EP4093889A1 - Thermal treatment of mineral raw materials using a mechanical fluidised bed reactor - Google Patents
Thermal treatment of mineral raw materials using a mechanical fluidised bed reactorInfo
- Publication number
- EP4093889A1 EP4093889A1 EP21700686.5A EP21700686A EP4093889A1 EP 4093889 A1 EP4093889 A1 EP 4093889A1 EP 21700686 A EP21700686 A EP 21700686A EP 4093889 A1 EP4093889 A1 EP 4093889A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat treatment
- bed reactor
- fluidized bed
- mineral raw
- fuel
- 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.)
- Granted
Links
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 17
- 239000011707 mineral Substances 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 title claims abstract description 17
- 238000007669 thermal treatment Methods 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005469 granulation Methods 0.000 claims abstract description 15
- 230000003179 granulation Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 22
- 239000000446 fuel Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000002817 coal dust Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052642 spodumene Inorganic materials 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052629 lepidolite Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052670 petalite Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052822 amblygonite Inorganic materials 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000174 eucryptite Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 229910052612 amphibole Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052652 orthoclase Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052655 plagioclase feldspar Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052643 α-spodumene Inorganic materials 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/2016—Arrangements of preheating devices for the charge
- F27B7/2025—Arrangements of preheating devices for the charge consisting of a single string of cyclones
- F27B7/2033—Arrangements of preheating devices for the charge consisting of a single string of cyclones with means for precalcining the raw material
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
- C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/14—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge
- F27B7/18—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being movable within the drum
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D13/00—Apparatus for preheating charges; Arrangements for preheating charges
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D15/00—Handling or treating discharged material; Supports or receiving chambers therefor
- F27D15/02—Cooling
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D3/00—Charging; Discharging; Manipulation of charge
- F27D2003/0034—Means for moving, conveying, transporting the charge in the furnace or in the charging facilities
- F27D2003/0083—Means for stirring the charge
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2003/00—Type of treatment of the charge
- F27M2003/03—Calcining
Definitions
- the invention relates to an apparatus and a method in particular from
- Lithium ores Lithium ores.
- a method for heat treatment of granular solids is known from WO 2017/144469 A1.
- the device has a preheating zone, a deacidification zone and a sintering zone.
- DE 102017202824 A1 discloses a plant for the production of cement, in particular cement clinker, with a preheater which has a plurality of cyclones, a calciner for deacidification and a rotary kiln.
- a method for drying granulated material is known from EP 3476812 A1.
- lithium mica is dried by flake drying to obtain a dried product, which is micromilled to obtain lithium mica powder and mixed with sodium salt, calcium oxide and water.
- the object of the invention is to provide a device and a method with which, above all, ores can be thermally treated, which on the one hand tend to build up more deposits and on the other hand can represent an increased load on the air circuit due to melting properties and / or particle sizes.
- the device according to the invention for the thermal treatment of mineral raw materials is used in particular for the thermal treatment of lithium ores, for example lithium aluminum silicate, such as spodumene (LiAI [Si 2 0e]) or petalite (LiAI [SUO-io]).
- the invention is particularly suitable for fine-grain lithium ores which have a high degree of contamination by sodium, potassium and / or iron components of> 0.5% by weight (based on Na 2 O, K 2 O, Fe 2 O 3).
- These impurities result primarily from one or mostly more of the following minerals as accompanying minerals:
- Amphibole (KAl 2 AISi30io (OH) 2 ), typical admixture> 1% by weight,
- Orthoclase KAIShOs typical admixture> 6% by weight
- the device has a comminution device, a granulation device and a heat treatment device.
- the granulation device is a mechanical fluidized bed reactor.
- the preheater can be designed as a direct current preheater.
- gas and solid are transported in the same direction, while the heat is transferred from the gas to the solid.
- An example of this are cyclones connected in series. The heat transfer takes place in the connections between the cyclones in cocurrent, the cyclones then serve to separate gas and solids.
- the preheater can be designed as a countercurrent preheater.
- a corresponding preheater is known for example and in particular from DE 38342 15 A1.
