CN219731021U - Spodumene smelting slag recycling comprehensive utilization system - Google Patents
Spodumene smelting slag recycling comprehensive utilization system Download PDFInfo
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- CN219731021U CN219731021U CN202321125517.4U CN202321125517U CN219731021U CN 219731021 U CN219731021 U CN 219731021U CN 202321125517 U CN202321125517 U CN 202321125517U CN 219731021 U CN219731021 U CN 219731021U
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- 239000002893 slag Substances 0.000 title claims abstract description 141
- 238000004064 recycling Methods 0.000 title claims abstract description 53
- 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 title claims abstract description 47
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 45
- 238000003723 Smelting Methods 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 155
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 155
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000007788 liquid Substances 0.000 claims abstract description 117
- 238000011084 recovery Methods 0.000 claims abstract description 114
- 238000002386 leaching Methods 0.000 claims abstract description 95
- 229910052742 iron Inorganic materials 0.000 claims abstract description 74
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000926 separation method Methods 0.000 claims abstract description 57
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010440 gypsum Substances 0.000 claims abstract description 52
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 52
- 238000004537 pulping Methods 0.000 claims abstract description 46
- 238000007885 magnetic separation Methods 0.000 claims description 77
- 238000001914 filtration Methods 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 52
- 238000005188 flotation Methods 0.000 claims description 37
- 230000005484 gravity Effects 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 21
- 239000000696 magnetic material Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 23
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- 230000029087 digestion Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 40
- 239000002002 slurry Substances 0.000 description 34
- 239000012141 concentrate Substances 0.000 description 31
- 230000005291 magnetic effect Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 230000002950 deficient Effects 0.000 description 12
- 239000006260 foam Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010409 ironing Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910004168 TaNb Inorganic materials 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052643 α-spodumene Inorganic materials 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The utility model relates to the technical field of solid waste recycling treatment for extracting lithium from ores, and discloses a spodumene smelting slag recycling comprehensive utilization system. The system comprises a lithium liquid circulation leaching unit, a gypsum recovery unit, an iron recovery unit, a tantalum-niobium recovery unit and a silicon-aluminum recovery unit; the lithium liquid circulation leaching unit comprises a first pulping device, a leaching device, a solid-liquid separation device and a lithium liquid collection device, wherein the first pulping device, the leaching device and the solid-liquid separation device are sequentially connected, a liquid outlet of the solid-liquid separation device is connected with a poor lithium liquid collection device, the poor lithium liquid collection device is connected with the first pulping device, and a liquid outlet of the solid-liquid separation device is also connected with a lithium-rich liquid outlet and is connected with the lithium liquid collection device through the lithium-rich liquid outlet. The method fundamentally solves the problem of the digestion of the lithium slag, realizes the comprehensive utilization of the lithium slag, changes waste into valuable, and can effectively improve the recovery rate of lithium and reduce the recovery cost compared with the existing comprehensive recovery method.
Description
Technical Field
The utility model relates to the technical field of solid waste recycling treatment for extracting lithium from ores, in particular to a spodumene smelting slag recycling comprehensive utilization system.
Background
The spodumene smelting slag is solid waste for extracting lithium from ores, the spodumene extracting lithium process is a current mature ore extracting lithium process, natural spodumene is roasted at 950-1100 ℃ to be converted into tetragonal beta-spodumene from monoclinic alpha-spodumene, and due to the crystal form conversion, the physical and chemical properties of minerals are obviously changed along with the change of crystal structures, so that the chemical activity is increased, and various reactions can be carried out with acid and alkali. In the lithium extraction process of spodumene, partial lithium is often unavoidable to remain in lithium slag, and the secondary recycling value of lithium in solid waste resources is fully excavated, so that the method has important significance.
The main chemical component in spodumene smelting slag is SiO 2 And Al 2 O 3 Mainly aluminosilicate and quartz, and secondly gypsum, little spodumene and iron mineral, and detecting SO in the lithium slag raw material 3 The content is 3 to 8 percent, fe 2 O 3 The content of Li is 0.8 to 1.2 percent 2 O content 0.3-0.6% (TaNb) 2 O 5 The content is 120-180 ppm, and the valuable metal lithium and tantalum-niobium have comprehensive recycling value.
In the process for producing lithium salt by spodumene, about 8-10 tons of lithium slag are discharged when one ton of lithium salt is produced, and a large amount of lithium slag can be produced according to the discharge amount, so that not only is the land resource wasted caused by stacking, but also the storage is poor, and the slag water containing alkali and acid is lost, so that farmland is harmed and the environment is polluted. At present, the comprehensive utilization of the lithium slag is mainly applied to the cement building material industry, the added value is low, a small amount of lithium, tantalum-niobium metal and gypsum are not recycled, and meanwhile, along with the explosive growth of the lithium slag quantity, the consumption of the lithium slag in the cement building material industry is close to saturation, so that the problem of the consumption of the lithium slag becomes a problem to be solved in the future.
The utility model patent with publication number of CN110015855A discloses a treatment method of lithium slag, wherein the leaching rate of lithium, rubidium, cesium, potassium, aluminum and sodium is over 88% by carrying out sulfuric acid leaching on lithium slag extracted from lepidolite, the main components in the obtained acid leaching slag are quartz and gypsum, and the quartz and gypsum can be used as concrete admixture for secondary use. Although valuable elements such as lithium in the slag are recovered, the recovery cost is relatively high, more solid slag or waste liquid is easy to cause, a certain environmental protection risk is provided, the problem of the digestion of the lithium slag is not substantially solved, and most of the lithium slag can still be used as an admixture of cheap cement building materials.
