CN115418498A - Treatment method of lithium carbonate clay - Google Patents
Treatment method of lithium carbonate clay Download PDFInfo
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- CN115418498A CN115418498A CN202211017078.5A CN202211017078A CN115418498A CN 115418498 A CN115418498 A CN 115418498A CN 202211017078 A CN202211017078 A CN 202211017078A CN 115418498 A CN115418498 A CN 115418498A
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- flotation
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- 239000004927 clay Substances 0.000 title claims abstract description 75
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005188 flotation Methods 0.000 claims abstract description 270
- 239000002245 particle Substances 0.000 claims abstract description 220
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 115
- 238000005201 scrubbing Methods 0.000 claims abstract description 74
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 49
- 230000023556 desulfurization Effects 0.000 claims abstract description 49
- 238000005261 decarburization Methods 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 42
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 38
- 239000012141 concentrate Substances 0.000 claims abstract description 34
- 239000011575 calcium Substances 0.000 claims abstract description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000006260 foam Substances 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000000344 soap Substances 0.000 claims description 26
- 239000003153 chemical reaction reagent Substances 0.000 claims description 25
- 238000012216 screening Methods 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 229920002472 Starch Polymers 0.000 claims description 17
- 239000008107 starch Substances 0.000 claims description 17
- 235000019698 starch Nutrition 0.000 claims description 17
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- -1 ether amine Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000002734 clay mineral Substances 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- 235000019794 sodium silicate Nutrition 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000012991 xanthate Substances 0.000 claims description 2
- 238000003672 processing method Methods 0.000 abstract description 19
- 239000012535 impurity Substances 0.000 abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 12
- 239000011707 mineral Substances 0.000 abstract description 12
- 238000000605 extraction Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 17
- 239000012188 paraffin wax Substances 0.000 description 14
- 239000003814 drug Substances 0.000 description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- 238000003723 Smelting Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052683 pyrite Inorganic materials 0.000 description 5
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 5
- 239000011028 pyrite Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910001760 lithium mineral Inorganic materials 0.000 description 2
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052631 glauconite Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- KAGBQTDQNWOCND-UHFFFAOYSA-M lithium;chlorite Chemical compound [Li+].[O-]Cl=O KAGBQTDQNWOCND-UHFFFAOYSA-M 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by 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
Abstract
The invention discloses a processing method of lithium carbonate clay, belonging to the technical field of mineral extraction. According to the method, through multiple scrubbing and mixed material particle grading, coarse-grained calcite in lithium carbonate clay can be effectively removed, small particle bodies are conveniently enriched, effective secondary separation is carried out according to particle size and impurity content, the particles with different compositions are distinguished and subjected to desulfurization and decarburization, calcite removal and lithium flotation step by step, the content of impurities such as iron and calcium in the product is further reduced, and finally the lithium enrichment multiple of the obtained lithium concentrate is more than 2 times, the comprehensive recovery rate of lithium is more than 75%, and the removal rate of impurity elements such as iron, calcium and sulfur is more than 80%; the processing method makes full use of the characteristics of the carbonate lithium clay, combines a scrubbing process with low investment and low operation cost and a flotation process with strong adaptability and good sorting property aiming at the condition of low lithium content, and has high applicability and economy.
Description
Technical Field
The invention relates to the technical field of mineral extraction, in particular to a method for treating lithium carbonate clay.
Background
A large source of lithium resources is salt lake brine, but the exploitation and utilization of the source have high requirements on industrial technology and are easy to damage the ecological environment.
Besides the salt lake brine resource, the lithium resource can also be derived from hard rock lithium minerals. At present, the development of lithium minerals mainly takes spodumene and lepidolite as main materials, and Li in lithium concentrate is enriched through mineral separation 2 The content of O can be increased to 3-6%, and industrial or electronic grade lithium salt can be produced after the procedures of calcining, leaching, impurity removal and purification, lithium precipitation and the like.
In recent years, a clay with high enriched lithium content is discovered, and the lithium carbonate equivalent can be predicted to exceed million tons, and the lithium content reaches 0.1% -0.3%, and the clay is defined as lithium carbonate clay. According to the process mineralogy of the lithium clay, the main mineral compositions of the lithium clay comprise calcite, glauconite, illite, kaolinite, quartz, mica, pyrite and the like. Aiming at the novel ore soil, people perform preliminary lithium extraction exploration, mainly adopt double salt roasting or sulfuric acid curing to release lithium from lithium clay into a solution, and the obtained lithium-containing leachate is subjected to impurity removal, concentration and lithium precipitation to prepare a lithium salt. However, because the lithium content in the lithium clay is very low, hundreds of tons of leaching slag are produced when one ton of lithium salt is produced, and meanwhile, the energy consumption for smelting the raw material is very high, the investment of a lithium smelting plant is large, the operation cost is high, and the cost performance is very low, so that the industrial development of the lithium carbonate clay is restricted.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a processing method of lithium carbonate clay, which removes coarse calcite and improves the purity of mineral lithium by the working procedures of multi-stage scrubbing, shunting, flotation and the like, can finally realize that the lithium enrichment multiple is improved to more than 2 times, the lithium recovery rate is more than 75%, the material yield of the subsequent smelting lithium extraction treatment only accounts for 30-40% of that of the lithium carbonate clay, has low requirements on equipment and reagents required by the treatment, does not need to introduce a smelting process with high energy consumption, and can realize industrial scale.
