CN114606383B - Method for comprehensively recovering valuable elements in spodumene industrial leaching residues - Google Patents
Method for comprehensively recovering valuable elements in spodumene industrial leaching residues Download PDFInfo
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- CN114606383B CN114606383B CN202210370700.4A CN202210370700A CN114606383B CN 114606383 B CN114606383 B CN 114606383B CN 202210370700 A CN202210370700 A CN 202210370700A CN 114606383 B CN114606383 B CN 114606383B
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- 238000002386 leaching Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 36
- 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 26
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 26
- 239000002893 slag Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 239000002667 nucleating agent Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000008188 pellet Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 229910052595 hematite Inorganic materials 0.000 claims description 3
- 239000011019 hematite Substances 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007885 magnetic separation Methods 0.000 abstract description 7
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 239000011575 calcium Substances 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910000640 Fe alloy Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
-
- 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
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for comprehensively recovering valuable elements in spodumene industrial leaching residues, which comprises the steps of washing spodumene industrial leaching at normal temperature to obtain calcium sulfate-rich water extract, and evaporating to obtain a calcium sulfate product; the water leaching slag is subjected to filter pressing and drying, then is mixed with an iron source, carbon powder and a nucleating agent for pelleting, and is placed in a smelting furnace for reduction roasting, and a reduction product is subjected to magnetic separation to obtain a ferrosilicon alloy and an oxygen-enriched aluminum oxide product; the method adopts a two-step treatment process, can effectively separate calcium, aluminum and silicon elements in the slag, and recover calcium sulfate, ferrosilicon and aluminum oxide, and has the characteristics of simple process flow, short time consumption, environmental friendliness and the like, and the problems of environmental pollution, resource waste and the like caused by accumulation and difficult treatment of the traditional lithium slag are solved by utilizing the lithium slag with high added value.
Description
Technical Field
The invention relates to a method for comprehensively recovering calcium, aluminum and silicon elements in industrial leaching residues of diaspore ore treated by a sulfuric acid method by a water leaching and reduction smelting method, belonging to the technical field of recycling of solid waste resources.
Background
Lithium is one of the most important new energy metals in the 21 st century, and acid treatment of diaspore is the main method for industrial extraction of lithium. However, about 10 tons of high-alumina-silica leaching slag is generated in each 1 ton of lithium carbonate produced in the process, the leaching slag is mainly HAlSi 2O6、SiO2 and a small amount of CaSO 4·nH2 O, the leaching slag is difficult to be effectively utilized by a wet process, so that a large amount of Ca, al and Si elements are wasted, and meanwhile, the environment is greatly damaged due to continuous generation and accumulation of waste slag.
At present, the most common applications of spodumene industrial leaching residues are: (1) The method is applied to the fields of construction and cement, adopts a rough machining mode, and is doped into construction raw materials to improve the performance of the construction materials; (2) The method is applied to the field of chemical industry, and adopts a leaching method to comprehensively recycle elements.
The prior method performs primary utilization of the building material field on the lithium slag in a doping mode, has simple process, but has low added value of products and limited economic benefit; or the elements are separated, but the products are intermediate products, the utilization degree is low, the use of alkaline solution cannot be avoided, the cost is high, and the overall economic benefit is low, so that in order to fully utilize the elements in the slag and increase the economic benefit, the invention is expected to provide a novel process for comprehensively recovering the calcium, silicon and aluminum elements in the lithium slag.
Disclosure of Invention
The invention discloses a method for comprehensively recovering valuable elements in spodumene industrial leaching residues, which adopts a two-step treatment process to effectively separate calcium, aluminum and silicon elements in the residues and recover calcium sulfate, ferrosilicon alloy and oxygen-enriched aluminum oxide residues; the method can solve the problems of environmental pollution, resource waste and the like caused by accumulation and difficult treatment of the traditional lithium slag, and has the characteristics of simple process flow, short time consumption, environmental friendliness and the like. The technical scheme of the invention is as follows:
a method for comprehensively recovering valuable elements in spodumene industrial leaching residues comprises the following specific steps:
(1) Leaching spodumene industrial leaching residue and water according to the mass ratio of 1:10-100, wherein a soluble component calcium sulfate CaSO 4·nH2 O enters a liquid phase;
(2) Evaporating the water leaching solution obtained in the step (1) to obtain a calcium sulfate product;
(3) And (3) carrying out filter pressing and drying on the water leaching slag obtained in the step (1), uniformly mixing the residual slag with an iron source, a carbon source and a nucleating agent, pelletizing the mixture, reducing the mixed pellets in an ore heating furnace, and carrying out magnetic separation on the reduction products to obtain ferrosilicon alloy and oxygen-enriched aluminum oxide slag.