The utility model patent with publication number of CN114702048A discloses a recycling process of solid waste of lithium slag, and products such as potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate and rubidium carbonate are obtained by respectively carrying out acid-base reaction on the lithium slag. The process is complex, the cost is high, hydrofluoric acid is also required to be introduced, environmental pollution is easy to cause, most of solid matters which are insoluble in acid in the lithium slag are used as building materials only, and the recycling treatment of the lithium slag cannot be really realized.
The utility model patent with publication number of CN113621811A discloses a method for recycling tantalum and niobium from spodumene slag, which has the technical precondition that a small amount of waste acid is required to be added to ensure that the pH value of slag slurry is 4-5, equipment is easy to corrode, and certain environmental protection risk is provided.
The utility model patent with publication number of CN114226413A discloses a comprehensive treatment process of lithium slag, which comprises the steps of adopting processes of ore grinding, magnetic separation, flotation, alkali conversion and the like to obtain silicon-aluminum micro powder, wherein the spodumene smelting slag is generally finer in fineness, the process does not carry out classified ore grinding on the lithium slag, and sulfur in the micro powder is reduced by adopting a mode of adding sodium carbonate or potassium carbonate for alkali conversion, so that ore grinding cost and desulfurization cost are higher; although the process can also obtain the silicon-aluminum micropowder for glass fiber, valuable metal lithium and gypsum in the lithium slag are not reasonably recovered, and the recycling treatment of the lithium slag is difficult to realize in a real sense.
The utility model patent with publication number of CN216459396U discloses a system for comprehensively recovering lithium, tantalum and niobium, silicon-aluminum micropowder, iron concentrate and gypsum from lithium slag, achieves the purposes of diversification and high-value utilization of deeply processed products of lithium slag, and can obtain silicon-aluminum micropowder with high silicon, high aluminum, low iron and low sulfur, high-quality gypsum concentrate, iron concentrate, tantalum and niobium concentrate and lithium-rich slag. However, the system is used for recycling lithium in lithium slag, only part of lithium in Gao Tiefu lithium materials with smaller yield is recycled, and Li in the silicon-aluminum micropowder product is recycled 2 O is not recovered, resulting in waste of lithium resources.
Disclosure of Invention
The utility model aims to solve the technical problem of providing a spodumene smelting slag recycling comprehensive utilization system capable of better realizing recovery of lithium and other resources.
The utility model discloses a spodumene smelting slag recycling comprehensive utilization system which comprises a lithium liquid circulating leaching unit, a gypsum recovery unit, an iron recovery unit, a tantalum-niobium recovery unit and a silicon-aluminum recovery unit;
the lithium liquid circulation leaching unit comprises a first pulping device, a leaching device, a solid-liquid separation device and a lithium liquid collection device, wherein the first pulping device, the leaching device and the solid-liquid separation device are sequentially connected, a liquid outlet of the solid-liquid separation device is connected with a lithium-poor liquid collection device, the lithium-poor liquid collection device is connected with the first pulping device, and a liquid outlet of the solid-liquid separation device is also connected with a lithium-rich liquid outlet and is connected with the lithium-liquid collection device through the lithium-rich liquid outlet;
and the gypsum recovery unit, the iron recovery unit, the tantalum-niobium recovery unit and the silicon-aluminum recovery unit are all connected with a solid outlet of the solid-liquid separation device.
Preferably, the lithium liquid circulation leaching unit further comprises a washing device, a feeding hole of the washing device is connected with a solid outlet of the solid-liquid separation device, a liquid outlet of the washing device is connected with the poor lithium liquid collecting device, and the gypsum recovery unit, the iron recovery unit, the tantalum-niobium recovery unit and the silicon-aluminum recovery unit are all connected with the solid outlet of the washing device.
Preferably, the lithium liquid circulation leaching unit further comprises a grading grinding subunit, the grading grinding subunit comprises a grading device and a grinding device, a feeding hole of the grading device is connected with a discharging hole of the first pulping device, a fine material outlet of the grading device is connected with the leaching device, a feeding hole of the grinding device is connected with a coarse material outlet of the grading device, and a discharging hole of the grinding device is connected with the leaching device.
Preferably, the solid outlet of the lithium liquid circulation leaching unit is connected with a second pulping device, and the gypsum recovery unit, the iron recovery unit, the tantalum-niobium recovery unit and the silicon-aluminum recovery unit are all connected with the outlet of the second pulping device.
Preferably, the second pulping device is provided with a pulping material feeding port.
Preferably, the gypsum recovery unit comprises a flotation device, a first concentration filtration device and a gypsum collection device, wherein a feed inlet of the flotation device is connected with an outlet of the second pulping device, a flotation product outlet of the flotation device is sequentially connected with the first concentration filtration device and the gypsum collection device, and the iron recovery unit, the tantalum-niobium recovery unit and the silicon-aluminum recovery unit are all connected with a slag outlet of the flotation device.
Preferably, the silicon-aluminum recovery unit comprises a first magnetic separation device, a second concentration and filtration device and a silicon-aluminum collection device, wherein a feed inlet of the magnetic separation device is connected with a slag outlet of the flotation device, and a non-magnetic material outlet of the magnetic separation device is sequentially connected with the second concentration and filtration device and the silicon-aluminum collection device.
Preferably, a drying device is arranged between the second concentration and filtration device and the silicon-aluminum collection device.
Preferably, the first magnetic separation device comprises a middle magnetic separation device and a strong magnetic separation device, wherein a feed inlet of the middle magnetic separation device is connected with a slag outlet of the flotation device, a feed inlet of the strong magnetic separation device is connected with a non-magnetic material outlet of the middle magnetic separation device, and a non-magnetic material outlet of the strong magnetic separation device is connected with the silicon-aluminum collection device through a second concentration filtration device.