- fine-grain lithium ores are used in which all the particles are smaller than 500 ⁇ m, preferably smaller than 350 ⁇ m.
- the lithium ore is selected from a group comprising:
- Lithium layered silicate especially zinnwaldite (KLiFe 2+ Al 2 Si30io (OH, F) 3 lithium layered silicate, especially lepidolite KLiAl 2 Si30io (OH, F) 3 Jadarite NaLi [B 3 Si0 7 (0H)]
- Clay minerals especially hectorite nao . 3 (Mg, Li) 3SUOio (OH) 2 Eucryptite LiAISi204 and mixtures thereof and mixtures of these lithium ores with other non-lithium-containing compounds, the mixture having a proportion of at least 70% by weight of these lithium ores.
- Heat treatment device on a preheater wherein the preheater has 2 to 8 cyclones. Cyclones allow the material to be heated quickly and efficiently. At the same time, the gas is cooled in countercurrent and the energy is recovered.
- Heat treatment device on a calciner The thermal treatment in a calciner is preferably limited to a dwell time of 1 to 3 seconds in the Clacini loop. In conventional systems, the calciner is typically designed for a dwell time of 60 s. This is made possible by the particularly good heat transfer in a device according to the invention due to the small but uniform particle size, in particular together with the possible influencing of the temperature profile via the loop by fuel and air grading.
- the calciner is a multi-deck furnace.
- a cooler is arranged next to the heat treatment device.
- the cooler consists of 2 to 8 cyclones. Cyclones allow the material to be cooled down quickly and efficiently. At the same time, the gas is heated in countercurrent. Alternatively, no indirect rapid cooling process can be used to stop the reaction in a controlled manner and without the use of oxygen.
- the cooler is connected directly to the calciner.
- a furnace in particular a rotary kiln, is thus completely dispensed with.
- By using the mechanical fluidized bed reactor it has been found that extremely uniform agglomeration of the starting material is achieved.
- the starting material has already been converted after it has passed through the calciner.
- the long heating in the oven which according to the prevailing opinion is necessary for complete implementation, can be dispensed with. This results in savings both in the construction of the system and, above all, in its operation.
- the heat treatment device has a rotary kiln. This embodiment can be preferred if a longer thermal treatment of the starting material leads to optimized product properties.
- a multi-deck furnace is used for the thermal treatment of the material instead of a rotary kiln.
- the device has both a rotary tube furnace and a multi-deck furnace. This leads to significantly longer residence times, for example and preferably to residence times of 30 minutes to 2 hours.
- a device according to this embodiment is particularly suitable for the thermal treatment of lithium sheet silicates (zinnwaldite and lepidolite), especially if these have additional additives, for example sulfate components and / or limestone. For the conversion of such a mixture, the solids / solids reactions require significantly longer residence times.
- the mechanical fluidized bed reactor has an essentially horizontally arranged container.
- a shaft is arranged centrally along the longitudinal axis of the container, with mixing tools being arranged radially on the shaft.
- these mixing tools can be arranged in the form of a rod and vertically on the shaft.
- the mixing tools are particularly preferably designed in the shape of a ploughshare. Examples of ploughshare-shaped mixing tools can be found in DE 2729477 C2 or DE 19706364 C2, for example.
- Essentially horizontal is to be understood in the context of the invention according to EP 0500561 B1.
- the mechanical fluidized bed reactor has at least one fluid supply. Further fluid feeds can also be arranged, in particular along the transport direction of the material.
- the fluid supply is particularly preferably used to supply water. Water supports the agglomeration and thus leads to more uniform particles. In particular, the addition of water reduces the proportion of the smallest particles, as a result of which dust formation and adhesion of material in the cyclones can be avoided particularly efficiently.
- a fluid feed is arranged upstream of the mechanical fluidized bed reactor. This can be present in addition or as an alternative to a fluid supply in the mechanical fluidized bed reactor.
