CN108004391B - A method of processing lepidolite extracts metallic element - Google Patents
A method of processing lepidolite extracts metallic element Download PDFInfo
- Publication number
- CN108004391B CN108004391B CN201711244405.XA CN201711244405A CN108004391B CN 108004391 B CN108004391 B CN 108004391B CN 201711244405 A CN201711244405 A CN 201711244405A CN 108004391 B CN108004391 B CN 108004391B
- Authority
- CN
- China
- Prior art keywords
- lepidolite
- processing
- metallic element
- clinker
- extracts metallic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052629 lepidolite Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000000284 extract Substances 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 31
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 22
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 21
- 238000002386 leaching Methods 0.000 claims abstract description 21
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 17
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 239000011591 potassium Substances 0.000 claims abstract description 16
- 239000012141 concentrate Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 238000004137 mechanical activation Methods 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 239000004411 aluminium Substances 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000011282 treatment Methods 0.000 claims abstract description 4
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000009938 salting Methods 0.000 claims abstract description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 16
- 238000000605 extraction Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 7
- 230000002535 lyotropic effect Effects 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 239000002184 metal Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002918 waste heat Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 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 2
- 239000012267 brine Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QMHYOQOXDJQUBB-UHFFFAOYSA-N [Ta].[Nb].[Li] Chemical compound [Ta].[Nb].[Li] QMHYOQOXDJQUBB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 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
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of methods that processing lepidolite extracts metallic element, and steps are as follows: 1) lepidolite concentrate mechanical activation；2) lepidolite powder is formed with reconstructors, binder according to mass ratio 1:1~2:0.2~0.5 after evenly mixing；3) green body in step 2) is first subjected to low temperature reconstruct, then carries out medium temperature decomposition, obtain clinker；4) Soaking treatment: by the clinker in step 3) prior to 0~30 DEG C under the conditions of, in leaching agent leach separation, obtain lithium salt solution；Again under the conditions of 70~100 DEG C, in leaching agent leach separation obtain containing sodium, potassium, rubidium, caesium, aluminium salting liquid；5) by the washed process of filter residue after the secondary leaching in step 4), high silicon slag is obtained.The present invention can make the very big limit of the metallic element in lepidolite ore be converted into lyotropic salt progress separation and Extraction, increase substantially the utilization rate and economic benefit of lepidolite ore, easy to operate, process costs are lower, and the metallic element rate of recovery is higher.
Description
Technical field
The present invention relates to a kind of processing methods of raw mineral materials, belong to technical field of mineral processing, and in particular to a kind of place
Manage the method that lepidolite extracts metallic element.
Background technique
Mineral of the China containing lithium are more at present, wherein mainly having spodumene (Li with industrial value2O·Al2O3·
4SiO2), lepidolite (KLi1.5Al1.5[AlSi3O10](OH,F)2), petalite (Li2O·Al2O3·8SiO2), phosphorus lepidolite
(LiAl[PO4] (OH, F)) and zinnwaldite (K (Li, Al, Fe) [AlSi3O10](OH,F)2).Salt lake bittern is to extract lithium simultaneously
The important sources of element have many producers using the technology due to extracting the low in cost of elemental lithium from brine at present, but
It is since the impurity contents such as Mg are high in brine, later period removal of impurities is cumbersome, and cause product purity not high, and as the demand of lithium increases,
Cause to mention lithium from ore by the favor of some producers, and gradually start to produce, is graduallyd mature so that proposing lithium technique in ore.
Lithium carbonate is a kind of important industrial chemicals, as emphasis of the country to lithium electric material supports that lithium electricity is green in high energy
The wide application of color energy field, both at home and abroad constantly increases lithium carbonate demand, price is gradually surging.And Rb, Cs are only because of it
Special photoelectric effect is applied to photocatalysis and military industry field, and Rb does not have individual ore that can exploit, scarcity of resources, far from
Meet demand, thus how comprehensive development and utilization lepidolite resource, have considerable economy and strategic importance.