Preferably, the tantalum-niobium recovery unit comprises a gravity separation device, a third concentration and filtration device and a tantalum-niobium collection device, wherein a feed inlet of the gravity separation device is connected with a magnetic material outlet of the first magnetic separation device, and a heavy material outlet of the gravity separation device is sequentially connected with the third concentration and filtration device and the tantalum-niobium collection device.
Preferably, the iron recycling unit comprises a fourth concentration and filtration device and an iron slag collecting device, and a light material outlet of the gravity separation device is sequentially connected with the fourth concentration and filtration device and the iron slag collecting device.
Preferably, the tantalum-niobium recovery unit further comprises a second magnetic separation device, the second magnetic separation device is a weak magnetic separation device, a feed inlet of the weak magnetic separation device is connected with a heavy material outlet of the gravity separation device, a non-magnetic material outlet of the weak magnetic separation device is connected with a third concentration filtration device, and a magnetic material outlet of the weak magnetic separation device is connected with a fourth concentration filtration device.
Preferably, the water recycling device is further included, at least one of the first concentration filtering device, the second concentration filtering device, the third concentration filtering device and the fourth concentration filtering device is connected with a water inlet of the water recycling device, and at least one of the first magnetic separation device, the second magnetic separation device, the gravity separation device, the flotation device, the second pulping device and the first pulping device is connected with a water outlet of the water recycling device.
Preferably, the first concentration and filtration device is connected with a water treatment device, and the water treatment device is connected with a water inlet of the water recovery device.
The beneficial effects of the utility model are as follows: the method has the advantages that the problem of the consumption of lithium slag is fundamentally solved, the comprehensive utilization of lithium slag resources is realized, waste is changed into valuable, meanwhile, compared with the existing comprehensive recovery method, the recovery rate of lithium can be effectively improved, and the recovery cost is reduced.
Drawings
Fig. 1 is a schematic diagram of the present utility model.
Reference numerals: a lithium liquid circulation leaching unit 100, a gypsum recovery unit 200, a silicon-aluminum recovery unit 300, a tantalum-niobium recovery unit 400 and an iron recovery unit 500;
the lithium slag storage device 1, the first pulping device 2, the classifying grinding subunit 3, the leaching device 4, the lean lithium liquid collecting device 5, the solid-liquid separation device 6, the lithium liquid collecting device 7, the washing device 8, the second pulping device 9, the first concentration and filtration device 10, the gypsum collecting device 11, the water treatment device 12, the flotation device 13, the medium magnetic separation device 14, the strong magnetic separation device 15, the second concentration and filtration device 16, the drying device 17, the silicon-aluminum collecting device 18, the gravity separation device 19, the weak magnetic separation device 20, the third concentration and filtration device 21, the tantalum-niobium collecting device 22, the fourth concentration and filtration device 23 and the iron slag collecting device 24.
Detailed Description
The utility model is further described below with reference to the accompanying drawings.
The utility model relates to a spodumene smelting slag recycling comprehensive utilization system which comprises a lithium liquid circulation leaching unit 100, a gypsum recovery unit 200, an iron recovery unit 500, a tantalum-niobium recovery unit 400 and a silicon-aluminum recovery unit 300;
the lithium liquid circulation leaching unit 100 comprises a first pulping device 2, a leaching device 4, a solid-liquid separation device 6 and a lithium liquid collection device 7, wherein the first pulping device 2, the leaching device 4 and the solid-liquid separation device 6 are sequentially connected, a liquid outlet of the solid-liquid separation device 6 is connected with a poor lithium liquid collection device 5, the poor lithium liquid collection device 5 is connected with the first pulping device 2, and a liquid outlet of the solid-liquid separation device 6 is also connected with a lithium-rich liquid outlet and is connected with the lithium liquid collection device 7 through the lithium-rich liquid outlet;
the gypsum recovery unit 200, the iron recovery unit 500, the tantalum-niobium recovery unit 400, and the silicon-aluminum recovery unit 300 are all connected to the solid outlet of the solid-liquid separator 6.
As shown in fig. 1, spodumene smelting slag is sent into a pulping device of a liquid circulation leaching unit from a lithium slag storage device 1, is uniformly mixed with water and stirred to prepare lithium slag slurry, sulfuric acid is added into a leaching device 4 for leaching, at the moment, leached liquid is lean lithium liquid, the lean lithium liquid is obtained after being separated by a solid-liquid separation device 6, the lean lithium liquid enters a lean lithium liquid collecting device 5, the lean lithium liquid collecting device 5 returns the lean lithium liquid into the pulping device, pulping, leaching and separation processes are repeated for a plurality of times, lithium-rich liquid can be obtained, and the lithium-rich liquid enters a lithium liquid collecting device 7 from a lithium-rich liquid outlet of the solid-liquid separation device 6 to be collected for subsequent utilization. Meanwhile, the solid separated by the solid-liquid separation device 6 can be respectively collected into gypsum, iron, tantalum and niobium and a compound with silicon-aluminum as a main component through the gypsum recovery unit 200, the iron recovery unit 500, the tantalum and niobium recovery unit 400 and the silicon-aluminum recovery unit 300, so that the comprehensive utilization of spodumene smelting slag is realized. The solid-liquid separation device 6 may be a screen type or centrifugal type filter, and the number of times of circulation leaching is usually 2 to 4.
In order to realize the recovery of part of lithium, the lithium-liquid circulation leaching unit 100 in a preferred embodiment of the present utility model further comprises a washing device 8, a feed inlet of the washing device 8 is connected with a solid outlet of the solid-liquid separation device 6, a liquid outlet of the washing device 8 is connected with the lithium-poor liquid collecting device 5, and the gypsum recovery unit 200, the iron recovery unit 500, the tantalum-niobium recovery unit 400 and the silicon-aluminum recovery unit 300 are all connected with the solid outlet of the washing device 8. The lithium-containing solution can be washed out by the washing device 8, and then the lithium-rich solution is formed by collecting and circulating the lithium-poor solution by the lithium-poor solution collecting device 5, and the washed solid is recycled for other materials.