In order to achieve the purpose, the invention adopts the technical scheme that:
a processing method of lithium carbonate clay comprises the following steps:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 100mm, placing the crushed lithium carbonate clay into a scrubbing machine for scrubbing for one time, and then performing vibration wet screening treatment to screen out particles which cannot be screened out to be used as tailings 1; sieving the obtained particles with the particle size less than 1mm, and placing the particles into a hydrocyclone for primary rotational flow to obtain underflow particles a and overflow particles b; mixing the rest particles with the underflow particles a, scrubbing the mixture for the second time, then carrying out vibration wet screening treatment with the screen mesh diameter of 1-2 mm, and screening out particles which cannot be screened out to be used as tailings 2; placing the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d; the bottom material particles c are used as tailings 3 or flow back to the hydrocyclone again to be mixed with the next batch of mixed materials for secondary scrubbing;
(2) If the calcium content of the overflow particles b is less than or equal to 3wt%, sequentially performing desulfurization and decarburization flotation treatment and lithium flotation treatment to obtain lithium concentrate 1; taking the flotation foam obtained by the desulfurization and decarburization flotation treatment as tailings 4, and taking the flotation foam obtained by the lithium flotation treatment as tailings 5; if the calcium content of the overflow particles b is more than 3wt%, subjecting the overflow particles b to the same treatment as the overflow particles d in the step (3);
(3) Sequentially carrying out desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment on the overflow particles d to obtain lithium concentrate 2; and (3) taking the flotation foam obtained by desulfurization and decarburization flotation as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation as tailings 8.
According to the processing method of the lithium carbonate clay, coarse calcite in the lithium carbonate clay can be effectively removed through multiple scrubbing and mixed particle grading, small particle bodies are enriched, effective secondary separation is carried out according to particle size and impurity content, desulfurization and decarburization, calcite removal and lithium flotation are carried out step by step, the content of impurities such as iron and calcium in the product is further reduced, the lithium enrichment multiple of the obtained lithium concentrate is up to more than 2 times, the comprehensive recovery rate of lithium is up to more than 75%, the removal rate of impurity elements such as iron, calcium and sulfur is more than 80%, and the material yield of subsequent smelting lithium extraction processing only accounts for 30% -40% of the lithium carbonate clay. The processing method fully utilizes the characteristics of the carbonate lithium clay, combines a scrubbing process with low investment and low running cost and a flotation process with strong adaptability and good sorting property aiming at the condition of low lithium content, reduces the investment of mineral processing equipment and the consumption of flotation reagents, and has high applicability and economy.
According to the processing method of the lithium carbonate clay, the physicochemical properties of the screened particles are utilized, firstly, sulfur-containing substances and carbon in the particles are preferentially removed, and the interference of the sulfur-containing substances and the carbon on the subsequent flotation is avoided; if the content of the granular calcium is higher, the pH value is further adjusted by alkali, and fine-fraction calcite is removed; and finally, after a large amount of acid-consuming calcite is removed, adjusting the pH value of the ore pulp to be 1-2.5 by using mixed acid, effectively enriching by lithium flotation to obtain lithium concentrate, fully considering the quality of the lithium carbonate clay of different batches, and treating different treated particles by a short-range route and a long-range route in a distinguishing manner, so that the waste of process reagents is reduced, and the overall product quality is improved.
Preferably, the lithium carbonate clay in the step (1) has a lithium content of more than or equal to 0.05wt% and a calcium content of more than or equal to 5wt%.
Preferably, the particle size of the crushed lithium carbonate clay is less than or equal to 50mm.
Preferably, the first scrubbing in the step (1) is cylindrical or vertical scrubbing, and the second scrubbing is vertical scrubbing.
More preferably, the concentration of scrubbing is 50 to 80% for the primary scrubbing and the secondary scrubbing.
Preferably, the agent used in the desulfurization and decarburization flotation treatment is at least one of an acidic pH regulator, an inhibitor, a foaming agent and a sulfur-carbon collector.
More preferably, the acidic pH regulator is at least one of sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid; the inhibitor is at least one of sodium silicate, starch, dextrin and/or a modifier; the foaming agent is at least one of No. two oil and methyl isobutyl carbinol; the sulfur-carbon collector is at least one of xanthate and/or modifier, black pigment and/or modifier, diesel oil and kerosene.
Preferably, the reagent used in the calcite-removing flotation treatment is at least one of an alkaline pH regulator, a depressant and a calcite collector.
More preferably, the alkaline pH adjusting agent is a mixture of sodium carbonate and sodium hydroxide; the inhibitor is at least one of sodium silicate, starch, dextrin and/or a modifier; the calcite collector is an anionic collector, and the anionic collector comprises fatty acid soap and sulfonated fatty acid.
Preferably, the agent for lithium flotation is at least one of an acidic pH regulator and a lithium clay mineral collector.
More preferably, the lithium clay mineral collector is at least one of an ether amine collector and a polyamine collector.
According to the characteristics of impurities in the treated particles and the target mineral lithium, the lithium element can be effectively enriched and various impurities can be removed by selecting a proper treatment environment and a proper treatment agent, and the purity of the finally obtained lithium concentrate is improved.
The processing method of the lithium carbonate clay has the beneficial effects that through multiple scrubbing and mixed particle grading, coarse-grained calcite in the lithium carbonate clay can be effectively removed, small particle bodies can be conveniently enriched, effective secondary separation is carried out according to the particle size and the impurity content of particles, and desulfurization, decarburization, calcite removal and lithium flotation are carried out on particles with different compositions step by step, so that the content of impurities such as iron, calcium and the like in the product is further reduced, the lithium enrichment multiple of the obtained lithium concentrate is up to more than 2 times, the comprehensive recovery rate of lithium is up to more than 75%, and the removal rate of impurity elements such as iron, calcium, sulfur and the like is more than 80%; the processing method fully utilizes the characteristics of the carbonate lithium clay, combines a scrubbing process with low investment and low operation cost and a flotation process with strong adaptability and good sorting property aiming at the condition of low lithium content, does not need to introduce a smelting process with high energy consumption, and has high applicability and economy.