Contain a variety of metal values and the nonmetallic members such as Li, Na, K, Rb, Cs, Al and F in the lepidolite ore of Yichuan
Element has great economic value, Li in lepidolite ore2O content is only second to 6~8wt.% of spodumene in 4~5wt.%,
K2O content may be up to 8.5wt.%, and Rb content can reach 1~1.5wt.%, since Rb does not find its individualism so far
Ore, therefore Rb has very big extraction value, therefore the great advantageous resources advantage of lepidolite extracted lithium.
The method of processing lepidolite ore mainly has conventional limestone roasting method, sulfuric acid process, sulfate process, chloridising roasting at present
And autoclaving method etc..Lime burning method, chlorinating roasting, traditional sulfuric acid process etc., are all made of high temperature sintering and carry out ore phase reconstruction
Mode, because of its energy consumption height, material circulation is big, and Li et al. alkali metal recovery rate is low, and the resources such as valuable metal rubidium, caesium cannot be filled
Divide and utilize, can not embody the advantage and value of the lepidolite ore utilization of resources, sulfuric acid process extracts alkali metal since its sulfuric acid dosage is big
Cause its plumper dosage big, mainly with Al in solution3+And F-Based on, in filter residue subsidiary alkali larger with alkali metal separating difficulty
Amount of metal is big, to reduce the rate of recovery of alkali metal in lepidolite.Existing sulfate process is mainly by lepidolite and potassium sulfate
The equal baking mixed leaching of auxiliary materials, this method are better than limestone-based process, but the current higher cost of this method, it is also necessary to further change
Into.A kind of emerging technique for handling lepidolite ore of autoclaving method.Autoclaving method is that lepidolite is first roasted defluorinate, then with sodium carbonate and
Lime etc. is leached, but in defluorinate roasting, defluorinate is not in place, and mechanical activation is inadequate, and autoclaving temperature is high, needs high pressure
Equipment, this just greatly limits the application of this method.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of processing lepidolite extraction metal
The method of element, it by control lepidolite mechanical activation degree and with reconstructors, binder formulation ratio, make in lepidolite ore
Metallic element greatly limit can be converted into lyotropic salt progress separation and Extraction, increase substantially the utilization rate and economy of lepidolite ore
Benefit, easy to operate, process costs are lower, and the metallic element rate of recovery is higher.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows: a kind of processing lepidolite extraction metallic element
Method, comprising the following steps:
1) lepidolite concentrate mechanical activation；
2) forming ingredient: by lepidolite powder and reconstructors, binder according to quality than lepidolite: reconstructors: binder
=1:1~2:0.2~0.5 is formed after evenly mixing, obtains green body；
3) low-temperature bake: being placed in 200~300 DEG C of 30~90min of processing in roller way kiln for the green body in step 2), into
The reconstruct of row low temperature carries out medium temperature decomposition, obtains clinker then then at 400~750 DEG C of 10~30min of processing；
4) by the clinker in step 3) first under the conditions of 0~30 DEG C, clinker: leaching agent Soaking treatment: is pressed into 1~2:1
Solid-to-liquid ratio leach separation, obtain lithium salt solution；Again under the conditions of 70~100 DEG C, clinker: leaching agent is pressed into the solid-to-liquid ratio of 1~2:1
Leach separation obtain containing sodium, potassium, rubidium, caesium, aluminium salting liquid；
5) residue washing: the filter residue after the secondary leaching in step 4) is washed, obtain high silicon slag.
The further technical solution of the present invention are as follows: lepidolite concentrate described in step 1) first uses drying and processing, then
Mechanical activation is to its granularity below 300 mesh.
Further, roasting clinker residual heat can be carried out the drying and processing that recycling is used for the wet mine of lepidolite in step 3).
Further, reconstructors described in step 2) are one of ammonium sulfate, potassium sulfate, sodium sulphate or ammonium chloride or several
Kind combination.