Since the slurry prepared from spodumene smelting slag contains both fine-fraction and coarse-fraction materials, the fine-fraction materials are generally materials with a particle size of 45 μm or less, and the coarse-fraction materials are generally materials with a particle size of more than 45 μm. The fine fraction material facilitates the leaching of lithium, while the coarse fraction material directly leaches lithium with unsatisfactory recovery rate, while the direct grinding of the whole material is less efficient and more energy-consuming, so that in a preferred embodiment of the utility model, the lithium liquid circulation leaching unit 100 further comprises a classifying grinding subunit 3, the classifying grinding subunit 3 comprises a classifying device and a grinding device, the feed inlet of the classifying device is connected with the discharge outlet of the first pulping device 2, the fine outlet of the classifying device is connected with the leaching device 4, the feed inlet of the grinding device is connected with the coarse outlet of the classifying device, and the discharge outlet of the grinding device is connected with the leaching device 4. The ore grinding device preferably adopts a wet ore grinding machine. The fine-fraction materials are separated by a classifying device, the rest coarse-fraction materials are ground by a grinding device, the ground slurry and the classified fine-fraction slurry are combined to prepare fine slurry, and the fine slurry enters a next-stage leaching device 4. Not only can the leaching recovery rate of lithium be improved, but also the energy consumption can be effectively reduced, and the efficiency is improved.
However, in order to facilitate the recovery of the materials such as the subsequent gypsum, as a preferred embodiment of the present utility model, the second pulping device 9 is connected to the solid outlet of the lithium liquid circulation leaching unit 100, and the gypsum recovery unit 200, the iron recovery unit 500, the tantalum-niobium recovery unit 400, and the silicon-aluminum recovery unit 300 are all connected to the outlet of the second pulping device 9. The solid outlet of the lithium liquid circulation leaching unit 100 may be the solid outlet of the solid-liquid separation device 6, or the solid outlet of the washing device 8 if the washing device 8 is provided. The solid slag is slurried again in the second slurrying device 9 for subsequent recovery of other materials.
Since the leaching is carried out with acid, both before and after washing, the solid slag is acidic, and in a preferred embodiment of the utility model the second pulping device 9 is provided with a pulp feed inlet. Limestone or quicklime or slaked lime can be added into the slurry mixing material inlet to adjust the pH of the ore slurry to 6-7, thereby being beneficial to the recovery of subsequent materials and reducing the corrosiveness of the slurry.
The gypsum recovery unit 200, the iron recovery unit 500, the tantalum-niobium recovery unit 400 and the silicon-aluminum recovery unit 300 may be used for recovering gypsum, iron, tantalum-niobium and silicon-aluminum respectively, and the specific arrangement mode thereof may refer to the recovery modes of these materials proposed in the background art, in the preferred embodiment of the present utility model, the gypsum recovery unit 200 includes a flotation device 13, a first concentration filtration device 10 and a gypsum collection device 11, the feed inlet of the flotation device 13 is connected with the outlet of the second pulping device 9, the flotation product outlet of the flotation device 13 is sequentially connected with the first concentration filtration device 10 and the gypsum collection device 11, and the iron recovery unit 500, the tantalum-niobium recovery unit 400 and the silicon-aluminum recovery unit 300 are all connected with the slag outlet of the flotation device 13. The slurry enters a flotation device 13 for flotation and desulfurization to obtain desulfurized lithium slag and a flotation foam product, the flotation foam product enters a first concentration and filtration device 10 from a flotation product outlet to obtain a gypsum product and filtrate, and the gypsum is sent to a gypsum collecting device 11 for collection.
In a preferred embodiment of the present utility model, the silica-alumina recovery unit 300 includes a first magnetic separation device, a second concentration filtration device 16 and a silica-alumina collection device 18, wherein a feed inlet of the magnetic separation device is connected to a slag outlet of the flotation device 13, and a non-magnetic material outlet of the magnetic separation device is sequentially connected to the second concentration filtration device 16 and the silica-alumina collection device 18. After the ferromagnetism material is removed from the desulfurization lithium slag through the first magnetic separation device, the desulfurization lithium slag is concentrated through the second concentration and filtration device 16 to obtain silicon aluminum slag, a drying device 17 can be arranged between the second concentration and filtration device 16 and the silicon aluminum collection device 18, the silicon aluminum slag is dried to obtain silicon aluminum refined powder, and the silicon aluminum refined powder is collected by the silicon aluminum collection device 18.
The first magnetic separation device can adopt a single middle magnetic separation device or a strong magnetic separation device 15, but the impurity content of the silicon aluminum refined powder can be influenced by single magnetic separation, so as to obtain the silicon aluminum refined powder with higher content, the first magnetic separation device comprises a middle magnetic separation device 14 and a strong magnetic separation device 15, a feed inlet of the middle magnetic separation device 14 is connected with a slag outlet of the flotation device 13, a feed inlet of the strong magnetic separation device 15 is connected with a non-magnetic material outlet of the middle magnetic separation device 14, and a non-magnetic material outlet of the strong magnetic separation device 15 is connected with a silicon aluminum collection device 18 through a second concentration filtration device 16. Through the two times of magnetic separation of the medium magnetic separation device 14 and the strong magnetic separation device 15, the content of ferromagnetic materials can be better reduced, so that the silicon-aluminum content of the silicon-aluminum refined powder is improved, and the follow-up utilization is facilitated. The field intensity of the medium magnetic separation is usually 0.2-0.6T, preferably 0.3-0.5T, and the field intensity of the strong magnetic separation is usually 1.0-1.7T, preferably 1.0-1.5T.