Drawings
Fig. 1 is a schematic flow chart of a processing method of lithium carbonate clay according to the present invention.
Fig. 2 is a schematic mineral diagram of lithium carbonate clay used in embodiment 1 of the present invention.
Fig. 3 is an XRD test pattern of lithium carbonate clay used in example 1 of the present invention.
Fig. 4 is a schematic flow chart of a processing method of lithium carbonate clay according to embodiment 1 of the present invention.
Fig. 5 is a schematic flow chart of a processing method of lithium carbonate clay according to embodiment 2 of the present invention.
Fig. 6 is a schematic flow chart of a processing method of lithium carbonate clay according to embodiment 3 of the present invention.
Fig. 7 is a schematic flow chart of a method for treating lithium carbonate clay according to comparative example 1 of the present invention.
Fig. 8 is a schematic flow chart of a method for treating lithium carbonate clay according to comparative example 2 of the present invention.
Fig. 9 is a schematic flow chart of a method for treating lithium carbonate clay according to comparative example 3 of the present invention.
Detailed Description
The treatment method of the lithium carbonate clay comprises the following steps:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 100mm, placing the crushed lithium carbonate clay into a scrubbing machine for scrubbing for one time, and then performing vibration wet screening treatment to screen out particles which cannot be screened out to be used as tailings 1; sieving the obtained particles with the particle size less than 1mm, and placing the particles into a hydrocyclone for primary rotational flow to obtain underflow particles a and overflow particles b; mixing the rest particles with the underflow particles a, scrubbing the mixture for the second time, then carrying out vibration wet screening treatment with the screen mesh diameter of 1-2 mm, and screening out particles which cannot be screened out to be used as tailings 2; placing the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d; the bottom material particles c are used as tailings 3 or flow back to the hydrocyclone again to be mixed with the next batch of mixed materials for secondary scrubbing;
(2) If the calcium content of the overflow particles b is less than or equal to 3wt%, sequentially performing desulfurization and decarburization flotation treatment and lithium flotation treatment to obtain lithium concentrate 1; taking the flotation foam obtained by the desulfurization and decarburization flotation treatment as tailings 4, and taking the flotation foam obtained by the lithium flotation treatment as tailings 5; if the calcium content of the overflow particles b is more than 3wt%, subjecting the overflow particles b to the same treatment as the overflow particles d in the step (3);
(3) Sequentially carrying out desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment on the overflow particles d to obtain lithium concentrate 2; and (3) taking the flotation foam obtained by desulfurization and decarburization flotation treatment as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation treatment as tailings 8.
The process of the present invention is schematically illustrated in fig. 1, and in order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples/comparative examples, which are intended to be a detailed understanding of the contents of the present invention and not to be limiting of the present invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents, raw materials and instruments designed in the practice of the invention and the comparative examples are common reagents, raw materials and instruments unless otherwise specified.
Example 1
An embodiment of the processing method of lithium carbonate clay according to the present invention, as shown in fig. 4, includes the following steps:
(1) Collecting lithium carbonate clay, wherein the mineral schematic diagram of the lithium carbonate clay is shown in FIG. 2; the XRD test pattern is shown in figure 3, and it can be seen that the mineral composition comprises large-particle size calcite Cc besides lithium chlorite 1 Small particle size calcite Cc 2 Quartz Q, etc. Crushing the lithium carbonate clay until the particle size is less than or equal to 15mm, placing the crushed lithium carbonate clay into a cylindrical scrubbing machine for scrubbing once, wherein the scrubbing concentration is 65%, then performing two-layer vibration wet screen treatment with the screen diameters of 10mm and 1mm, and screening out particles with the particle size of more than 10mm to serve as tailings 1; sieving the obtained granules with a particle size of < 1mm and adding waterPerforming primary rotational flow in the hydrocyclone to obtain underflow particles a and overflow particles b with the particle size of below 38 mu m; mixing the obtained particles with the residual particle size of 1-10 mm with the underflow particles a, placing the obtained mixed material in a vertical scrubbing machine for secondary scrubbing, scrubbing the mixed material with the concentration of 75%, then performing vibration wet screening treatment with the screen mesh size of 2mm, and screening out the particles with the particle size of more than 2mm, which cannot be screened, to obtain tailings 2; placing the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d with the particle size of below 250 mu m; the bottom material particles c are used as tailings 3;
(2) The calcium content of the overflow particles b is less than or equal to 3wt%, and desulfurization and decarburization flotation treatment and lithium flotation treatment are sequentially carried out to obtain lithium concentrate 1; taking the flotation foam obtained by the desulfurization and decarburization flotation treatment as tailings 4, and taking the flotation foam obtained by the lithium flotation treatment as tailings 5;
the dosage of the reagent used for desulfurization and decarburization flotation and the corresponding feed of the treated particles is as follows: 3 kg/ton of sulfuric acid flotation feed, 300 g/ton of starch flotation feed, 40 g/ton of No. 2 oil flotation feed, 100 g/ton of butyl xanthate flotation feed and 30 g/ton of diesel oil flotation feed; the flotation concentration of the desulfurization and decarburization flotation treatment is 30 percent;
the dosage of the medicament used for lithium flotation treatment and the corresponding feed of the treated particles is as follows: 5 kg/ton of sulfuric acid flotation feed, 2 kg/ton of hydrofluoric acid flotation feed and 300 kg/ton of ether amine modified collecting agent;
