ores are usually required to undergo a crystal transformation by heat treatment / decrepitation at a temperature of about 800 ° C to 1200 ° C to make the lithium available for further use.
  • Such a process has hitherto been carried out in a rotary kiln.
  • a rotary kiln there is an increasing temperature profile, which is characterized by a particularly hot zone in the region of the kiln outlet.
  • this temperature profile leads to temperatures above the melting temperature of some components of lithium ores and, consequently, to increased formation of deposits and melt phase formation, which negatively influences the process and the product quality.
  • the invention had the object of specifying a method for the thermal treatment of lithium ores, in the implementation of this problem is avoided or at least reduced.
  • a process for the thermal treatment of a lithium ore, for example of spodumene or petalite, in which a flow-current treatment is carried out in which particles of the lithium ore of Hot gas to be carried along an air flow treatment line. It is envisaged that in the air flow treatment, a heat treatment of the lithium ore at temperatures in the range between 800 ° C and 1200 ° C, preferably between 1000 ° C and 1150 ° C, takes place.
  • a heat treatment of the lithium ore can be realized in an advantageous manner, which is characterized by relatively constant temperatures over a sufficiently long residence time, on the one hand ensures a secure crystal transformation in the lithium ore and on the other hand, a thermal overload, which leads to melting or even crusting Components of lithium ore could be safely avoided.
  • An apparatus provided for carrying out such a method according to the invention and correspondingly designed comprises at least one feed device for the supply of lithium ore to a fly-flow reactor, to which, preferably directly, an outlet device for discharging the preferably finally thermally treated material follows, wherein the fly-current reactor forms the air-flow treatment section along which, during operation of the plant, particles of the lithium ore of hot gas producible by a hot gas generating device are carried.
  • the sole focus of the thermal treatment of the lithium ore is in a crystal transformation, and thus in the goal of making the lithium in the lithium ore available as the end product of the process for further use. Accordingly, it can be provided that within the scope of a method according to the invention or that exclusively the lithium ore and, if appropriate, a mixture of lithium ore and other materials (if appropriate additives) are / are treated by means of the air flow treatment. Accordingly, a plant according to the invention can have only a single material feeding device, namely the feed device provided for the supply of exclusively lithium ore to the entrained flow reactor.
  • the hot gas used in the course of the air flow treatment for the transport of the particles of lithium ore and for heat transfer to the particles of lithium ore must not only comprise gaseous components, but in particular also one or more components, in particular fuel, in the liquid or may include solid phase.
  • hot gas is supplied or generated at a plurality of points along the air flow treatment section.
  • a temperature which is as constant as possible over the length of the air flow treatment section for heat treatment of the particles of lithium ore, because the temperature of the hot gas is lowered at least once, preferably several times, as a result of a transition of thermal energy from the hot gas to the particles of lithium ore (possibly only partially) is compensated.
  • the hot gas at the beginning of the air flow treatment section to have such a high (and therefore excessively high) temperature that its thermal energy is sufficient for the complete heat treatment along the transport of the air flow treatment section.
  • a system according to the invention may comprise a plurality of devices for introducing hot gas and / or oxygen-containing gas and / or fuel, optionally as part of a fuel-containing gas, along the air flow treatment section.
  • a supply of hot gas at several points along the air flow treatment line can be realized on the one hand, that each of these feeders is assigned a separate burner for the production of hot gas.
  • this solution can be associated with a relatively high design effort.
  • supplying hot gas at multiple locations along the air flow treatment path can also be realized by providing one or more burners having (a plurality of) each Supply points is connected gas-conducting / are.
  • this may require hot gas to be routed outside of the air flow treatment line over relatively long feed lines, either accompanying a relevant loss of thermal energy or, to avoid such loss, driving a relatively high design effort for adequate thermal isolation of the feed lines would.
  • a burner it is also possible to supply fuel in solid, liquid or gaseous form via a lance, nozzle or another type of device.