The spodumene industrial leaching residue in the step (1) can also be other lithium residues; the particle size of spodumene industrial leaching residue is <0.2cm.
The water immersion time in the step (1) is 18-30 h.
And (3) performing filter pressing and drying on the water leaching residues, namely removing excessive water from the water leaching residues by using a filter press, and drying the water leaching residues at 90-400 ℃ for 4-48 hours.
The raw materials in the step (3) are as follows: the mass ratio of the residual slag to the carbon source is 1:1-4, the molar ratio of Si to Fe in the mixed material is 1:0.6-2.5, and the mass ratio of the residual slag to the nucleating agent is 1:0.05-0.2.
The iron source in the step (3) is waste iron, ferric oxide powder or high-grade hematite, magnetite and the like.
The carbon powder in the step (3) is coking coal, semi-coke, charcoal and the like.
The nucleating agent in the step (3) is ferrosilicon powder with the mass percentage of silicon being lower than 45 percent, such as ferrosilicon powder with the silicon content of 33 percent, ferrosilicon powder with the silicon content of 45 percent and the like.
And (3) pelletizing, namely adding a binder to perform pelletizing, wherein the binder is white mud or bentonite, and the addition amount of the binder is not less than 5% of the mass of the mixture.
The reducing atmosphere in the step (3) is N 2 or Ar atmosphere, the reducing temperature is 1100-1500 ℃, and the reducing roasting time is not less than 3 hours.
The ferrosilicon alloy prepared by the method comprises the following main components in percentage by mass: si: 44-56 wt%, fe:43 to 52 weight percent, and the total impurity is less than or equal to 2.0 weight percent; the content of Al 2O3 in the obtained oxygen-enriched aluminum oxide slag is more than or equal to 87 percent.
The invention has the advantages and positive effects that:
(1) The invention separates CaSO 4·nH2 O in the lithium slag in a harmless water leaching mode, and naturally evaporates and recovers the CaSO 4·nH2 O.
(2) The invention separates refractory silicon and aluminum through fire reduction smelting, adds nucleating agent, promotes small alloy particles generated by reaction to quickly aggregate and grow up to the nucleating agent, simultaneously greatly increases liquid phase alloy liquid, promotes the separation of alloy and aluminum oxide, and finally recovers silicon in a ferrosilicon alloy form through magnetic separation, and recovers aluminum in an aluminum oxide form.
(3) Compared with the prior art, the method has the advantages of strong raw material adaptability, simple process flow, easier achievement of reaction conditions, high comprehensive utilization rate of resources, high added value of products, no generation of solid waste, environmental friendliness and the like, and greatly improves the economic benefit of lithium slag utilization.
Detailed Description
The invention will now be described in further detail with reference to specific examples, the scope of which is not limited to the examples.
Example 1
A method for comprehensively recovering valuable elements in spodumene industrial leaching residues comprises the following specific steps:
step 1, placing spodumene industrial leaching residues (particle size is smaller than 0.2 cm) and water in a reaction kettle according to a mass ratio of 1:20, and carrying out water leaching to remove CaSO 4 in the residues for 18 hours to obtain water leaching liquid and water leaching residues, wherein the leaching rate of the CaSO 4 is 94.6%; evaporating the water immersion liquid to obtain a calcium sulfate product;
Step 2, removing excessive moisture from the water immersed slag in the step 1 by using a filter press, drying at 90 ℃ for 48 hours to obtain residual slag, uniformly mixing the residual slag with an iron source, a carbon source and a nucleating agent, and adding a clay binder (white mud) accounting for 5% of the total mass of the mixed materials to prepare balls to obtain mixed balls, wherein the mass ratio of the residual slag to the carbon source (coking coal) is 1:1; the mass ratio of the residual slag to the nucleating agent (silicon-iron alloy powder with the silicon content of 45 percent) is 1:0.05; the iron source is waste iron, and the molar ratio of Si/Fe in the mixed material is 1:0.6; adding the mixed pellets into an ore heating furnace, heating to 1100 ℃ under the atmosphere of N 2 for reduction roasting, preserving heat for 3 hours, and magnetically separating to obtain the ferrosilicon alloy with the direct yield of 87.2% and the rest of the magnetically separated aluminum oxide slag; the ferrosilicon alloy comprises the following main components in percentage by mass: si: 44-56 wt%, fe:43 to 52 weight percent, and the total impurity is less than or equal to 2.0 weight percent; the content of Al 2O3 in the obtained oxygen-enriched aluminum oxide slag is 91 percent.
