CN115180637B - Method for echelon recovery of lithium hydroxide by using tungsten-tin tailings - Google Patents
Method for echelon recovery of lithium hydroxide by using tungsten-tin tailings Download PDFInfo
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 80
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000011084 recovery Methods 0.000 title claims description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 239000000706 filtrate Substances 0.000 claims abstract description 40
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010937 tungsten Substances 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 238000005188 flotation Methods 0.000 claims description 25
- 239000002585 base Substances 0.000 claims description 21
- 229910052629 lepidolite Inorganic materials 0.000 claims description 21
- 239000011268 mixed slurry Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- 230000001502 supplementing effect Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004482 other powder Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000007667 floating Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 42
- 229910052744 lithium Inorganic materials 0.000 abstract description 41
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 12
- 239000011707 mineral Substances 0.000 abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 18
- 239000000956 alloy Substances 0.000 description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 description 6
- 150000004692 metal hydroxides Chemical class 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XMFMIGHRZUZPLB-UHFFFAOYSA-L P(=O)([O-])([O-])[O-].[NH4+].[W+2] Chemical compound P(=O)([O-])([O-])[O-].[NH4+].[W+2] XMFMIGHRZUZPLB-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application discloses a method for echelonly recycling lithium hydroxide by utilizing tungsten tin tailings, which comprises the following steps: step S1, collecting tungsten tin tailings; s2, ball milling for the first time; s3, floatation; s4, performing secondary ball milling; s5, roasting with concentrated sulfuric acid; s6, filtering for the first time; s62, neutralizing filter residues with alkali liquor and filtering again; step S7, adding alkali and stirring filtrate; s8, secondary filtration; and S82, adding alcohol, stirring the filtrate, adding the alcohol into the filtrate obtained in the step S8, stirring and filtering to obtain filter residues containing lithium hydroxide precipitate and an alkali metal hydroxide solution. The method combines the characteristics of containing a plurality of lithium-containing minerals with different lithium contents and having high tungsten content in the tungsten tin tailings, and the method is integrally designed and utilized in a gradient manner, so that not only is lithium resources recovered to form high-purity lithium carbonate and lithium hydroxide, but also valuable tungsten resources are recovered, and meanwhile, a high-performance ceramic raw material is obtained, the formation of waste residues is greatly reduced, waste materials are changed into valuable materials, and higher economic value is generated.
Description
Technical Field
The application relates to the field of mine resource recovery, in particular to the field of tungsten-tin tailing recovery.
Background
Along with the development of new energy industry in China, the lithium battery scale is increasingly enlarged, the demands on upstream raw materials such as lithium hydroxide, lithium carbonate, lithium fluoride and the like are increasingly enlarged, the existing lithium ore resources cannot meet the demands of lithium resources which are increased at a high speed, but a large amount of lithium residues are remained in tailings remained in the existing lithium ore lithium extraction process, and how to formulate a targeted recovery process is a key for solving the problem of shortage of lithium resources.
Disclosure of Invention
In order to solve the problems in the prior art, the application discloses a method for recovering lithium hydroxide in a echelon manner by utilizing tungsten tin tailings, which comprises the following steps:
step S1, collecting tungsten tin tailings;
step S2, performing primary ball milling, and performing ball milling on the tungsten tin tailings collected in the step S1;
s3, floating, namely floating the tungsten-tin tailing powder subjected to primary ball milling, and separating to obtain lepidolite powder and other powder mixed liquid;
s4, performing secondary ball milling, namely adding sulfate and calcium sucrose into the other powder mixed solution obtained by flotation to perform wet ball milling to obtain mixed slurry;
s5, roasting the mixed slurry with concentrated sulfuric acid after evaporating part of the solvent;
s6, filtering for the first time, and filtering the slurry after roasting the concentrated sulfuric acid to obtain filtrate and filter residues;
step S62, neutralizing filter residues with alkali liquor and filtering again, adding weak alkali solution into the filter residues obtained in the step S6, stirring and heating, filtering again, drying the filter residues after filtering again to obtain ceramic raw materials, and crystallizing the filtrate after filtering again to obtain ammonium tungstate crystals;
step S7, adding alkali to stir the filtrate, and mixing and stirring the weak alkali solution and the filtrate obtained in the step S6;
s8, performing secondary filtration, and filtering the mixed solution stirred in the step S7 to obtain hydroxide filter residues and filtrate;
and S82, adding alcohol, stirring the filtrate, adding the alcohol into the filtrate obtained in the step S8, stirring and filtering to obtain filter residues containing lithium hydroxide precipitate and an alkali metal hydroxide solution.