The magnetic material separated by the first magnetic separation device contains elements such as tantalum, niobium, and iron, so in a preferred embodiment of the present utility model, the tantalum-niobium recovery unit 400 includes a gravity separation device 19, a third concentration filtration device 21, and a tantalum-niobium collection device 22, wherein a feed port of the gravity separation device 19 is connected to a magnetic material outlet of the first magnetic separation device, and a heavy material outlet of the gravity separation device 19 is sequentially connected to the third concentration filtration device 21 and the tantalum-niobium collection device 22. The tantalum-niobium concentrate and the iron ore can be separated by the gravity separation device 19, the tantalum-niobium concentrate with higher density is sent out by a heavy material outlet of the gravity separation device 19, and then the tantalum-niobium concentrate is obtained by concentration by the third concentration and filtration device 21. Correspondingly, the iron recycling unit 500 comprises a fourth concentration and filtration device 23 and an iron slag collecting device 24, and the light material outlet of the gravity separation device 19 is sequentially connected with the fourth concentration and filtration device 23 and the iron slag collecting device 24. The remainder is iron slag, which is filtered by the fourth concentration and filtration device 23 and collected by the iron slag collection device 24. The gravity separation device 19 can adopt spiral chute, shaking table or blanket machine, shaking table or centrifugal concentrator, shaking table or other devices.
The tantalum-niobium concentrate separated by the gravity separation device 19 further contains a small amount of iron ore, in order to improve the purity of the tantalum-niobium concentrate, the tantalum-niobium recovery unit 400 further comprises a second magnetic separation device, the second magnetic separation device is a weak magnetic separation device 20, a feed inlet of the weak magnetic separation device 20 is connected with a heavy material outlet of the gravity separation device 19, a non-magnetic material outlet of the weak magnetic separation device 20 is connected with a third concentration and filtration device 21, and a magnetic material outlet of the weak magnetic separation device 20 is connected with a fourth concentration and filtration device 23. The tantalum-niobium concentrate after magnetic separation by the low-intensity magnetic separation device 20 is sent to the third concentration and filtration device 21 from the non-magnetic material outlet for concentration and filtration, and the iron ore after magnetic separation is sent to the fourth concentration and filtration device 23 for concentration and filtration. The field intensity of the weak magnetic separation is usually 0.1-0.2T; preferably 0.12 to 0.16T.
After the first, second, third and fourth concentration and filtration devices 10, 16, 21 and 23, more filtered liquid is produced, which still contains more usable components, so that in the preferred embodiment of the utility model, the spodumene smelting slag recycling system further comprises a water recovery device, at least one of the first, second, third and fourth concentration and filtration devices 10, 16, 21 and 23 is connected with a water inlet of the water recovery device, and at least one of the first, second, gravity separation devices 19, flotation device 13, second pulping device 9 and first pulping device 2 is connected with a water outlet of the water recovery device. Therefore, the elements in the filtrate can be recycled, the recycling rate of water can be improved, and no wastewater is generated. The filtrate in the iron recovery unit 500, the tantalum-niobium recovery unit 400 and the silicon-aluminum recovery unit 300 can be directly reused, and the direct reuse of the filtrate in the gypsum recovery unit 200 may adversely affect the production, so that in the preferred embodiment of the present utility model, the first concentration filtration device 10 is connected to the water treatment device 12, and the water treatment device 12 is connected to the water inlet of the water recovery device. The water treatment device 12 can directly adopt the existing gypsum filtration water treatment device 12, and the details are omitted herein, so that the treated water can be recycled. Only the wastewater of the gypsum recovery unit 200 is treated, so that the treatment capacity of the wastewater can be greatly reduced, and the production cost can be saved.
In order to describe the present utility model in more detail, the following is an example of the method for recycling and comprehensively utilizing spodumene smelting slag according to the present utility model.
The lithium slag of examples 1 to 3 was derived from lithium extraction smelting slag of spodumene in Sichuan, jiangsu and Jiangxi, and the main chemical compositions are shown in Table 1.
Table 1 chemical composition of lithium smelting slag/%
| Spodumene smelting slag | SO 3 | Fe 2 O 3 | Al 2 O 3 | SiO 2 | Li 2 O | Ta 2 O 5 | Nb 2 O 5 |
| Example 1 | 4.43 | 1.16 | 20.10 | 54.60 | 0.39 | 0.0078 | 0.0063 |
| Example 2 | 5.39 | 0.89 | 21.33 | 52.58 | 0.53 | 0.0085 | 0.0071 |
| Example 3 | 6.87 | 1.08 | 19.87 | 53.26 | 0.56 | 0.0098 | 0.0076 |
Example 1
The spodumene smelting slag of the example is from Sichuan and the composition of the spodumene smelting slag is shown in table 1. The implementation steps of the specific utilization are as follows:
1. adding water into spodumene smelting slag, stirring and pulping to prepare slurry with a solid-to-liquid ratio of 1:1; classifying the slurry by a cyclone, and grinding the coarse-grain slurry with the fineness of more than 45 mu m in a ball mill by adopting a ceramic medium until the fineness of the coarse-grain slurry is-45 mu m accounting for 92%; the ground slurry is combined with fine-fraction slurry of less than 45 mu m classified by a cyclone as leaching raw material.
2. Adding the leaching raw materials into a reaction kettle or a reaction tank, adding concentrated acid to adjust the pH to 1.0, heating to 80 ℃, and stirring and leaching for 2h.
3. After leaching, carrying out solid-liquid separation by adopting a centrifugal machine to obtain leaching residues and lithium-deficient leaching liquid A; washing the leaching slag to obtain a lithium-deficient leaching solution B, merging the lithium-deficient leaching solution A and the lithium-deficient leaching solution B, returning to the stirring pulping process, and carrying out cyclic leaching; and (3) circularly leaching the obtained lithium-rich liquid for 2 times, and returning the lithium-rich liquid to a leaching working section of a lithium carbonate factory to continuously produce a lithium carbonate product. The lithium content and lithium leaching rate of the lithium-rich liquid are shown in Table 2.