Example 2
A method for comprehensively recovering valuable elements in spodumene industrial leaching residues comprises the following specific steps:
Step 1, placing spodumene industrial leaching residues (particle size is smaller than 0.2 cm) and water in a reaction kettle according to a mass ratio of 1:40, and carrying out water leaching to remove CaSO 4 in the residues for 24 hours to obtain water leaching liquid and water leaching residues, wherein the leaching rate of the CaSO 4 is 96.2%; evaporating the water immersion liquid to obtain a calcium sulfate product;
Step 2, removing excessive moisture from the water immersed slag in the step 1 by using a filter press, drying for 4 hours at 400 ℃ to obtain residual slag, uniformly mixing the residual slag with an iron source, a carbon source and a nucleating agent, and adding a clay binder (bentonite) accounting for 5% of the total mass of the mixture to obtain mixed pellets, wherein the mass ratio of the residual slag to the carbon source (coking coal) is 1:1.2; the mass ratio of the residual slag to the nucleating agent (silicon-iron alloy powder with the silicon content of 35 percent) is 1:0.15; the iron source is ferric oxide powder, and the molar ratio of Si/Fe in the mixed material is 1:0.8; adding the mixed pellets into an ore heating furnace, heating to 1200 ℃ under the atmosphere of N 2 for reduction roasting, preserving heat for 8 hours, and magnetically separating to obtain ferrosilicon alloy with a direct yield of 90.6% and oxygen-enriched aluminum oxide residues as the rest after the reaction; the ferrosilicon alloy comprises the following main components in percentage by mass: si: 44-56 wt%, fe:43 to 52 weight percent, and the total impurity is less than or equal to 2.0 weight percent; the content of Al 2O3 in the obtained oxygen-enriched aluminum oxide slag is 89%.
Example 3
A method for comprehensively recovering valuable elements in spodumene industrial leaching residues comprises the following specific steps:
Step 1, placing spodumene industrial leaching residues (particle size is smaller than 0.2 cm) and water in a reaction kettle according to a mass ratio of 1:100, and carrying out water leaching to remove CaSO 4 in the residues for 18 hours to obtain water leaching liquid and water leaching residues, wherein the leaching rate of the CaSO 4 is 98.2%; evaporating the water immersion liquid to obtain a calcium sulfate product;
Step 2, removing excessive moisture from the water immersed slag in the step 1 by using a filter press, drying at 100 ℃ for 36 hours to obtain residual slag, uniformly mixing the residual slag with an iron source, a carbon source and a nucleating agent, and adding a clay binder (white mud) accounting for 6% of the total mass of the mixed materials to prepare balls to obtain mixed balls, wherein the mass ratio of the residual slag to the carbon source (charcoal) is 1:2; the mass ratio of the residual slag to the nucleating agent (silicon-iron alloy powder with the silicon content of 33 percent) is 1:0.1; the iron source is high-grade hematite, and the molar ratio of Si/Fe in the mixed material is 1:2.5; adding the mixed pellets into an ore heating furnace, heating to 1400 ℃ for reduction roasting under the atmosphere of N 2, and preserving heat for 5 hours, wherein after the reaction is finished, the direct yield of the ferrosilicon alloy obtained by magnetic separation is 92.3%, the rest of the magnetic separation is oxygen-enriched aluminum slag, and the ferrosilicon alloy comprises the following main components in percentage: si: 44-56 wt%, fe:43 to 52 weight percent, and the total impurity is less than or equal to 2.0 weight percent; the content of Al 2O3 in the obtained oxygen-enriched aluminum oxide slag is 87%.