The tungsten-tin tailings in the step S1 contain tungsten, tin, lepidolite and quartz, wherein the mass percentage of the tungsten in the tungsten-tin tailings is 0.5% -1%.
The step S2 is ball-milled to obtain powder materials with the grain size of 0.1-0.15mm;
and (3) performing flotation in the step (S3) to obtain lepidolite, wherein the activating agent used in the flotation is sulfuric acid, and the collecting agent is dodecyl amine.
In the step S4, the sulfate and the sucrose calcium powder are directly added into the other powder mixed solution after the flotation in the step S3 for secondary ball milling; the sulfate includes sodium sulfate and calcium sulfate.
Evaporating part of the solvent from the mixed slurry obtained by the wet ball milling in the step S4, so that the water content in the evaporated mixed slurry is not more than 10 percent by mass; in the step S5, the concentrated sulfuric acid is 98% by mass, and the roasting temperature is 700-1000 ℃.
In the step S5, the mixing sequence of the mixed slurry and the concentrated sulfuric acid is as follows: the concentrated sulfuric acid is added to the mixed slurry in multiple portions and stirring is continued.
In the step S62, the weak base solution is a weak base solution of ammonia water, and the heating temperature is 60-100 ℃;
adding the ammonia weak base solution into the filter residue in the step S6, and continuously supplementing the ammonia solution after heating and stirring to maintain the pH value of the solution in the filter residue to be 8-9 in the stirring and heating process;
the heating and stirring process of the step S62 is performed in a closed container, the closed container comprises a device for automatically displaying the pH value of the solution in the container, the closed container comprises a one-way liquid supplementing port, the one-way liquid supplementing port is used for supplementing the ammonia solution, the closed container further comprises an exhaust channel, the exhaust channel is closed in the heating and stirring process, and after the heating and stirring process of the step S62 is completed, ammonia in the closed container is led into an ammonia recovery device outside the closed container through the exhaust channel, because the ammonia solution is huge in the whole step S62 process, and the recovery device can recycle the ammonia without polluting the environment.
Performing heating evaporation crystallization on the filtrate filtered in the step S62, wherein the heating evaporation crystallization comprises a primary crystallization process and a secondary crystallization process, and a large amount of ammonia generated in the primary crystallization process is introduced into the ammonia recovery device, and meanwhile, ammonium tungstate crystals containing crystal water are obtained; and (3) carrying out the secondary crystallization process on the ammonium tungstate crystal containing the crystallization water, wherein the heating temperature in the secondary crystallization process is 100-150 ℃, and obtaining the anhydrous ammonium tungstate crystal after the secondary crystallization process.
In the step S7, the filtrate obtained in the step S6 is introduced into the bottom of a container containing weak base aqueous solution, and stirring is continued until no sediment is generated; in the step S8, the mixed solution after the stirring in the step S7 is subjected to secondary filtration to obtain hydroxide filter residues and filtrate.
And step S82 is to add ethanol into the filtrate obtained in the step S8, stir and filter the filtrate until no more precipitate is generated, filter the precipitate and crystallize filter residues to obtain lithium hydroxide crystals.
The method disclosed by the application has the following advantages:
firstly, the method combines the characteristics that the tungsten tin tailings contain a plurality of lithium-containing minerals with different lithium contents and the tungsten content is high, combines the step S3 of flotation and extraction of lepidolite with other lithium resource extraction steps, and ensures that the step S3 of flotation is focused on the purity of the extracted lepidolite due to the existence of other lithium resource extraction steps, so that the flotation procedure with stronger pertinence is adopted, the purity of the lepidolite in the flotation process can be improved, high-purity lithium carbonate is further obtained, and meanwhile, the lithium extraction rate of the whole tungsten tin tailings resource is ensured due to the existence of other lithium resource extraction steps. Meanwhile, precious tungsten resources in the process are effectively recovered;
second, since a metal hydroxide such as tin hydroxide is previously precipitated with a weak base before precipitating lithium hydroxide with ethanol. Since the metal hydroxide impurities have been removed, a large amount of cations in the solution are alkali metal ions before the start of step S82. While lithium hydroxide is insoluble in ethanol, the solution is subjected to step S82, and then the solution is filtered to obtain high-purity lithium hydroxide.