4. Adding limestone into the washed leaching slag to neutralize residual acid in the leaching slag, regulating the pH of ore pulp to 6-7, regulating the concentration of ore pulp to 32%, adding a high-efficiency collector and a regulator of gypsum, respectively carrying out rough concentration, scavenging and carefully selecting flotation desulfurization to obtain a foam product and desulfurized lithium slag slurry, concentrating the foam product in a concentration tank and filtering the foam product by a filter to obtain a gypsum product, and returning filtered water to a water tank for recycling after chemical flocculation precipitation treatment. The chemical composition of the gypsum product is shown in Table 3.
5. And carrying out magnetic separation and iron removal on the lithium slag slurry subjected to flotation desulfurization by a magnetic machine in a roller with the magnetic field intensity of 0.3T and a high-gradient strong magnetic machine with the magnetic field intensity of 1.5T to obtain an iron-removing slag material, an iron-containing material A and an iron-containing material B.
6. Combining the iron-containing material A and the iron-containing material B, and carrying out gravity separation on the mixture by a spiral chute and a shaking table to obtain tantalum-niobium rough concentrate and iron slag A; removing magnetic iron impurities from the tantalum-niobium rough concentrate through a low-intensity magnetic separator with the magnetic field intensity of 0.12T to obtain tantalum-niobium concentrate and iron slag B, concentrating and filtering the tantalum-niobium concentrate through a concentration tank to obtain a tantalum-niobium concentrate product, and recycling filtered water after backwater treatment; and combining the iron slag A and the iron slag B, concentrating by a concentration tank, filtering to obtain iron slag, concentrating and filtering the tantalum-niobium concentrate by the concentration tank to obtain a tantalum-niobium concentrate product, and recycling filtered water in a water return tank. The grade and recovery rate of the tantalum-niobium concentrate are shown in Table 4.
7. The de-ironing slag material is concentrated in a concentration tank and filtered by a filter, and then dried to obtain a refined silicon aluminum powder product, and filtered water enters a water return tank for recycling. The chemical compositions of the silicon aluminum refined powder products are shown in Table 5.
Example 2
The spodumene smelting slag of the embodiment is from Jiangsu, and the composition of the spodumene smelting slag is shown in table 1. The implementation steps of the specific utilization are as follows:
1. adding water into spodumene smelting slag, stirring and pulping to prepare slurry with a solid-to-liquid ratio of 1:2; classifying the slurry by a cyclone, and grinding the coarse-grain slurry with the fineness of more than 45 mu m in a ball mill by adopting a ceramic medium until the fineness of the coarse-grain slurry is-45 mu m accounting for 90%; the ground slurry is combined with fine-fraction slurry of less than 45 mu m classified by a cyclone as leaching raw material.
2. Adding the leaching raw materials into a reaction kettle or a reaction tank, adding concentrated acid to adjust the pH to 1.2, heating to 85 ℃, and stirring and leaching for 2.5 hours.
3. After leaching, carrying out solid-liquid separation by adopting filtration to obtain leaching residues and a lithium-deficient leaching solution A; washing the leaching slag to obtain a lithium-deficient leaching solution B, merging the lithium-deficient leaching solution A and the lithium-deficient leaching solution B, returning to the stirring pulping process, and carrying out cyclic leaching; and (3) circularly leaching the obtained lithium-rich liquid for 3 times, and returning the lithium-rich liquid to a leaching working section of a lithium carbonate factory to continuously produce a lithium carbonate product. The lithium content and lithium leaching rate of the lithium-rich liquid are shown in Table 2.
4. Adding quicklime into the washed leaching residue to neutralize residual acid in the leaching residue, regulating the pH of ore pulp to 6-7, regulating the concentration of ore pulp to 28%, adding a high-efficiency collector and regulator of gypsum, respectively carrying out rough concentration, scavenging and carefully selecting flotation desulfurization processes to obtain a foam product and desulfurized lithium slag slurry, concentrating the foam product in a concentration tank and filtering the foam product by a filter to obtain a gypsum product, and returning filtered water to a water tank for recycling after activated carbon adsorption treatment. The chemical composition of the gypsum product is shown in Table 3.
5. And carrying out magnetic separation and iron removal on the lithium slag slurry subjected to flotation desulfurization by a magnetic machine in a roller with the magnetic field intensity of 0.4T and a high-gradient strong magnetic machine with the magnetic field intensity of 1.0T to obtain an iron-removing slag material, an iron-containing material A and an iron-containing material B.
6. Combining the iron-containing material A and the iron-containing material B, and carrying out gravity separation by a blanket machine and a shaking table to obtain tantalum-niobium rough concentrate and iron slag A; removing magnetic iron impurities from the tantalum-niobium rough concentrate by a low-intensity magnetic separator with the magnetic field intensity of 0.15T to obtain tantalum-niobium concentrate and iron slag B; and mixing the iron slag A and the iron slag B, concentrating and filtering the mixture in a concentration tank to obtain iron slag, concentrating and filtering the tantalum-niobium concentrate in the concentration tank to obtain a tantalum-niobium concentrate product, and recycling filtered water in a water return tank. The grade and recovery rate of the tantalum-niobium concentrate are shown in Table 4.
7. The de-ironing slag material is concentrated in a concentration tank and filtered by a filter, and then dried to obtain a refined silicon aluminum powder product, and filtered water enters a water return tank for recycling. The chemical compositions of the silicon aluminum refined powder products are shown in Table 5.