Further, binder described in step 2) be one of polyacrylamide, methylcellulose or sesbania powder or
Several combinations.
Further, leaching agent is the combination of one or more of sinker mother liquor, tap water or deionized water in step 4).
Further, generated kiln tail gas is inhaled through packed absorber after low temperature reconstruct, medium temperature are decomposed in step 3)
Receipts are converted into ammonium salt solution, and then the ammonium salt solution is back in the burden process in step 2).
Further, the washing process in step 5) is to carry out countercurrent washing using 80~100 DEG C of hot water.
For the present invention by taking ammonium sulfate as an example, the equation for the main chemical reactions being related to is as follows:
4(NH4)2SO4+Al2O3=(NH4)Al(SO4)2+6NH3+3H2O；
Me2O+(NH4)2SO4=Me2SO4+2NH3+H2O (wherein Me:Li, Na, K, Rb, Cs)；
(NH4)2SO4=2NH3+SO3+H2O；
(NH4)Al(SO4)2+Me2SO4=2MeAl (SO4)2+(NH4)2SO4(wherein Me:Na, K, Rb, Cs)；
The reaction mechanism of other reconstructors is similar with above-mentioned reaction mechanism.
Compared with the prior art, the advantages of the present invention are as follows:
1, the present invention handles lepidolite concentrate using mechanical activation, and the granularity of lepidolite concentrate is made to become smaller, and specific surface area increases
Add, to increase the contact area with reconstructors, and make to generate crystal defect in crystal structure, reduces the surface that Mica Mine shows
Activation energy, intensified response activity, so that valuable metal be made to be easier to leach；
2, the present invention uses low temperature ore phase reconstruction technology, with ammonium sulfate, potassium sulfate, sodium sulphate, one kind of ammonium chloride or several
Kind is reconstructors, using low temperature reconstruct, decomposed and reconstituted dose of medium temperature and the resource-effective and environmentally friendly technique road recycled
Line, reconstructors utilization rate, the rate of recovery are high, it can be achieved that resource circulation utilization, the waste heat of reconstruction process step for the drying of lepidolite concentrate,
Low in conjunction with remodeling temperature, simple to operate, alkali metal and Al extraction efficiency are high, easy to industrialized production；
3, the big lithium salts of solubility is dissolved out first, is obtained single using separating step by step by Soaking treatment process of the invention
Then lithium salt solution leaches the sulfate for extracting sodium, potassium, rubidium, caesium, aluminium；On the one hand can effectively by acidleach generate sodium, potassium,
Rubidium, caesium, aluminium salt and lithium salts efficiently separate, so that the later period, which is effectively reduced, neutralizes the pressure for removing aluminium, alleviate scavenging solution purification
Process solves the critical problem of aluminium and alkali metal separation difficulty, in addition can also reduce sodium, potassium, rubidium, caesium in dedoping step
Loss realizes that resource maximally utilizes；
4, the present invention has step simple, and easy to operate, low energy consumption, and the alkali metal rate of recovery is high, and high silicon slag can be with deep processing
The advantages of carrying out resource utilization provides advantage for further comprehensive utilization and industrialized production；
5, the present invention uses low-temperature bake process, and highest maturing temperature is not higher than 750 DEG C, middle compared with the existing technology to pass
For 950~1100 DEG C of the maturing temperature of system, temperature is lower, and the requirement to heating equipment is lower, have low energy consumption, save energy
The advantages that source, reduction process costs.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Lepidolite used in following embodiments uses the tantalum niobium lithium mine of Yichuan production, and each ingredient of lepidolite is shown in Table
Shown in 1.Process flow in following embodiments is referring to figure 1.
The composition of 1 lepidolite concentrate of table
| Component | K | Na | Rb | Cs | Fe | Mn | Li2O | CaO | F | SiO2 | Al2O3 |
| Wt | 6.45 | 1.25 | 1 | 0.2 | 0.13 | 0.24 | 4.2 | 0.14 | 4.46 | 50.78 | 26.93 |
Note: each component content is mass fraction in lepidolite ore described in table.