(3) Sequentially carrying out desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment on the overflow particles d to obtain lithium concentrate 2; taking the flotation foam obtained by the desulfurization and decarburization flotation treatment as tailings 6, taking the flotation foam obtained by the calcite removal flotation as tailings 7, and taking the flotation foam obtained by the lithium flotation treatment as tailings 8;
the dosage of the reagent used for desulfurization and decarburization flotation and the corresponding feed of the treated particles is as follows: 6 kg/ton of sulfuric acid flotation feed, 600 g/ton of starch flotation feed, 50 g/ton of No. 2 oil flotation feed, 150 g/ton of butyl xanthate flotation feed and 50 g/ton of diesel oil flotation feed; the flotation concentration of the desulfurization and decarburization flotation treatment is 30 percent;
the calcite-removing flotation treatment stage comprises a rough flotation stage and a fine flotation stage, and the dosage of the medicament used in the rough flotation stage and the dosage of the feed material for correspondingly treating particles are as follows: 2 kg/ton of sodium carbonate, 2 kg/ton of sodium hydroxide, 3 kg/ton of sodium silicate and 3 kg/ton of modified oxidized paraffin soap; the fine flotation stage comprises 0.5kg of sodium hydroxide per ton of flotation feed, 0.5kg of sodium silicate per ton of flotation feed and 0.5kg of modified oxidized paraffin soap per ton of flotation feed;
the dosage of the medicament used for the lithium flotation treatment and the corresponding particle feeding material for the lithium flotation treatment is as follows: 10 kg/ton of sulfuric acid flotation feed, 4 kg/ton of hydrofluoric acid flotation feed and 500 kg/ton of ether amine modified collecting agent.
And (3) carrying out statistics on element content, yield and the like on products in each stage, wherein lithium concentrate 1 and 2 are combined, tailings 5 and 8 are combined, tailings 4 and 6 are combined, tailings 1-3 are combined, and the test results are shown in table 1.
TABLE 1
It can be seen that the yield of the lithium concentrate obtained by the treatment method in example 1 reaches 45%, the distribution rate of lithium element reaches 88.62%, the tailings obtained by the mineral separation in each stage are low in grade, and the lithium extraction efficiency is high. Meanwhile, the yield of 1-3 tailings removed by simple scrubbing is about 30%, the Li grade is improved from 0.25% of raw ore to 0.34%, and the Li grade is enriched by 1.36 times; the subsequent flotation feed only accounts for 70% of the raw ore, and pyrite, carbon, calcite, quartz and the like are respectively removed by flotation, so that the concentrate grade is further improved to 0.50%. Compared with the existing processes (low crushing efficiency and low scrubbing concentration of raw ores, and high-concentration scrubbing and coarse polishing and selective ore grinding which cannot be achieved) which carry out processing by means of physical scrubbing and the like independently, the technical scheme has higher processing efficiency, and the grade of finally obtained lithium is further improved.
Example 2
An embodiment of the processing method of lithium carbonate clay according to the present invention, as shown in fig. 5, includes the following steps:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 100mm, placing the crushed lithium carbonate clay into a cylindrical scrubbing machine for scrubbing for one time, wherein the scrubbing concentration is 70%, then performing two-layer vibration wet screen treatment with the screen diameters of 40mm and 1mm, and screening out particles with the particle size of more than 40mm to serve as tailings 1; sieving the obtained particles with the particle size of less than 1mm, and placing the particles into a hydraulic cyclone for primary cyclone to obtain underflow particles a and overflow particles b with the particle size of less than 250 mu m; mixing the obtained particles with the residual particle size of 1-40 mm with the underflow particles a, placing the obtained mixed material in a vertical scrubbing machine for secondary scrubbing, scrubbing the mixed material with the concentration of 55%, then performing vibration wet screening treatment with the screen mesh size of 2mm, and screening out the particles with the particle size of more than 2mm, which cannot be screened, to obtain tailings 2; placing the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d with the particle size of below 250 mu m; the bottom material particles c are used as tailings 3;
(2) The calcium content of the overflow particles b is more than 3wt%, and the overflow particles b and the overflow particles d are combined to be sequentially subjected to desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment to obtain lithium concentrate 2; taking the flotation foam obtained by desulfurization and decarburization flotation as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation as tailings 8;
wherein the reagent system used for the desulfurization and decarburization flotation treatment is as follows: 2kg of sodium silicate per ton of flotation feed, 100g of methyl isobutyl carbinol per ton of flotation feed and 250g of amyl xanthate per ton of flotation feed; the flotation concentration of the desulfurization and decarburization flotation treatment is 28%;
the calcite-removing flotation treatment comprises a primary rough flotation stage and a secondary fine flotation stage, wherein the dosage of reagents used in the rough flotation stage and the dosage of corresponding treatment particle feeding materials are as follows: 4 kg/ton of sodium carbonate, 4 kg/ton of sodium hydroxide, 1 kg/ton of starch and 3.5 kg/ton of a mixture of oxidized paraffin soap and oleic soap; the first fine flotation stage reagent comprises 0.5 kg/ton of sodium hydroxide, 0.75 kg/ton of sodium silicate and 0.75 kg/ton of a mixture of oxidized paraffin soap and oleic soap; the second fine flotation stage comprises 0.5 kg/ton of sodium hydroxide, 0.25 kg/ton of sodium silicate and 0.25 kg/ton of a mixture of oxidized paraffin soap and oleic soap;
the dosage of the medicament used for lithium flotation treatment and the corresponding feed of the treated particles is as follows: 15 kg/ton of sulfuric acid flotation feed, 4 kg/ton of hydrofluoric acid flotation feed and 800 kg/ton of ether amine modified collector.