The method combines the characteristics of various lithium-containing minerals with different lithium contents in the tungsten tin tailings and high tungsten content, and the method is integrally designed and utilized in a gradient manner, so that not only is lithium resources recovered, but also valuable tungsten resources are recovered, and meanwhile, the high-performance ceramic raw material is obtained, the formation of waste residues is greatly reduced, meanwhile, ammonia gas is absorbed in a closed loop and is recycled, and the cost is saved.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described.
FIG. 1 is a schematic diagram of steps of a method for echelon recovery of lithium resources by using tungsten tin tailings.
Detailed Description
The following will describe the technical scheme of the embodiment of the application clearly and completely;
as shown in fig. 1, the application discloses a method for recovering lithium hydroxide in a echelon by utilizing tungsten tin tailings, which comprises the following steps:
step S1, collecting tungsten tin tailings; not all tailings are suitable for the method, and the method combines various lithium-containing different lithium resource minerals (such as lepidolite, quartz and the like) and tungsten resources with certain content in the tungsten-tin tailings, wherein the mass percentage of tungsten in the tungsten-tin tailings is 0.5% -1%.
Step S2, performing primary ball milling, and performing ball milling on the tungsten tin tailings collected in the step S1; the step is preferably wet ball milling, the wet ball milling saves more energy compared with the dry ball milling, and the following step S3 also needs liquid to participate in the flotation process, so that the infiltration process and time in the powder particle re-solution are saved, and the overall work efficiency is improved.
S3, floating, namely floating the tungsten-tin tailing powder subjected to primary ball milling, and separating to obtain lepidolite powder and other powder mixed liquid; the step S3 is combined with other lithium resource extraction steps after the step S3 is performed with flotation, and the purity of the lepidolite is mainly extracted in the step S3 flotation process due to the existence of other lithium resource extraction steps, so that a flotation procedure with stronger pertinence is adopted, the purity of the lepidolite in the flotation process can be improved, high-purity lithium carbonate is further obtained, and meanwhile, the lithium extraction rate of the whole tungsten tin tailing resources is ensured due to the existence of other lithium resource extraction steps. Lepidolite is preferentially extracted because it has a higher lithium content than other minerals. The following table shows the content differences of lithium oxide in different minerals in Jiangxi large Yu Wuxi tailings:
s4, performing secondary ball milling, namely adding sulfate and calcium sucrose into the other powder mixed solution obtained by flotation to perform wet ball milling to obtain mixed slurry; the purpose of the sulphate here is to provide sufficient sulphate to facilitate the subsequent sulphuric acid roasting process, whereas the calcium sucrose will decompose to calcium oxide during the subsequent roasting process at around 200 degrees celsius, which may help to reduce caking in the mixed slurry. The wet ball milling is adopted because the solution state is favorable for uniform mixing, and because the sucrose calcium is dissolved in water, the wet ball milling can be more favorable for weakening caking reaction and is favorable for full mixing compared with the direct mixing of other calcium salt forms such as calcium oxide or calcium carbonate.
S5, roasting the mixed slurry by using concentrated sulfuric acid, and roasting the mixed slurry together with the concentrated sulfuric acid after evaporating part of the solvent, wherein the excessive water reacts with the concentrated sulfuric acid to release a large amount of heat, so that the roasting reaction is uneven, the subsequent mixing and lithium extraction processes are affected, and part of the solvent is evaporated in advance before roasting;
s6, filtering for the first time, and filtering the slurry after roasting the concentrated sulfuric acid to obtain filtrate and filter residues; after roasting reaction, alkali metals (including lithium, sodium, potassium, rubidium and the like) exist in the filtrate in the step S6 in the form of sulfate, and other non-reacted minerals such as silicon oxide, quartz and the like (including tungsten oxide) exist in the filtered filter residues in the solid form, and the filter residues are powder materials with uniform granularity due to the fact that the filter residues are subjected to ball milling for many times; the ceramic raw material obtained later is uniform and fine in particles and is a high-quality ceramic raw material due to the fact that the ceramic raw material undergoes roasting and multiple ball milling processes.