Example 3
The spodumene smelting slag of this example is from Jiangxi and its composition is shown in Table 1. The implementation steps of the specific utilization are as follows:
1. adding water into spodumene smelting slag, stirring and pulping to prepare slurry with a solid-to-liquid ratio of 1:3; classifying the slurry by a cyclone, and grinding the coarse-grain slurry with the fineness of more than 45 mu m in a ball mill by adopting a ceramic medium until the fineness of-45 mu m accounts for 95%; the ground slurry is combined with fine-fraction slurry of less than 45 mu m classified by a cyclone as leaching raw material.
2. Adding the leaching raw materials into a reaction kettle or a reaction tank, adding concentrated acid to adjust the pH to 1.5, heating to 90 ℃, and stirring and leaching for 3 hours.
3. After leaching, carrying out solid-liquid separation by adopting filtration to obtain leaching residues and a lithium-deficient leaching solution A; washing the leaching slag to obtain a lithium-deficient leaching solution B, merging the lithium-deficient leaching solution A and the lithium-deficient leaching solution B, returning to the stirring pulping process, and carrying out cyclic leaching; and (3) circularly leaching the obtained lithium-rich liquid for 4 times, and returning the lithium-rich liquid to a leaching working section of a lithium carbonate factory to continuously produce a lithium carbonate product. The lithium content, and the lithium leaching rate or yield of the lithium-rich liquid are shown in Table 2.
4. Adding limestone into the washed leaching slag to neutralize residual acid in the leaching slag, regulating the pH of ore pulp to 6-7, regulating the concentration of ore pulp to 32%, adding a high-efficiency collector and a regulator of gypsum, respectively carrying out rough concentration, scavenging and carefully selecting flotation desulfurization to obtain a foam product and desulfurized lithium slag slurry, concentrating the foam product in a concentration tank and filtering the foam product by a filter to obtain a gypsum product, and treating the filtered water by an activated sludge method and returning the filtered water to a water tank for recycling. The chemical composition of the gypsum product is shown in Table 3.
5. And carrying out magnetic separation and iron removal on the lithium slag slurry subjected to flotation desulfurization by a magnetic machine in a roller with the magnetic field strength of 0.5T and a high-gradient strong magnetic machine with the magnetic field strength of 1.3T to obtain an iron-removing slag material, an iron-containing material A and an iron-containing material B.
6. Combining the iron-containing material A and the iron-containing material B, and carrying out gravity separation on the mixture by a centrifugal concentrator and a shaking table to obtain tantalum-niobium rough concentrate and iron slag A; removing magnetic iron impurities from the tantalum-niobium rough concentrate by a low-intensity magnetic separator with the magnetic field intensity of 0.16T to obtain tantalum-niobium concentrate and iron slag B; and combining the iron slag A and the iron slag B, concentrating by a concentration tank, filtering by a filter to obtain iron slag, concentrating the tantalum-niobium concentrate by the concentration tank, filtering to obtain a tantalum-niobium concentrate product, and recycling filtered water in a water return tank. The grade and recovery rate of the tantalum-niobium concentrate are shown in Table 4.
7. The de-ironing slag material is concentrated in a concentration tank and filtered by a filter, and then dried to obtain a refined silicon aluminum powder product, and filtered water enters a water return tank for recycling. The chemical compositions of the silicon aluminum refined powder products are shown in Table 5.
Table 2 examples 1 to 3 lithium slag acid leaching indices
TABLE 3 chemical composition/%of gypsum products obtained in examples 1-3
| Description of the embodiments | SO 3 | Fe 2 O 3 |
| Example 1 | 40.82 | 0.26 |
| Example 2 | 41.03 | 0.21 |
| Example 3 | 42.76 | 0.18 |
Table 4 index/%of the tantalum-niobium concentrate products obtained in examples 1 to 3
TABLE 5 chemical composition/%of the fine silica alumina powder products obtained in examples 1 to 3
| Refined silicon-aluminum powder | SO 3 | Fe 2 O 3 | Al 2 O 3 | SiO 2 | Li 2 O |
| Example 1 | 0.28 | 0.39 | 24.54 | 67.32 | 0.11 |
| Example 2 | 0.27 | 0.36 | 23.88 | 68.61 | 0.10 |
| Example 3 | 0.25 | 0.38 | 24.76 | 67.17 | 0.11 |
Therefore, the method can comprehensively recycle the elements such as lithium, tantalum, niobium, silicon, aluminum and the like in the lithium slag, does not generate waste water and waste residues, can solve the problem of future lithium slag digestion, reduces environmental pollution and realizes the comprehensive utilization of lithium slag resources.
Claims (14)
1. The spodumene smelting slag recycling comprehensive utilization system is characterized by comprising a lithium liquid circulating leaching unit (100), a gypsum recovery unit (200), an iron recovery unit (500), a tantalum-niobium recovery unit (400) and a silicon-aluminum recovery unit (300);
the lithium liquid circulation leaching unit (100) comprises a first pulping device (2), a leaching device (4), a solid-liquid separation device (6) and a lithium liquid collecting device (7), wherein the first pulping device (2), the leaching device (4) and the solid-liquid separation device (6) are sequentially connected, a liquid outlet of the solid-liquid separation device (6) is connected with a poor lithium liquid collecting device (5), the poor lithium liquid collecting device (5) is connected with the first pulping device (2), and a liquid outlet of the solid-liquid separation device (6) is also connected with a lithium-rich liquid outlet and is connected with the lithium liquid collecting device (7) through the lithium-rich liquid outlet;
the gypsum recovery unit (200), the iron recovery unit (500), the tantalum-niobium recovery unit (400) and the silicon-aluminum recovery unit (300) are all connected with a solid outlet of the solid-liquid separation device (6).