And (3) carrying out statistics on element content, yield and the like on products at each stage, wherein tailings 1-3 are combined, and the test results are shown in table 2.
TABLE 2
It can be seen that the yield of the lithium concentrate obtained by the treatment method in example 2 reaches 33%, the distribution rate of lithium element reaches 75.30%, the tailings obtained by smelting in each stage are low in grade, and the lithium extraction efficiency is high. Meanwhile, the yield of 1-3 tailings removed by simple scrubbing is about 40%, the Li grade is improved to 0.22% from 0.15% of raw ore, and the Li grade is enriched by 1.47 times; the subsequent flotation feed only accounts for 60% of the raw ore, and pyrite, carbon, calcite, quartz and the like are respectively removed by flotation, so that the concentrate grade is further improved to 0.34%.
Example 3
An embodiment of the processing method of lithium carbonate clay according to the present invention, as shown in fig. 6, includes the following steps:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 30mm, placing the crushed lithium carbonate clay into a cylindrical scrubbing machine for scrubbing for one time, scrubbing the lithium carbonate clay with the concentration of 65%, and then performing two-layer vibration wet-screen treatment with the screen diameters of 15mm and 1mm, and screening out particles with the particle size of more than 15mm to be used as tailings 1; sieving the obtained particles with the particle size of less than 1mm, placing the particles into a hydrocyclone for primary rotational flow to obtain underflow particles a and overflow particles b with the particle size of less than 38 mu m; mixing the obtained particles with the residual particle size of 1-15 mm with the underflow particles a, placing the obtained mixed material in a vertical scrubbing machine for secondary scrubbing, scrubbing the mixed material with the concentration of 75%, then performing vibration wet screening treatment with the screen mesh aperture of 1mm, and screening out the particles with the particle size larger than 1mm, which cannot be screened, to obtain tailings 2; placing the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d with the particle size of below 38 mu m; the backing material particles c are placed into the vertical scrubbing machine again to be mixed with the subsequent particles for secondary scrubbing;
(2) The calcium content of the overflow particles b is more than 3wt%, and the overflow particles b and the overflow particles d are combined to be sequentially subjected to desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment to obtain lithium concentrate 2; taking the flotation foam obtained by desulfurization and decarburization flotation as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation as tailings 8;
the desulfurization and decarburization flotation treatment comprises a rough flotation stage and a fine flotation stage, wherein the dosage of reagents used in the rough flotation stage and corresponding treatment particle feeding materials is as follows: 300 g/ton of starch, 100 g/ton of No. 2 oil, 250 g/ton of butyl xanthate and 100 g/ton of diesel oil; the agent used in the fine flotation stage is starch 100 g/ton flotation feed, and the flotation concentration of the desulfurization and decarburization flotation treatment is 32%;
the calcite-removing flotation treatment comprises a rough flotation stage and a fine flotation stage, wherein the dosage of reagents used in the rough flotation stage and the dosage of corresponding treatment particle feeding materials are as follows: 5 kg/ton of sodium hydroxide, 0.6 kg/ton of starch and 3.5 kg/ton of a mixture of oxidized paraffin soap and oleic soap; the reagents in the fine flotation stage comprise 0.25 kg/ton of sodium hydroxide, 0.25 kg/ton of starch and 0.5 kg/ton of a mixture of oxidized paraffin soap and oleic soap;
the dosage of the medicament used for the lithium flotation treatment and the corresponding particle feeding material for the lithium flotation treatment is as follows: 20 kg/ton of sulfuric acid flotation feed, 6 kg/ton of hydrofluoric acid flotation feed and 700 kg/ton of ether amine modified collecting agent.
The product at each stage is subjected to statistics of element content, yield and the like, wherein tailings 1 and 2 are combined, and the test results are shown in table 3.
TABLE 3
It can be seen that the yield of the lithium concentrate obtained by the treatment method in example 3 reaches 40%, the distribution rate of lithium element reaches 83.54%, the tailings obtained by the mineral separation in each stage are low in grade, and the lithium extraction efficiency is high. Meanwhile, the yield of 1-2 tailings removed by simple scrubbing is about 35%, the Li grade is improved to 0.29% from 0.20% of raw ore, and the Li grade is enriched by 1.45 times; the subsequent flotation feed only accounts for 65% of the raw ore, and pyrite, carbon, calcite, quartz and the like are respectively removed by flotation, so that the concentrate grade is further improved to 0.42%.