  • the air flow treatment section is arranged at least one and preferably exactly one point fuel-containing hot gas and at least one, preferably a plurality of second locations, which, with respect to the flow direction of the hot gas through the air flow treatment line, downstream of the first location (s) / are, oxygen, in particular oxygen-containing gas, which may optionally be preheated and which is, for example, air, in particular compressed air to exhaust gas, which originates from the Klistrom awarenesssumble to pure oxygen to process gas, ie exhaust, which comes from other processes , or may be a mixture of two or more of these gases, is supplied.
  • oxygen in particular oxygen-containing gas
  • air in particular compressed air to exhaust gas
  • This procedure is based on the idea that hot gas within the air flow treatment section in the area of the (s) oxygen-containing gas is supplied by a preferably flameless oxidation of the unburned or partially burned fuel components, in the previously supplied and the supply point (s) reaching hot gas are still contained or explicitly additionally fed at different locations in the air flow treatment section, thereby providing additional thermal energy in the then due to the supply of the oxygen-containing gas hot gas stream is provided.
  • the flow velocity of the air flow treatment section at at least one second point supplied gas is relatively high, whereby an advantageous mixing of this gas with the Hot gas already contained in the air flow treatment section can be achieved.
  • the fuel can be supplied in solid, liquid and / or gaseous form and in particular also part of a fuel-containing gas, which also comprises at least one gas that is not fuel.
  • exhaust gas is used to generate the hot gas.
  • exhaust gas is already used to generate that hot gas flow (primary flow of the hot gas) which flows through the air flow treatment path over the full length.
  • the exhaust gas may be exhaust gas originating from the air flow treatment line. Furthermore, this may be process gas, ie exhaust gas from one or more other processes.
  • exhaust gas to generate the hot gas may be that only a portion of the thermal energy still contained in the exhaust gas is used for the production of the hot gas, for example, by fresh gas, which is used to generate the Hot gas is supplied to a burner is preheated by a heat exchange by means of a corresponding heat exchanger of the system according to the invention.
  • the exhaust gas used to generate the hot gas is a component of the hot gas itself, for example by being supplied to a burner in addition to fresh gas. This procedure has the advantage of full utilization of the thermal energy contained in this exhaust gas.
  • a further advantage of this approach may be that the combustion gas supplied to the burner is relatively low in oxygen, thereby enabling generation of a relatively large flow of hot gas which can be simultaneously fed with relatively much fuel, that is metered in a substoichiometric ratio, thereby allowing to effect one or more oxidations by supplying oxygen-containing gas in the manner described.
  • the supply of relatively much fuel does not lead to an unintentionally high temperature of the hot gas leaving the burner, since only a part of it is converted in the burner.
  • an exhaust gas recirculation line for returning exhaust gas originating from the air flow treatment section into the air flow treatment section and / or
  • a process gas supply line for introducing process gas into the air flow treatment section and / or
  • a heat exchange device for preheating a gas flow to be introduced into the air flow treatment section through a transition of thermal energy of exhaust gas emerging from the Air flow treatment line comes, and / or process gas on the gas flow
  • the lithium ore to be treated thermally is supplied at a plurality of locations distributed along the air flow treatment section.
  • a system according to the invention can be designed in such a way that the feeding device comprises a plurality of feed stations for the lithium ore distributed along the air flow treatment section.
  • the air flow treatment line to be supplied lithium ore is first, for example, by a screening, divided into subsets of different grain size fractions and the subsets of lithium ore separately to the plurality Be supplied to the air flow treatment section.
  • a system according to the invention can comprise a material preheater, which is set up to heat lithium ore to be supplied to the air flow treatment section by a heat transfer of exhaust gas originating from the air flow treatment section.
  • the lithium ore to be supplied to the air flow treatment section can then be provided for preheating only a portion (ie one or more, but not all) of the portions of the lithium ore.
  • a portion ie one or more, but not all
  • it can be provided that only relatively large particles of lithium ore are preheated.
  • the oxygen content in the air flow treatment section is set to values of less than 12% by volume, preferably to values of between 8% by volume and 10% by volume.
  • a combustion atmosphere can be adjusted, which is characterized by a very uniform temperature distribution.