2. The spodumene smelting slag recycling comprehensive utilization system as claimed in claim 1, wherein: the lithium liquid circulation leaching unit (100) further comprises a washing device (8), a feeding hole of the washing device (8) is connected with a solid outlet of the solid-liquid separation device (6), a liquid outlet of the washing device (8) is connected with the poor lithium liquid collecting device (5), and the gypsum recovery unit (200), the iron recovery unit (500), the tantalum-niobium recovery unit (400) and the silicon-aluminum recovery unit (300) are all connected with the solid outlet of the washing device (8).
3. The spodumene smelting slag recycling comprehensive utilization system as claimed in claim 1, wherein: the lithium liquid circulation leaching unit (100) further comprises a grading grinding subunit (3), the grading grinding subunit (3) comprises a grading device and a grinding device, a feeding port of the grading device is connected with a discharging port of the first pulping device (2), a fine material outlet of the grading device is connected with the leaching device (4), a feeding port of the grinding device is connected with a coarse material outlet of the grading device, and a discharging port of the grinding device is connected with the leaching device (4).
4. The spodumene smelting slag recycling comprehensive utilization system as claimed in claim 1, 2 or 3, wherein: the solid outlet of the lithium liquid circulation leaching unit (100) is connected with a second pulping device (9), and the gypsum recovery unit (200), the iron recovery unit (500), the tantalum-niobium recovery unit (400) and the silicon-aluminum recovery unit (300) are all connected with the outlet of the second pulping device (9).
5. The spodumene smelting slag recycling comprehensive utilization system as claimed in claim 4, wherein: the second pulping device (9) is provided with a pulping material feeding port.
6. The spodumene smelting slag recycling comprehensive utilization system as claimed in claim 4, wherein: the gypsum recovery unit (200) comprises a flotation device (13), a first concentration filtering device (10) and a gypsum collecting device (11), a feed inlet of the flotation device (13) is connected with an outlet of a second pulping device (9), a flotation product outlet of the flotation device (13) is sequentially connected with the first concentration filtering device (10) and the gypsum collecting device (11), and the iron recovery unit (500), the tantalum-niobium recovery unit (400) and the silicon-aluminum recovery unit (300) are all connected with a slag outlet of the flotation device (13).
7. The spodumene smelting slag recycling comprehensive utilization system as claimed in claim 6, wherein: the silicon-aluminum recovery unit (300) comprises a first magnetic separation device, a second concentration and filtration device (16) and a silicon-aluminum collection device (18), wherein a feed inlet of the magnetic separation device is connected with a slag outlet of the flotation device (13), and a non-magnetic material outlet of the magnetic separation device is sequentially connected with the second concentration and filtration device (16) and the silicon-aluminum collection device (18).
8. The spodumene smelting slag recycling comprehensive utilization system as recited in claim 7, wherein: a drying device (17) is arranged between the second concentration and filtration device (16) and the silicon-aluminum collection device (18).
9. The spodumene smelting slag recycling comprehensive utilization system as recited in claim 7, wherein: the first magnetic separation device comprises a middle magnetic separation device (14) and a strong magnetic separation device (15), wherein a feed inlet of the middle magnetic separation device (14) is connected with a slag outlet of the flotation device (13), a feed inlet of the strong magnetic separation device (15) is connected with a non-magnetic material outlet of the middle magnetic separation device (14), and a non-magnetic material outlet of the strong magnetic separation device (15) is connected with a silicon-aluminum collection device (18) through a second concentration filtration device (16).
10. The spodumene smelting slag recycling comprehensive utilization system as recited in claim 7, wherein: the tantalum-niobium recovery unit (400) comprises a gravity separation device (19), a third concentration and filtration device (21) and a tantalum-niobium collection device (22), wherein a feed inlet of the gravity separation device (19) is connected with a magnetic material outlet of the first magnetic separation device, and a heavy material outlet of the gravity separation device (19) is sequentially connected with the third concentration and filtration device (21) and the tantalum-niobium collection device (22).
11. The spodumene smelting slag recycling comprehensive utilization system as recited in claim 10, wherein: the iron recycling unit (500) comprises a fourth concentration and filtration device (23) and an iron slag collecting device (24), and a light material outlet of the gravity separation device (19) is sequentially connected with the fourth concentration and filtration device (23) and the iron slag collecting device (24).
12. The spodumene smelting slag recycling comprehensive utilization system as recited in claim 11, wherein: the tantalum-niobium recovery unit (400) further comprises a second magnetic separation device, the second magnetic separation device is a low-intensity magnetic separation device (20), a feed inlet of the low-intensity magnetic separation device (20) is connected with a heavy material outlet of the gravity separation device (19), a non-magnetic material outlet of the low-intensity magnetic separation device (20) is connected with a third concentration and filtration device (21), and a magnetic material outlet of the low-intensity magnetic separation device (20) is connected with a fourth concentration and filtration device (23).
13. The spodumene smelting slag recycling comprehensive utilization system as recited in claim 12, wherein: the water recycling device is characterized by further comprising a water recycling device, at least one of a first concentration filtering device (10), a second concentration filtering device (16), a third concentration filtering device (21) and a fourth concentration filtering device (23) is connected with a water inlet of the water recycling device, and at least one of a first magnetic separation device, a second magnetic separation device, a gravity separation device (19), a flotation device (13), a second pulping device (9) and a first pulping device (2) is connected with a water outlet of the water recycling device.
14. The spodumene smelting slag recycling comprehensive utilization system as recited in claim 13, wherein: the first concentration and filtration device (10) is connected with a water treatment device (12), and the water treatment device (12) is connected with a water inlet of the water recovery device.
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| CN118026239A (en) * | 2024-04-12 | 2024-05-14 | 中国科学院过程工程研究所 | Method for preparing high-purity calcium sulfate by desulfurizing and decalcification of lithium slag |
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