Comparative example 1
A comparative example of the processing method of lithium carbonate clay according to the present invention, as shown in fig. 7, includes the following steps:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 40mm, placing the crushed lithium carbonate clay into a cylindrical scrubbing machine for scrubbing for one time, wherein the scrubbing concentration is 65%, then performing two-layer vibration wet screen treatment with the screen diameters of 10mm and 3mm, and screening out particles with the particle size of more than 10mm to serve as tailings 1; sieving the obtained particles with the particle size less than 3mm, and placing the particles into a hydrocyclone for primary rotational flow to obtain underflow particles a and overflow particles b; mixing the obtained particles with the residual particle size of 3-10 mm with the underflow particles a, feeding the obtained mixed material into a ball mill for ore grinding, wherein the ore grinding concentration is 65%, and placing the overflow of the ball mill into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d with the particle size of below 250 mu m; returning the bottom material particles c to the ball mill for continuous grinding;
(2) The calcium content of the overflow particles b is more than 3wt%, and the overflow particles b and the overflow particles d are combined to be sequentially subjected to desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment to obtain lithium concentrate 2; taking the flotation foam obtained by desulfurization and decarburization flotation as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation as tailings 8;
wherein the desulfurization decarbonization flotation treatment comprises a rough flotation stage and a fine flotation stage, wherein the dosage of the reagent used in the rough flotation stage and the corresponding feed of the treated particles is as follows: 500g of starch per ton of flotation feed, 300g of No. 2 oil per ton of flotation feed, 350g of butyl xanthate per ton of flotation feed and 200g of diesel oil per ton of flotation feed; the agent used in the fine flotation stage is starch 200 g/ton flotation feed, and the flotation concentration of the desulfurization and decarburization flotation treatment is 30%;
the calcite-removing flotation treatment comprises a rough flotation stage and a fine flotation stage, wherein the dosage of reagents used in the rough flotation stage and the dosage of corresponding treatment particle feeding materials are as follows: 5 kg/ton of sodium hydroxide, 0.7 kg/ton of starch and 4.5 kg/ton of a mixture of oxidized paraffin soap and oleic soap; the reagents in the fine flotation stage comprise 0.5 kg/ton of sodium hydroxide, 0.3 kg/ton of starch and 0.8 kg/ton of a mixture of oxidized paraffin soap and oleic soap;
the dosage of the medicament used for the lithium flotation treatment and the corresponding particle feeding material for the lithium flotation treatment is as follows: 10 kg/ton of sulfuric acid flotation feed, 8 kg/ton of hydrofluoric acid flotation feed and 800 kg/ton of ether amine modified collector.
The product at each stage was subjected to statistics of element content, yield, etc., and the test results are shown in table 4.
TABLE 4
It can be seen that the treatment described in comparative example 1 gives a lithium concentrate yield of 30% and a lithium element distribution (recovery) of only 62.61%, much lower than in examples 1, 2 and 3. According to the comparative example, only one section of cylinder is adopted for scrubbing, the yield of the scrubbed and removed tailings is about 15%, the Li grade is improved to 0.16% from 0.14% of raw ore and is only enriched by 1.14 times, the granularity of materials with the size of 3-10 mm below the screen after scrubbing is coarse, the materials are not suitable for direct flotation, and the ore grinding and grading operation with high equipment investment is increased; and the materials with the diameter less than 3mm enter the overflow product generated by the cyclone 1, the Ca content of the overflow product exceeds the standard, and the overflow product must enter a route 2; the yield of the raw ore occupied by the subsequent flotation feed is up to 85%, and pyrite, carbon, calcite, quartz and the like are removed by flotation respectively, so that the concentrate grade is further improved to 0.29%, but the dosage of the flotation reagent is greatly increased.
Comparative example 2
A comparative example of the processing method of lithium carbonate clay according to the present invention, as shown in fig. 8, includes the following steps:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 15mm, placing the crushed lithium carbonate clay into a cylindrical scrubbing machine for scrubbing once, wherein the scrubbing concentration is 65%, then performing two-layer vibration wet screen treatment with the screen diameters of 10mm and 3mm, and screening out particles with the particle size of more than 10mm to serve as tailings 1; sieving the obtained particles with the particle size less than 3mm, placing the particles into a hydrocyclone for primary rotational flow to obtain underflow particles a and overflow particles b with the particle size less than 250 mu m; mixing the obtained particles with the rest particle size of 3-10 mm with the underflow particles a, placing the obtained mixed material in a vertical scrubbing machine for secondary scrubbing, scrubbing the mixed material with the concentration of 75%, then performing vibration wet screening treatment with the screen mesh size of 2mm, and screening out the particles with the particle size of more than 2mm, which cannot be screened, to obtain tailings 2; placing the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d with the particle size of below 250 mu m; the bottom material particles c are used as tailings 3;
(2) The calcium content of the overflow particles b is more than 3wt%, and the overflow particles b and the overflow particles d are combined to be sequentially subjected to desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment to obtain lithium concentrate 2; taking the flotation foam obtained by desulfurization and decarburization flotation as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation as tailings 8;
wherein the reagent system used for the desulfurization and decarburization flotation treatment is as follows: 2kg of sodium silicate per ton of flotation feed, 100g of methyl isobutyl carbinol per ton of flotation feed and 250g of amyl xanthate per ton of flotation feed; the flotation concentration of the desulfurization and decarburization flotation treatment is 28 percent;
the calcite-removing flotation treatment comprises a primary rough flotation stage and a secondary fine flotation stage, wherein the dosage of reagents used in the rough flotation stage and the dosage of corresponding treatment particle feeding materials are as follows: 4 kg/ton of sodium carbonate, 4 kg/ton of sodium hydroxide, 3 kg/ton of sodium silicate and 4.5 kg/ton of a mixture of oxidized paraffin soap and oleic soap; the first fine flotation stage reagent comprises 0.5 kg/ton of sodium hydroxide, 0.75 kg/ton of sodium silicate and 0.75 kg/ton of a mixture of oxidized paraffin soap and oleic soap; the second fine flotation stage comprises 0.5 kg/ton of sodium hydroxide, 0.25 kg/ton of sodium silicate and 0.25 kg/ton of a mixture of oxidized paraffin soap and oleic soap;
the dosage of the medicament used for lithium flotation treatment and the corresponding feed of the treated particles is as follows: 15 kg/ton of sulfuric acid flotation feed, 4 kg/ton of hydrofluoric acid flotation feed and 800 kg/ton of ether amine modified collector.
And (3) carrying out statistics on element content, yield and the like on products at each stage, wherein 1-3 tailings are combined, and the test results are shown in table 5.