Embodiment 1:
Lepidolite concentrate is milled to 100 mesh hereinafter, taking mechanical activation Mica Mine and ammonium sulfate, methylcellulose by quality
Than being mixed for 1:1.2:0.2,90min is reacted under the conditions of 220 DEG C, 400 DEG C of heat treatments are then warming up to 20 DEG C/min speed
20min, then cooling to obtain clinker, waste gas recovery prepares ammonium salt and returns to reconstruct burden process in roasting process, and waste heat is for doing
Dry lepidolite.Gained clinker reacts 30min under the conditions of 10 DEG C, liquid-solid ratio 2:1, filters preferential separation lithium salt solution, filter residue in
96 DEG C, react 60min under the conditions of liquid-solid ratio 2:1, filter sodium, potassium, rubidium, caesium, aluminium solution, secondary leaching filter residue is through 90 DEG C of warm
Water counter current washes.
Ore phase reconstruction lithium, sodium, potassium, rubidium, caesium recovery rate are respectively up to 85.16,25.13,84.39,82.09 and 81.12%；
Al extraction efficiency is up to 74.52%；Lithium salts and otheralkali metal salt separation rate are up to 85.45% in leaching process；In high silicon slag
Al2O3Content is 8.08wt.%.
Embodiment 2:
Lepidolite concentrate is milled to 200 mesh hereinafter, taking mechanical activation Mica Mine and ammonium sulfate, methylcellulose by quality
Than being mixed for 1:1.2:0.2,75min is reacted under the conditions of 250 DEG C, 480 DEG C of heat treatments are then warming up to 20 DEG C/min speed
30min, then cooling to obtain clinker, waste gas recovery prepares ammonium salt and returns to reconstruct burden process in roasting process, and waste heat is for doing
Dry lepidolite.Gained clinker reacts 30min under the conditions of 15 DEG C, liquid-solid ratio 1.8:1, filters preferential separation lithium salt solution, filter residue
React 60min under the conditions of 90 DEG C, liquid-solid ratio 2:1, filter sodium, potassium, rubidium, caesium, aluminium solution, secondary leaching filter residue is through 90 DEG C
Hot water countercurrent washing.
Ore phase reconstruction lithium, sodium, potassium, rubidium, caesium recovery rate are respectively up to 88.35,26.35,86.51,85.12 and 83.06%；
Al extraction efficiency is up to 76.52%；Lithium salts and otheralkali metal salt separation rate are up to 86.06% in leaching process；In high silicon slag
Al2O3Content is 7.29wt.%.
Embodiment 3:
Lepidolite concentrate is milled to 200 mesh hereinafter, taking mechanical activation Mica Mine and ammonium sulfate, methylcellulose by quality
Than being mixed for 1:1.2:0.2,75min is reacted under the conditions of 300 DEG C, 600 DEG C of heat treatments are then warming up to 20 DEG C/min speed
30min, then cooling to obtain clinker, waste gas recovery prepares ammonium salt and returns to reconstruct burden process in roasting process, and waste heat is for doing
Dry lepidolite.Gained clinker reacts 30min under the conditions of 10 DEG C, liquid-solid ratio 2:1, filters preferential separation lithium salt solution, filter residue in
80 DEG C, react 60min under the conditions of liquid-solid ratio 2:1, filter sodium, potassium, rubidium, caesium, aluminium solution, secondary leaching filter residue is through 90 DEG C of warm
Water counter current washes.
Ore phase reconstruction lithium, sodium, potassium, rubidium, caesium recovery rate are respectively up to 86.52,25.71,85.69,82.92 and 82.09%；
Al extraction efficiency is up to 75.68%；Lithium salts and otheralkali metal salt separation rate are up to 87.52% in leaching process；In high silicon slag
Al2O3Content is 7.37wt.%.