- the mechanical fluidized bed reactor has a fuel feed. Alternatively or additionally, fuel can also be fed in upstream of the mechanical fluidized bed reactor. This allows the fuel to be incorporated into the particles formed by agglomeration in the mechanical fluidized bed reactor. This fuel ignites in a later process after its ignition temperature is exceeded, for example in the calciner, and thus leads to a much more targeted heating of the raw material.
- a rising tube dryer is arranged between the mechanical fluidized bed reactor and the preheater.
- the riser dryer has two advantages. On the one hand, in particular water, which is used in the agglomeration in the mechanical fluidized bed reactor, can be discharged. On the other hand, the material can be transported to the entrance height of the preheater.
- the riser dryer can also be used to adjust the particle size. Particles that are too large can in particular be separated off and, in particular, returned for renewed grinding via the gas velocity and, if necessary, via a separation cyclone at the upper end of the riser dryer.
- a homogenization stage is arranged between the comminution device and the mechanical fluidized bed reactor.
- a homogenization stage is particularly advantageous if fuel and / or binding agent is added before the homogenization stage.
- a rising tube dryer is arranged between the mechanical fluidized bed reactor and the heat treatment device.
- the riser dryer has two advantages. On the one hand, in particular water, which is used in the agglomeration in the mechanical fluidized bed reactor, can be discharged. On the other hand, the material can be transported to the entrance height of the preheater.
- the invention relates to a method for the thermal treatment of mineral raw materials, in particular lithium ores, the method having the following steps: a) comminuting the mineral raw material in a comminuting device, b) granulating the product from step a) in a granulating device, c) Heat treatment of the product from step b) in a heat treatment device.
- the method is characterized in that after step b) 90% of all particles have a particle size between 50 ⁇ m and 500 ⁇ m.
- the starting material can advantageously be ground very finely.
- the finer the materials are ground the better and more homogeneous the firing process is.
- particles that are too small are disruptive to the process. Due to the upstream processing steps, for example and in particular flotation, however, small particle sizes are necessary in these upstream processing steps in order to achieve a sufficiently large enrichment.
- these particles are unfavorable for the thermal treatment, since these small particle sizes lead to large losses via the filter dust.
- the above-mentioned thermally sensitive components can lead to the formation of melts, which in turn reduces the extractable lithium content and reduces the production output due to batches or leads to failure.
- this limitation does not apply.
- fine-grain lithium ores in which all particles are smaller than 500 ⁇ m, preferably smaller than 350 ⁇ m, are used in the process.
- the lithium ore is selected from a group comprising:
- Lithium layer silicate especially zinnwaldite (KLiFe 2+ Al 2 Si30io (OH, F) 3 Lithium layer silicate, in particular lepidolite KLiAl 2 Si30io (OH, F) 3 Jadarit NaLi [B 3 Si0 7 (0H)]
- Clay minerals especially hectorite nao . 3 (Mg, Li) 3SUOio (OH) 2 Eucryptite LiAISi204 and mixtures thereof and mixtures of these lithium ores with other non-lithium-containing compounds, the mixture having a proportion of at least 70% by weight of these lithium ores.
- the particles have a pellet strength of at least 5N.
- a mechanical fluidized bed reactor is selected as the granulation device.
- a granulating plate is selected as the granulating device.
- a material bed roller mill is selected as the granulation device.
- a bricket press is selected as the granulation device.
- a fuel in particular a fuel with an ignition temperature of 500.degree. C. to 650.degree. C., is added before and / or in step b).
- the fuel is preferably selected from the group comprising coal, coal dust and cellulose.
- fuel ignites in a later process after its ignition temperature is exceeded, for example in the calciner, and thus leads to a much more targeted heating of the raw material.
- fuel is supplied up to a mass content of at most 50%, preferably of at most 20%.
- fuel is supplied up to a mass content of at least 0.1%, preferably of at least 5%.
- a binder is added before and / or in step b).
- aluminum silicate or a sulfate is selected as the binder.
- the binder is preferably added in a proportion of 3% by weight to 10% by weight.
- other additives can be added to support the reaction.
- the heat treatment in step c) is carried out at a temperature of at least 600.degree. C., preferably at least 800.degree. C., more preferably at least 850.degree. C., particularly preferably at least 950.degree.