TABLE 5
From the statistics of the test results of the two schemes of example 1 and comparative example 2, it can be seen that the first group of cyclones in the treatment method described in comparative example 2 is fed with a size fraction material with a particle size of < 3mm, the overflow product is fine mud with a particle size of < 250 μm, the Ca content of the overflow product is high, and the overflow product needs to enter the route 2 for treatment, so that the yield of the scouring tailings is reduced from 30% to 26%, the yield of the flotation tailings 7 is increased from 10% to 17%, the beneficiation cost such as reagent consumption is increased, the yield of the lithium concentrate is reduced from 45% to 40%, and the Li grade and Li recovery of the concentrate are reduced from 0.50% and 88.62% to 0.44% and 81.75%, respectively.
Comparative example 3
A comparative example of the processing method of lithium carbonate clay according to the present invention, as shown in fig. 9, includes the following steps:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 15mm, placing the crushed lithium carbonate clay into a cylindrical scrubbing machine for scrubbing once, wherein the scrubbing concentration is 65%, then performing two-layer vibration wet screen treatment with the screen diameters of 10mm and 1mm, and screening out particles with the particle size of more than 10mm to serve as tailings 1; sieving the obtained particles with the particle size of less than 1mm, placing the particles into a hydrocyclone for primary rotational flow to obtain underflow particles a and overflow particles b with the particle size of less than 38 mu m; mixing the obtained particles with the rest particle size of 1-10 mm with the underflow particles a, feeding the obtained mixed material into a ball mill for ore grinding, wherein the ore grinding concentration is 65%, and placing mill overflow into a hydrocyclone for secondary rotational flow to obtain underflow particles c and overflow particles d with the particle size of below 250 mu m; returning the bottom material particles c to the ball mill for continuous grinding;
(2) The calcium content of the overflow particles b is less than or equal to 3wt%, and desulfurization and decarburization flotation treatment and lithium flotation treatment are sequentially carried out to obtain lithium concentrate 1; taking the flotation foam obtained by the desulfurization and decarburization flotation treatment as tailings 4, and taking the flotation foam obtained by the lithium flotation treatment as tailings 5;
the agent used for desulfurization and decarburization flotation treatment and the amount of the corresponding treated particle feed are as follows: 3 kg/ton of sulfuric acid flotation feed, 300 g/ton of starch flotation feed, 40 g/ton of No. 2 oil flotation feed, 100 g/ton of butyl xanthate flotation feed and 30 g/ton of diesel oil flotation feed; the flotation concentration of the desulfurization and decarburization flotation treatment is 30 percent;
the dosage of the medicament used for the lithium flotation treatment and the corresponding particle feeding material for the lithium flotation treatment is as follows: 5 kg/ton of sulfuric acid flotation feed, 2 kg/ton of hydrofluoric acid flotation feed and 300 kg/ton of ether amine modified collecting agent;
(3) Sequentially carrying out desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment on the overflow particles d to obtain lithium concentrate 2; taking the flotation foam obtained by desulfurization and decarburization flotation as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation as tailings 8;
the dosage of the reagent used for desulfurization and decarburization flotation and the corresponding feed of the treated particles is as follows: 6 kg/ton of sulfuric acid flotation feed, 600 g/ton of starch flotation feed, 100 g/ton of No. 2 oil flotation feed, 250 g/ton of butyl xanthate flotation feed and 100 g/ton of diesel oil flotation feed; the flotation concentration of the desulfurization and decarburization flotation treatment is 30 percent;
the calcite-removing flotation treatment stage comprises a rough flotation stage and a fine flotation stage, and the dosage of the medicament used in the rough flotation stage and the dosage of the feed material for correspondingly treating particles are as follows: 2 kg/ton of sodium carbonate, 4 kg/ton of sodium hydroxide, 5 kg/ton of sodium silicate and 6 kg/ton of modified oxidized paraffin soap; the fine flotation stage comprises 0.5kg of sodium hydroxide per ton of flotation feed, 0.5kg of sodium silicate per ton of flotation feed and 0.75kg of modified oxidized paraffin soap per ton of flotation feed;
the dosage of the medicament used for the lithium flotation treatment and the corresponding particle feeding material for the lithium flotation treatment is as follows: 8 kg/ton of sulfuric acid flotation feed, 8 kg/ton of hydrofluoric acid flotation feed and 850 kg/ton of ether amine modified collecting agent.
The product from each stage was subjected to statistics of element content, yield, etc., where lithium concentrate 1 and 2 were combined, tailings 5 and 8 were combined, and tailings 4 and 6 were combined, and the test results are shown in table 6.
TABLE 6
As can be seen from the test results of both the example 1 and comparative example 3 processes, the treatment process described in comparative example 3, using only one stage of scrubbing, resulted in only a 15% yield of the scrub tailings 1, an increase in the flotation tailings 7 yield from 10% to 30%, a substantial increase in the grinding costs and the reagent costs, a reduction in the lithium concentrate yield from 45% to 40%, and a reduction in the concentrate Li grade and Li recovery from 0.50% and 88.62% to 0.44% and 78.81%, respectively.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The method for treating the lithium carbonate clay is characterized by comprising the following steps of:
(1) Crushing the lithium carbonate clay until the particle size is less than or equal to 100mm, placing the crushed lithium carbonate clay into a scrubbing machine for scrubbing for one time, and then performing vibration wet screening treatment to screen out particles which cannot be screened out to be used as tailings 1; sieving the obtained particles with the particle size less than 1mm, and placing the particles into a hydrocyclone for primary rotational flow to obtain underflow particles a and overflow particles b; mixing the rest particles with the underflow particles a, scrubbing the mixture for the second time, then carrying out vibration wet screening treatment with the screen mesh diameter of 1-2 mm, and screening out particles which cannot be screened out to be used as tailings 2; placing the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d; the bottom material particles c are used as tailings 3 or flow back to the hydrocyclone again to be mixed with the next batch of mixed materials for secondary scrubbing;
(2) If the calcium content of the overflow particles b is less than or equal to 3wt%, sequentially performing desulfurization and decarburization flotation treatment and lithium flotation treatment to obtain lithium concentrate 1; taking the flotation foam obtained by the desulfurization and decarburization flotation treatment as tailings 4, and taking the flotation foam obtained by the lithium flotation treatment as tailings 5; if the calcium content of the overflow particles b is more than 3wt%, subjecting the overflow particles b to the same treatment as the overflow particles d in step (3);
(3) Sequentially carrying out desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment on the overflow particles d to obtain lithium concentrate 2; and (3) taking the flotation foam obtained by desulfurization and decarburization flotation as tailings 6, taking the flotation foam obtained by calcite removal flotation as tailings 7, and taking the flotation foam obtained by lithium flotation as tailings 8.