Example 4
A method for comprehensively recovering valuable elements in spodumene industrial leaching residues comprises the following specific steps:
Step 1, placing spodumene industrial leaching residues (particle size is smaller than 0.2 cm) and water in a reaction kettle according to a mass ratio of 1:10, and carrying out water leaching to remove CaSO 4 in the residues for 30 hours to obtain water leaching liquid and water leaching residues, wherein the leaching rate of the CaSO 4 is 95.2%; evaporating the water immersion liquid to obtain a calcium sulfate product;
Step 2, removing excessive moisture from the water immersed slag in the step 1 by using a filter press, drying for 20 hours at 120 ℃ to obtain residual slag, uniformly mixing the residual slag with an iron source, a carbon source and a nucleating agent, and adding a clay binder (bentonite) accounting for 7% of the total mass of the mixture to obtain mixed pellets, wherein the mass ratio of the residual slag to the carbon source (semi-coke) is 1:4; the mass ratio of the residual slag to the nucleating agent (silicon-iron alloy powder with the silicon content of 33 percent) is 1:0.2; the iron source is magnetite, and the molar ratio of Si/Fe in the mixed material is 1:1; adding the mixed pellets into an ore heating furnace, heating to 1500 ℃ for reduction roasting under Ar atmosphere, and preserving heat for 3 hours, wherein after the reaction is finished, the direct yield of the ferrosilicon alloy obtained by magnetic separation is 94.2%, the rest of the magnetic separation is oxygen-enriched aluminum oxide slag, and the ferrosilicon alloy comprises the following main components in percentage: si: 44-56 wt%, fe:43 to 52 weight percent, and the total impurity is less than or equal to 2.0 weight percent; the content of Al 2O3 in the obtained oxygen-enriched aluminum oxide slag is 88 percent.
Claims (6)
1. A method for comprehensively recovering valuable elements in spodumene industrial leaching residues is characterized by comprising the following specific steps:
(1) Leaching spodumene industrial leaching residues and water according to a mass ratio of 1:10-100 for 18-30 h, wherein calcium sulfate enters a liquid phase;
(2) Evaporating the water leaching solution obtained in the step (1) to obtain a calcium sulfate product;
(3) After the water leaching slag obtained in the step (1) is subjected to filter pressing and drying, uniformly mixing the residual slag with an iron source, a carbon source and a nucleating agent, pelletizing the mixed material, reducing the mixed pellets, and magnetically separating a reduction product to obtain ferrosilicon alloy and oxygen-enriched aluminum oxide slag;
the mass ratio of the residual slag to the carbon source is 1:1-4, the molar ratio of Si to Fe in the mixed material is 1:0.6-2.5, and the mass ratio of the residual slag to the nucleating agent is 1:0.05-0.2;
the nucleating agent is ferrosilicon alloy powder with the mass percentage of silicon being lower than 45%;
the reducing atmosphere is N 2 or Ar atmosphere, the reducing temperature is 1100-1500 ℃, and the time is not less than 3 hours.
2. The method for comprehensively recovering valuable elements in spodumene industrial leaching residue according to claim 1, wherein the particle size of the spodumene industrial leaching residue in step (1) is <0.2cm.
3. The method for comprehensively recovering valuable elements in spodumene industrial leaching residue according to claim 1, wherein the step (3) of leaching residue is subjected to filter pressing and drying, namely, surplus water is removed from the leaching residue by using a filter press, and the leaching residue is dried for 4-48 hours at 90-400 ℃.
4. The method for comprehensively recovering valuable elements in spodumene industrial leaching residues according to claim 1, wherein the iron source in the step (3) is waste iron, ferric oxide powder, high-grade hematite or magnetite.
5. The method for comprehensively recovering valuable elements in spodumene industrial leaching residues according to claim 1, wherein the carbon source in the step (3) is coking coal, semi-coke or charcoal.
6. The method for comprehensively recovering valuable elements in spodumene industrial leaching residues, as claimed in claim 1, wherein the binder is white mud or bentonite, and the addition amount of the binder is not less than 5% of the mass of the mixed materials.
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