Embodiment 4:
Lepidolite concentrate is milled to 300 mesh hereinafter, taking mechanical activation Mica Mine and ammonium sulfate, methylcellulose by quality
Than being mixed for 1:1.5:0.15,50min is reacted under the conditions of 250 DEG C, 750 DEG C of heat treatments are then warming up to 20 DEG C/min speed
30min, then cooling to obtain clinker, waste gas recovery prepares ammonium salt and returns to reconstruct burden process in roasting process, and waste heat is for doing
Dry lepidolite.Gained clinker reacts 20min under the conditions of 5 DEG C, liquid-solid ratio 2:1, filters preferential separation lithium salt solution, filter residue in
100 DEG C, react 20min under the conditions of liquid-solid ratio 2:1, filter sodium, potassium, rubidium, caesium, aluminium solution, secondary leaching filter residue is through 80 DEG C
Hot water countercurrent washing.
Ore phase reconstruction lithium, sodium, potassium, rubidium, caesium recovery rate are respectively up to 93.93,28.12.71,92.56,91.78 Hes
91.65%；Al extraction efficiency is up to 85.36%；Lithium salts and otheralkali metal salt separation rate are up to 88.94% in leaching process；It is high
Al in silicon slag2O3Content is 4.95wt.%.
Embodiment 5:
Lepidolite concentrate is milled to 100 mesh hereinafter, taking mechanical activation Mica Mine and ammonium sulfate, methylcellulose by quality
Than being mixed for 1:2:0.4,60min is reacted under the conditions of 280 DEG C, 550 DEG C of heat treatments are then warming up to 20 DEG C/min speed
60min, then cooling to obtain clinker, waste gas recovery prepares ammonium salt and returns to reconstruct burden process in roasting process, and waste heat is for doing
Dry lepidolite.Gained clinker reacts 30min under the conditions of 15 DEG C, liquid-solid ratio 2:1, filters preferential separation lithium salt solution, filter residue in
80 DEG C, react 30min under the conditions of liquid-solid ratio 2:1, filter sodium, potassium, rubidium, caesium, aluminium solution, secondary leaching filter residue is through 80 DEG C of warm
Water counter current washes.
Ore phase reconstruction lithium, sodium, potassium, rubidium, caesium recovery rate are respectively up to 93.45%, 27.68%, 93.01%, 91.11% He
90.78%；Al extraction efficiency is up to 89.56%；Lithium salts and otheralkali metal salt separation rate are up to 88.94% in leaching process；It is high
Al in silicon slag2O3Content is 3.87wt.%.
Claims (8)
1. a kind of method that processing lepidolite extracts metallic element, which comprises the following steps:
1) lepidolite concentrate mechanical activation；
2) forming ingredient: by lepidolite powder and reconstructors, binder according to quality than lepidolite: reconstructors: binder=1:1
~2:0.2~0.5 is formed after evenly mixing, obtains green body；
3) low-temperature bake: the green body in step 2) is placed in 200~300 DEG C of 30~90min of processing in roller way kiln, is carried out low
Temperature reconstruct carries out medium temperature decomposition, obtains clinker then then at 400~750 DEG C of 10~30min of processing；
4) Soaking treatment: by the clinker in step 3) first under the conditions of 0~30 DEG C, clinker: leaching agent is consolidated as 1~2:1's
Liquor ratio leaches separation, obtains lithium salt solution；Again under the conditions of 70~100 DEG C, clinker: leaching agent is leached by the solid-to-liquid ratio of 1~2:1
Separation obtain containing sodium, potassium, rubidium, caesium, aluminium salting liquid；
5) residue washing: by the washed process of filter residue after the secondary leaching in step 4), high silicon slag is obtained.
2. the method that processing lepidolite according to claim 1 extracts metallic element, which is characterized in that described in step 1)
Lepidolite concentrate first use drying and processing, then mechanical activation to its granularity is below 300 mesh.
3. the method that processing lepidolite according to claim 2 extracts metallic element, which is characterized in that roasting in step 3)
Clinker residual heat can be carried out the drying and processing that recycling is used for the wet mine of lepidolite.