2. The method for processing lithium carbonate clay according to claim 1, wherein the lithium carbonate clay in step (1) has a lithium content of 0.05wt% or more and a calcium content of 5wt% or more.
3. The method for treating lithium carbonate clay according to claim 1, wherein the primary scrubbing in step (1) is cylindrical or vertical scrubbing, and the secondary scrubbing is vertical scrubbing; the scrubbing concentration of the primary scrubbing and the secondary scrubbing is 50-80%.
4. The method for processing lithium carbonate clay according to claim 1, wherein the reagent used in the desulfurization/decarburization flotation process is at least one of an acidic pH regulator, an inhibitor, a foaming agent, and a sulfur-carbon collector.
5. The method for processing lithium carbonate clay according to claim 4, wherein the acidic pH regulator is at least one of sulfuric acid, phosphoric acid, hydrochloric acid, and hydrofluoric acid; the inhibitor is at least one of sodium silicate, starch, dextrin and/or a modifier; the foaming agent is at least one of No. two oil and methyl isobutyl carbinol; the sulfur-carbon collector is at least one of xanthate and/or modifier, black pigment and/or modifier, diesel oil and kerosene.
6. The method for treating lithium carbonate clay according to claim 1, wherein the agent used in the delicatecalcite flotation treatment is at least one of an alkaline pH regulator, an inhibitor and a calcite collector.
7. The method for processing lithium carbonate clay according to claim 6, wherein the alkaline pH adjuster is a mixture of sodium carbonate and sodium hydroxide; the inhibitor is at least one of sodium silicate, starch, dextrin and/or a modifier; the calcite collector is an anionic collector, and the anionic collector comprises fatty acid soap and sulfonated fatty acid.
8. The method for processing lithium carbonate clay according to claim 1, wherein the agent for lithium flotation is at least one of an acidic pH regulator and a lithium clay mineral collector.
9. The method for treating lithium carbonate clay according to claim 8, wherein the lithium clay mineral collector is at least one of an ether amine collector and a polyamine collector.
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| WO2024040891A1 (en) * | 2022-08-23 | 2024-02-29 | 广东邦普循环科技有限公司 | Treatment method for carbonate lithium clay |
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| WO2019141098A1 (en) * | 2018-01-17 | 2019-07-25 | 成都绿锂环保科技有限公司 | High-value comprehensive utilization method for lithium slag |
| CN110694788A (en) * | 2019-10-30 | 2020-01-17 | 中蓝长化工程科技有限公司 | Beneficiation method for high-calcium-magnesium type low-grade spodumene ore |
| CN111330743A (en) * | 2020-04-09 | 2020-06-26 | 北京矿冶科技集团有限公司 | Spodumene ore flotation collector, preparation method thereof and spodumene ore dressing process for clay mineralization |
| CN113825848A (en) * | 2019-03-29 | 2021-12-21 | 锂业美洲公司 | Method for extracting lithium from sedimentary clay |
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| JP7158332B2 (en) * | 2019-03-29 | 2022-10-21 | Ｊｘ金属株式会社 | Method for concentrating lithium and method for producing lithium hydroxide |
| CN115418498B (en) * | 2022-08-23 | 2023-12-12 | 广东邦普循环科技有限公司 | Treatment method of carbonate lithium clay |
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| CN1270927A (en) * | 1999-04-20 | 2000-10-25 | 中国地质科学院盐湖与热水资源研究发展中心 | Lithium salt extraction process from carbonate type bittern |
| WO2019141098A1 (en) * | 2018-01-17 | 2019-07-25 | 成都绿锂环保科技有限公司 | High-value comprehensive utilization method for lithium slag |
| CN113825848A (en) * | 2019-03-29 | 2021-12-21 | 锂业美洲公司 | Method for extracting lithium from sedimentary clay |
| CN110038737A (en) * | 2019-05-17 | 2019-07-23 | 贵州三稀新能源科技股份有限公司 | A method of the silicalite physical upgrading of shale containing lithium |
| CN110694788A (en) * | 2019-10-30 | 2020-01-17 | 中蓝长化工程科技有限公司 | Beneficiation method for high-calcium-magnesium type low-grade spodumene ore |
| CN111330743A (en) * | 2020-04-09 | 2020-06-26 | 北京矿冶科技集团有限公司 | Spodumene ore flotation collector, preparation method thereof and spodumene ore dressing process for clay mineralization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024040891A1 (en) * | 2022-08-23 | 2024-02-29 | 广东邦普循环科技有限公司 | Treatment method for carbonate lithium clay |
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| CN115418498B (en) | 2023-12-12 |
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