- the heat treatment in step c) is carried out at a temperature of at most 1200.degree. C., preferably at most 1100.degree. C., particularly preferably at most 1000.degree.
- the product is cooled after step c), the product preferably being cooled to below 600.degree.
- the product is comminuted after step c).
- wet grinding takes place in step a) and subsequent agglomeration in step b) without prior drying.
- the nitrogen content of the gas phase in the preheater is less than 30% by volume, preferably less than 15% by volume, particularly preferably less than 5% by volume.
- This is preferably achieved by adding pure oxygen as secondary air to the burners.
- the advantage is that a subsequent separation of the resulting carbon dioxide from the gas phase is facilitated. This is advantageous with the agglomeration of the starting material, since dusts interfere with the deposition of the carbon dioxide. Dusts are, however, particularly greatly reduced by the method according to the invention.
- the separation of the carbon dioxide serves to avoid the emission of climate-damaging gases.
- a first embodiment of a device for the thermal treatment of mineral raw materials is shown.
- the device has a comminuting device 10, for example a mill.
- a flomogenization stage 20 is then arranged, in which the ground mineral raw material is mixed with a fuel and a binding agent.
- the starting material is then granulated in the granulation device 30, a mechanical fluidized bed reactor.
- the granulated material is conveyed in a riser dryer 40 and transported into a preheater 50, which preferably consists of four to six cyclones.
- the calciner 60 adjoins the preheater 50 and the rotary kiln 70 adjoins the calciner 60.
- Preheater 50, calciner 60 and rotary kiln 70 form the heat treatment device.
- the cooler 80 is connected to the heat treatment device
- the second embodiment shown in FIG. 2 differs from the first embodiment in that the heat treatment device does not have a rotary kiln 70, but rather the cooler 80 is directly connected to the calciner 60.
- the calciner 60 has a burner 90 to generate the heat connected.
- the cooler 80 is preferably made up of four to six cyclones.
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Crushing And Pulverization Processes (AREA)
- Crushing And Grinding (AREA)
- Processing Of Solid Wastes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
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Priority Applications (1)
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RS20231083A RS64839B1 (en) | 2020-01-20 | 2021-01-11 | Thermal treatment of mineral raw materials using a mechanical fluidised bed reactor |
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DE102020200602.4A DE102020200602A1 (en) | 2020-01-20 | 2020-01-20 | Thermal treatment of mineral raw materials with a mechanical fluidized bed reactor |
LU101613A LU101613B1 (en) | 2020-01-20 | 2020-01-20 | Thermal treatment of mineral raw materials with a mechanical fluidized bed reactor |
PCT/EP2021/050370 WO2021148267A1 (en) | 2020-01-20 | 2021-01-11 | Thermal treatment of mineral raw materials using a mechanical fluidised bed reactor |
Publications (2)
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EP4093889A1 true EP4093889A1 (en) | 2022-11-30 |
EP4093889B1 EP4093889B1 (en) | 2023-10-25 |
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EP21700686.5A Active EP4093889B1 (en) | 2020-01-20 | 2021-01-11 | Thermal treatment of mineral raw materials using a mechanical fluidised bed reactor |
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US (1) | US20230047215A1 (en) |