4. the method that processing lepidolite according to claim 1 extracts metallic element, which is characterized in that described in step 2)
Reconstructors are the combination of one or more of ammonium sulfate, potassium sulfate, sodium sulphate or ammonium chloride.
5. the method that processing lepidolite according to claim 3 extracts metallic element, which is characterized in that described in step 2)
Binder is the combination of one or more of polyacrylamide, methylcellulose or sesbania powder.
6. the method that processing lepidolite according to claim 1 extracts metallic element, which is characterized in that leached in step 4)
Agent is the combination of one or more of sinker mother liquor, tap water or deionized water.
7. the method that processing lepidolite according to claim 1 to 6 extracts metallic element, which is characterized in that step
It is rapid 3) in through low temperature reconstruct, medium temperature decompose after generated kiln tail gas through packed absorber sorption enhanced be ammonium salt solution, so
The ammonium salt solution is back in the burden process in step 2) afterwards.
8. the method that processing lepidolite according to claim 1 to 6 extracts metallic element, which is characterized in that step
It is rapid 5) in the washing process be using 80~100 DEG C hot water carry out countercurrent washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711244405.XA CN108004391B (en) | 2017-11-30 | 2017-11-30 | A method of processing lepidolite extracts metallic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711244405.XA CN108004391B (en) | 2017-11-30 | 2017-11-30 | A method of processing lepidolite extracts metallic element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108004391A CN108004391A (en) | 2018-05-08 |
| CN108004391B true CN108004391B (en) | 2019-08-09 |
Family
ID=62055876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711244405.XA Active CN108004391B (en) | 2017-11-30 | 2017-11-30 | A method of processing lepidolite extracts metallic element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108004391B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517423B (en) * | 2018-05-21 | 2020-06-02 | 江西南氏锂电新材料有限公司 | Method for extracting lithium and lithium salt by roasting lepidolite in rotary kiln |
| CN110578054A (en) * | 2019-09-30 | 2019-12-17 | 山东瑞福锂业有限公司 | Method for preparing granular spodumene by granulating fine powder spodumene |
| CN110983071B (en) * | 2019-12-31 | 2022-03-01 | 江西南氏锂电新材料有限公司 | Method for extracting lithium salt from low-grade lithium ore raw material |
| CN110983035A (en) * | 2019-12-31 | 2020-04-10 | 江西南氏锂电新材料有限公司 | Method and device for extracting lithium by pressing, molding, roasting and lithium mica |
| CN113083510A (en) * | 2021-04-07 | 2021-07-09 | 宜春市金地锂业有限公司 | Method for efficiently recycling tantalum, niobium and tin from lepidolite ore |
| CN115216646B (en) * | 2022-07-28 | 2023-03-21 | 江西鼎盛新材料科技有限公司 | Process method for calcining lepidolite clinker by using roller kiln |
| CN115821060A (en) * | 2022-11-18 | 2023-03-21 | 宜丰国轩锂业有限公司 | Method for extracting lithium from lepidolite through composite salt method sectional roasting |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586587B (en) * | 2012-03-24 | 2013-10-23 | 宜春合纵锂业科技有限公司 | Method for treating lepidolite ore |
| CN105803188A (en) * | 2016-05-30 | 2016-07-27 | 江西旭锂矿业有限公司 | Method for preferential segregation of potassium, rubidium and cesium through chloridizing roasting treatment of lepidolite |
-
2017
- 2017-11-30 CN CN201711244405.XA patent/CN108004391B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108004391A (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108004391B (en) | A method of processing lepidolite extracts metallic element | |
| CN102718234B (en) | Method for extracting lithium carbonate from lepidolite | |
| CN102586587B (en) | Method for treating lepidolite ore | |
| CN105039699B (en) | The solid fluorine reconstruct extraction alkali metal Slag treatment of lepidolite and resource utilization method | |