  • a targeted entry of fuel along the air flow treatment section can also be partially or along the entire air flow treatment section set a reducing atmosphere, which has a favorable effect on the crystalline conversion of spodumene or other lithium forms
  • structural internals may be provided within the Flugstrom treatment section, which - possibly exclusively - serve by the generation of turbulence in the flow of hot gas, a mixing of the hot gas with the particles of lithium ore and optionally also in the hot gas introduced to improve oxygen-containing gas and / or fuel.
  • the Flugstrom adaptationsumble comprises at least one section in which the Flugstrom accentsumble formed in such a way is that there is a lower (average) flow velocity of the hot gas in this section compared to at least one other section of the flight treatment path.
  • FIG. 1 shows a schematic representation of a plant according to the invention for the thermal treatment of lithium ores
  • FIG. 2 shows in a diagram a profile of the temperature along the
  • FIG. 1 shows an inventive system for the thermal treatment of
  • Lithium ores By means of these, in the context of a method according to the invention, a lithium ore 1 can be heat-treated in such a way that a crystal transformation takes place, by means of which the lithium contained in the lithium ore 1 is made available for a subsequent use.
  • the plant comprises a fly-flow reactor 2 in which the lithium ore 1 of hot gas 18 comminuted by means of a mill (not shown) into particles having relatively small particle sizes is transported along a relatively long stream Air flow treatment section 3, which may be, for example, about 25 m, is carried, wherein thermal energy is transferred from the hot gas 18 to the particles of the lithium ore 1 to achieve the heat treatment.
  • the entrained flow reactor 2 is preceded with respect to the transport direction of the lithium ore 1, a material preheater 4, which is designed as a multi-stage cyclone preheater.
  • the already to be treated thermally treated, already crushed lithium ore 1 is supplied to the material preheater 4 by means of a feeding device 5 and thereby introduced into the flow of the exhaust stream 6 coming from the entrained flow reactor 2.
  • the particles of the lithium ore 1 are carried by this exhaust gas stream into a first cyclone separator 7 of the material preheater 4 and are separated therefrom again from the exhaust gas stream.
  • a material outlet of this first cyclone separator 7 opens into an exhaust pipe, via which the exhaust gas is passed from a third cyclone separator 9 to a second cyclone separator 8 of the material preheater 4. Consequently, the lithium ore 1 deposited in the first cyclone separator 7 is introduced into the second via this waste gas stream
  • Cyclone 8 introduced.
  • the lithium ore 1 is in turn separated from the exhaust gas, this exhaust gas stream then being conducted via a corresponding exhaust pipe into which the outlet of the task device 5 leads to the first cyclone separator 7, while the separated lithium ore 1 is introduced into an exhaust pipe , which connects an exhaust gas outlet of a material separator 10, likewise designed as a cyclone separator, which constitutes an outlet device of the plant, to an inlet of the third cyclone separator 9 of the material preheater 4.
  • the exhaust gas flowing in this exhaust pipe carries the lithium ore 1 separated in the second cyclone separator 8 into the third cyclone separator 9, in which it is separated from the exhaust gas stream and introduced via a first transfer line 11 into an initial section of the air flow treatment section 3 of the entrained flow reactor 2.
  • the relatively small particles may be provided relatively small particles, for example, with particle sizes of less than 0.2 mm, directly via the second transfer line, ie, bypassing the Vorwarmers 4 and a portion of the air flow treatment section 3 in the air flow treatment section 3, while the larger particles of the lithium ore first through the material preheater 4 and then over the entire air flow treatment section 3 are performed. It can thereby be achieved that, on the one hand, the relatively large particles of the lithium ore 1 are sufficiently thermally treated, while avoiding thermal overloading of the relatively small particles, which could lead to melting or crusting of at least some components of the lithium ore 1 only a relatively low heat transfer to the relatively small particles is realized.
  • the hot gas 18 flowing through the air flow treatment section 3 and carrying the particles of the lithium ore 1 is generated on the one hand by means of a burner 13 arranged on the inlet side of the air flow treatment section 3, to which combustion gas 15 and fuel 16 are fed by means of a fan 14 and combusted in a combustion chamber 17 of the burner 13 become.