EP (1) | EP4093889B1 (en) |
AU (1) | AU2021211083B2 (en) |
CA (1) | CA3162196C (en) |
ES (1) | ES2963642T3 (en) |
FI (1) | FI4093889T3 (en) |
PT (1) | PT4093889T (en) |
RS (1) | RS64839B1 (en) |
WO (1) | WO2021148267A1 (en) |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1051250B (en) | 1954-02-20 | 1959-02-26 | Wilhelm Loedige | Method and device for the discontinuous mixing of powdery or fine-grained masses with liquids |
DE2726138A1 (en) | 1977-06-10 | 1978-12-21 | Kloeckner Humboldt Deutz Ag | METHOD AND DEVICE FOR MANUFACTURING CEMENT CLINKERS FROM WET AGGLOMERATED CEMENT RAW MATERIAL |
DE2729477A1 (en) | 1977-06-30 | 1979-01-11 | Loedige Maschbau Gmbh Geb | POWLED MIXING TOOL |
US4350523A (en) | 1979-04-12 | 1982-09-21 | Kabushiki Kaisha Kobe Seiko Sho | Porous iron ore pellets |
DE3834215A1 (en) | 1988-10-07 | 1990-04-12 | Krupp Polysius Ag | Counterflow heat exchanger |
ATE108090T1 (en) | 1989-10-24 | 1994-07-15 | Loedige Maschbau Gmbh Geb | METHOD AND DEVICE FOR MIXING AND THERMAL TREATMENT OF SOLID PARTICLES. |
US5358715A (en) | 1992-09-02 | 1994-10-25 | Cygnus Therapeutic Systems | Enhancement of transdermal drug delivery using monoalkyl phosphates and other absorption promoters |
JP3160501B2 (en) | 1994-09-21 | 2001-04-25 | 川崎製鉄株式会社 | Method for producing sinter from high-crystalline hydroiron ore |
UA41437C2 (en) * | 1995-01-24 | 2001-09-17 | Фоест-Альпіне Індустріанлагенбау Гмбх | A method for THE utilization of dust PRODUCED DURING reduction of iron ore and a plant for ITS realizATION |
GB9523229D0 (en) | 1995-11-14 | 1996-01-17 | Allied Dust Processing Ltd | Method of processing finely divided material incorporating metal based constituents |
DE19706364C2 (en) | 1997-02-19 | 1999-06-17 | Loedige Maschbau Gmbh Geb | Mixing tool |
CN106906359B (en) * | 2015-12-22 | 2018-12-11 | 理查德.亨威克 | Lithium is collected from silicate mineral |
DE102016103100A1 (en) | 2016-02-23 | 2017-08-24 | Outotec (Finland) Oy | Process and apparatus for the thermal treatment of granular solids |
DE102017202824A1 (en) | 2017-02-22 | 2018-08-23 | Thyssenkrupp Ag | Plant for the production of cement clinker and method for operating such a plant |
SK288899B6 (en) | 2017-10-25 | 2021-09-29 | Považská Cementáreň, A.S. | Method for production of stone aggregates for concrete and mortar |
DE102017125707A1 (en) | 2017-11-03 | 2019-05-09 | Thyssenkrupp Ag | Process and installation for the thermal treatment of a lithium ore |
CN108179264B (en) | 2018-01-11 | 2019-04-19 | 江西云威新材料有限公司 | A method of boiling reconstruction processing lepidolite |
-
2021
- 2021-01-11 PT PT217006865T patent/PT4093889T/en unknown
- 2021-01-11 US US17/792,942 patent/US20230047215A1/en active Pending
- 2021-01-11 AU AU2021211083A patent/AU2021211083B2/en active Active
- 2021-01-11 WO PCT/EP2021/050370 patent/WO2021148267A1/en active Application Filing
- 2021-01-11 FI FIEP21700686.5T patent/FI4093889T3/en active
- 2021-01-11 RS RS20231083A patent/RS64839B1/en unknown
- 2021-01-11 ES ES21700686T patent/ES2963642T3/en active Active
- 2021-01-11 CA CA3162196A patent/CA3162196C/en active Active
- 2021-01-11 EP EP21700686.5A patent/EP4093889B1/en active Active
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WO2021148267A1 (en) | 2021-07-29 |
CA3162196C (en) | 2024-06-11 |
US20230047215A1 (en) | 2023-02-16 |
CA3162196A1 (en) | 2021-07-29 |
AU2021211083A1 (en) | 2022-07-07 |
PT4093889T (en) | 2023-11-21 |
ES2963642T3 (en) | 2024-04-01 |
AU2021211083B2 (en) | 2023-01-05 |
FI4093889T3 (en) | 2023-11-20 |
EP4093889B1 (en) | 2023-10-25 |
RS64839B1 (en) | 2023-12-29 |
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