| CN104876250B (en) | Method for extracting lithium and removing aluminum by treating lepidolite with sulfuric acid | |
| CN108517423B (en) | Method for extracting lithium and lithium salt by roasting lepidolite in rotary kiln | |
| CN103103349B (en) | Method for decomposing bayan obo rare earth ore concentrate by acid and alkali combination at low temperature | |
| CN102502721B (en) | Method for preparing lithium carbonate through extracting lithium from lithium ore | |
| CN110550644A (en) | method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite | |
| CN115216645B (en) | Method for extracting lithium from electrolytic aluminum waste residue by mixed salt calcination | |
| CN104817099A (en) | Improved method for extracting alkali metal compound from solid fluorine reconstruction lepidolite | |
| CN102943177A (en) | Method for recovering cooper and silicon powder from organosilicon waste residue | |
| CN104140117A (en) | Process for extracting lithium salt by adopting method for autoclaving lepidolite with sulfuric acid | |
| CN110042225A (en) | A kind of roasting of lepidolite ore sodium sulphate and leaching method | |
| CN104692436B (en) | It is a kind of by coal ash for manufacturing for cryolite method | |
| CN107758705B (en) | Zinnwaldite extracts lithium carbonate technique | |
| CN107344725A (en) | The preparation technology of elemental lithium in sulfuric acid straight dipping process extraction lithium ore | |
| CN107964597B (en) | Method for extracting alkali metal by treating lepidolite | |
| CN105883843A (en) | Method for efficiently manufacturing borax by treating boron-bearing tailings through alkaline hydrolysis | |
| CN104611559B (en) | A kind of method from the fluorite chats synthetical recovery rubidium of tungsten containing rubidium, tungsten and potassium | |
| CN106350623A (en) | Method for dechlorinating and decarbonizing titanium-extraction tailing slag | |
| CN102899488B (en) | Resource transforming method for separating rare earth from fluorine by utilizing rare earth ore concentrate hydrochloric leachate | |
| CN103014316B (en) | Novel method for processing lepidolite material | |
| CN102628105B (en) | Method for comprehensively recycling and using baric waste slag in refined aluminum production process | |
| CN101824531A (en) | Liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220111 Address after: 410000 Room 502, building 16, gaojiaping, Yuelu District, Changsha City, Hunan Province Patentee after: Li Jiayi Address before: 410000 No. 1301, building 1, Yanggu Jinyuan, No. 39, Luhu Road, high tech Development Zone, Changsha, Hunan Patentee before: HUNAN ZHONGDA TECHNOLOGY ESTABLISH A BUSINESS INCUBATOR CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220307 Address after: 410699 shitoukeng village, suburban street, Ningxiang City, Changsha City, Hunan Province (in Hunan new lithium era Energy Technology Co., Ltd.) Patentee after: Hunan Yisheng Technology Co.,Ltd. Address before: 410000 Room 502, building 16, gaojiaping, Yuelu District, Changsha City, Hunan Province Patentee before: Li Jiayi |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 410699 shitoukeng village, suburban street, Ningxiang City, Changsha City, Hunan Province (in Hunan new lithium era Energy Technology Co., Ltd.) Patentee after: Changsha New Lithium Times Energy Technology Co., Ltd. Address before: 410699 shitoukeng village, suburban street, Ningxiang City, Changsha City, Hunan Province (in Hunan new lithium era Energy Technology Co., Ltd.) Patentee before: Hunan Yisheng Technology Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 410600 Shitoukeng Village, Chengjiao Street, Ningxiang City, Changsha City, Hunan Province (within Hunan New Lithium Era Energy Technology Co., Ltd.) Patentee after: Hunan Jixin Lithium Industry Technology Co.,Ltd. Address before: 410699 shitoukeng village, suburban street, Ningxiang City, Changsha City, Hunan Province (in Hunan new lithium era Energy Technology Co., Ltd.) Patentee before: Changsha New Lithium Times Energy Technology Co.,Ltd. |