  • the combustion gas 15 is primarily fresh gas 19, in particular ambient air, to which optionally a portion of the exhaust gas 6 provided for removal from the system can be admixed, which on the one hand uses the heat energy contained in this part of the exhaust gas 6 in a recuperating manner and, on the other hand, as a result Reduction of the reactivity of the combustion gas 15, the temperature of the hot gas 18 generated by means of the burner 13 can be limited.
  • the system for such recirculation of exhaust gas 6, the system according to the invention comprises an exhaust gas recirculation line 20 downstream of the material preheater 4 (With respect to the flow direction of the exhaust gas 6) branches off from an exhaust line of the plant and in a fresh gas inlet of the burner 13 downstream (with respect to the flow direction of the combustion gas 15) of the likewise integrated therein fan 14, opens.
  • the exhaust gas recirculation line 20 which includes a control valve 21 for controlling or regulating the amount of introduced into the fresh gas 19 exhaust gas 6 and / or preferably an additional fan 25, downstream of the Staubabscheiders 22 and upstream of the dust separator 22 downstream fan 14 from the exhaust line.
  • Alternative arrangements of the mouth of the exhaust gas recirculation line 20, in particular for a supply of dust-free exhaust gas to one or more supply lines 23, which are arranged along the air flow treatment line 3 downstream of the combustion chamber 17 are also possible.
  • the particles of the lithium ore 1 are to be heated until temperatures between 1000 ° C. and 1200 ° C. are reached and these temperatures are kept long enough to effect a crystal transformation.
  • heating of the particles of the lithium ore 1 to temperatures above 1200 ° C is to be avoided, since otherwise the already mentioned melting or even crusting of at least components of the lithium ore 1 could occur, which then leads to increased formation of mixtures within the entrained flow reactor 2 and could lead within this downstream material separator 10. This in turn could negatively affect the process and quality of the finally thermally treated lithium ore 1.
  • a sufficiently high but at the same time not too high a temperature of the hot gas 18 carrying the particles of the lithium ore 1 should be set over the entire or at least a relatively long section of the air flow treatment section 3. This is achieved by keeping the temperature of the hot gas 18, which is primarily generated by the burner 13, relatively low by setting a substoichiometric oxygen ratio and optionally by admixing the exhaust gas 6 with the fresh gas 19. Furthermore, by the setting of the substoichiometric oxygen ratio ensures that the hot gas 18 leaving the burner 13 and flowing into the air flow treatment section 3 is still fuel-containing and consequently comprises relevant quantities of unburned or only partially combusted fuel components.
  • Fig. 2 illustrates this advantage.
  • the dashed curve 26 shows the course of the temperature T of the hot gas 18 over the transport path L of the lithium ore in the air flow treatment section 3 of the entrained flow reactor 2 of a plant according to the invention as shown in FIG. 1. It can be seen that the temperature over the entire length of the air flow treatment section in Maintained within the temperature window (Tu to T s ).
  • the temperature T of hot gas from a material inlet of a comparable thermal power rotary kiln would increase continuously (see dash-dotted curve 27), the temperature upon reaching the material outlet, usually at the burner of a Rotary kiln is arranged, would be well above the upper limit value T s of the temperature window.
  • the temperature profile (see dotted curve 28) of hot gas of an airflow calciner having a comparable thermal output is shown in FIG.
  • Such an airflow calciner is usually preceded by a (pre) calciner of a plant for burning cement clinker a rotary kiln with respect to the material transport and in this only hot gas in the region of an inlet of a flight treatment section is supplied. It can be seen that in such a flow-current calciner, the temperature of the hot gas from a material inlet continuously drops, the temperature initially well above the upper limit T s of the temperature window and during a temporal end portion of the thermal treatment well below the lower limit Tu of the temperature window would.
  • hot gas 18 by means of the burner 13, which still contains a relevant amount of oxygen as a result of an appropriately adjusted superstoichiometric oxygen ratio in which defined amounts of fuel, optionally as a component of a fuel-containing gas, are introduced into the hot gas 18 flowing in the air flow treatment section 3 via the supply lines 23.
  • This fuel can then oxidize with the oxygen contained in the hot gas 18 and thereby cause the desired compensation of an already made lowering of the temperature of the hot gas 18.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé pour le traitement thermique d'un minerai de lithium (1) dans lequel un traitement par flux entraîné est effectué, lors duquel des particules du minerai de lithium (1) sont portées par du gaz chaud (18) le long d'une zone de traitement (3) par flux entraîné. Selon l'invention, lors du traitement par flux entraîné, un traitement thermique du minerai de lithium (1) à des températures dans la plage entre 800°C et 1200°C est effectué. Le traitement par flux entraîné permet de réaliser avantageusement un traitement thermique du minerai de lithium (1), qui est caractérisé par des températures relativement constantes sur un temps de séjour suffisamment long, suite à quoi, d'une part, une conversion cristalline sûre dans le minerai de lithium (1) est garanti et, d'autre part, une surcharge thermique, qui pourrait conduire à la fusion de composants du minerai de lithium (1), peut être évitée de manière sûre. Ceci est en particulier le cas lorsque le gaz chaud (18) est introduit ou généré en une multitude d'endroits le long de la zone de traitement (3) par flux entraîné car de cette manière, parce qu'une diminution de la température du gaz chaud (18) est compensée au moins une fois, de préférence plusieurs fois, suite à un passage de l'énergie thermique du gaz chaud (18) aux particules du minerai de lithium (1)
PCT/EP2018/079818 2017-11-03 2018-10-31 Procédé et installation pour le traitement thermique d'un minerai de lithium Ceased WO2019086511A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017125707.1 2017-11-03
DE102017125707.1A DE102017125707A1 (de) 2017-11-03 2017-11-03 Verfahren und Anlage zur thermischen Behandlung eines Lithiumerzes

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WO2019086511A1 true WO2019086511A1 (fr) 2019-05-09

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WO (1) WO2019086511A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU101613B1 (de) * 2020-01-20 2021-08-06 Thyssenkrupp Ag Thermische Behandlung von mineralischen Rohstoffen mit einem mechanischen Wirbelbettreaktor
FI4093889T3 (fi) 2020-01-20 2023-11-20 Smidth As F L Mineraaliraaka-aineiden lämpökäsittely mekaanisella leijukerrosreaktorilla

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132102A (en) * 1989-12-21 1992-07-21 Fuller Company Method for heat treatment of fines with atmosphere control
CN101224900A (zh) * 2007-10-11 2008-07-23 钟辉 一种锂辉石煅烧转型新方法
US20100047141A1 (en) * 2008-08-20 2010-02-25 Hnat James G Method and Apparatus for the Recovery of Molybdenum from Spent Catalysts
DE102013203058A1 (de) * 2013-02-25 2014-08-28 Siemens Aktiengesellschaft Verfahren zur Gewinnung von Seltenerdmetallen
US20170175228A1 (en) * 2015-12-22 2017-06-22 Richard Hunwick Recovery of lithium from silicate minerals

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087782A (en) * 1959-12-23 1963-04-30 Texaco Development Corp Recovery of metal values from lithium ores

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132102A (en) * 1989-12-21 1992-07-21 Fuller Company Method for heat treatment of fines with atmosphere control
CN101224900A (zh) * 2007-10-11 2008-07-23 钟辉 一种锂辉石煅烧转型新方法
US20100047141A1 (en) * 2008-08-20 2010-02-25 Hnat James G Method and Apparatus for the Recovery of Molybdenum from Spent Catalysts
DE102013203058A1 (de) * 2013-02-25 2014-08-28 Siemens Aktiengesellschaft Verfahren zur Gewinnung von Seltenerdmetallen
US20170175228A1 (en) * 2015-12-22 2017-06-22 Richard Hunwick Recovery of lithium from silicate minerals

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