Step S62, neutralizing filter residues with alkali liquor and filtering again, adding weak alkali solution into the filter residues obtained in the step S6, stirring and heating, filtering again, drying the filter residues after filtering again to obtain ceramic raw materials, and crystallizing the filtrate after filtering again to obtain ammonium tungstate crystals; ammonium tungstate is formed because of the strong oxidizing property of concentrated sulfuric acid, and tungsten in the tungsten tin tailings is oxidized into tungsten oxide in the presence of sulfate (sodium sulfate) after the concentrated sulfuric acid roasting reaction. Then tungsten oxide and ammonia water are heated and reacted to generate ammonium tungstate, and the chemical formula is as follows: WO3+2 nh3.h2o= (NH 4) 2wo4+ h2o. The other reason for selecting weak base is that a great amount of silicon oxide exists in the filter residue and is powder material, so that the filter residue is easy to react with the strong base, and therefore, weak base is selected. The main application of the ammonium tungstate is as follows: can be used for preparing ammonium tungsten phosphate and the like. Raw materials for producing ammonium phosphotungstate and other tungsten compounds. Metallic tungsten and catalysts can also be produced. The alloy material can be used for manufacturing tungsten trioxide or blue tungsten oxide to prepare tungsten powder, wherein downstream products of the tungsten powder comprise tungsten material series, such as tungsten bars, tungsten wires and other electric vacuum materials, alloy series, such as tungsten carbide, hard alloy, alloy blades, alloy drills, alloy molds and the like, and other wear-resistant, pressure-resistant and high-temperature-resistant mechanical equipment parts and the like. It is also used as additive for preparing ammonium meta-tungstate and other tungsten compounds in petrochemical industry.
Step S7, adding alkali to stir the filtrate, and mixing and stirring the weak alkali solution and the filtrate obtained in the step S6; here, the weak base is used to precipitate other metal ions in the filtrate, mainly including tin ions, and tin hydroxide is soluble in a strong base solution, so that a weak base solution is required. The weak base solution here is preferably a dilute sodium hydroxide solution.
S8, performing secondary filtration, and filtering the mixed solution stirred in the step S7 to obtain hydroxide filter residues and filtrate; the filter residue at this time is a metal hydroxide containing tin hydroxide.
And S82, adding alcohol, stirring the filtrate, adding the alcohol into the filtrate obtained in the step S8, stirring and filtering to obtain filter residues containing lithium hydroxide precipitate and an alkali metal hydroxide solution. Since the metal hydroxide impurities have been removed by step S8, the cations in the solution are largely alkali metal ions before the start of said step S82. While lithium hydroxide is insoluble in ethanol, after the step S82, high purity lithium hydroxide is filtered to obtain; other alkali metal hydroxides may be recovered by extraction or electrolysis.
The tungsten-tin tailings in the step S1 contain tungsten, tin, lepidolite and quartz, wherein the mass percentage of the tungsten in the tungsten-tin tailings is 0.5% -1%. As described above, not all tailings are suitable for the method, and the method combines the characteristics of the tungsten-tin tailings that a plurality of lithium-containing minerals with different lithium contents and tungsten content are high, and if the tungsten content is lower than 0.5%, the yield ratio is negative when the method is used for collecting ammonium tungstate, so that the process consumes much energy and equipment. The tungsten content is higher than 1%, more tungsten is used as normal minerals instead of tailings, and the normal minerals are recovered by mature methods, such as flotation methods of flotation before gravity and the like and resin separation technologies, and the cost performance of the methods is higher.
The step S2 is ball-milled to obtain powder materials with the grain size of 0.1-0.15mm; the ore grinding cost accounts for a larger proportion of the ore preparation cost, and the economic benefit of comprehensive utilization of tailings is also restricted.
The lepidolite is obtained by floatation in the step S3, the activating agent used by floatation is sulfuric acid, the collecting agent is dodecylamine, and the combination of the activating agent and the collecting agent can float high-purity lepidolite, and has the defect of low lepidolite recovery rate, but can still ensure high overall lithium recovery rate by combining other lithium extraction steps in the method.
In the step S4, the sulfate and the sucrose calcium powder are directly added into the other powder mixed solution after the flotation in the step S3 for secondary ball milling; the sulfate includes sodium sulfate and calcium sulfate.
Evaporating part of the solvent from the mixed slurry obtained by the wet ball milling in the step S4, so that the water content in the evaporated mixed slurry is not more than 10 percent by mass; in the step S5, the concentrated sulfuric acid is 98% by mass, and the roasting temperature is 700-1000 ℃.
In the step S5, the mixing sequence of the mixed slurry and the concentrated sulfuric acid is as follows: the concentrated sulfuric acid is added to the mixed slurry in multiple portions and stirring is continued. Reducing the influence of mass heat generation in the process of mixing the concentrated sulfuric acid with the aqueous solution.
In the step S62, the weak base solution is a weak base solution of ammonia water, and the heating temperature is 60-100 ℃;
adding the ammonia weak base solution into the filter residue in the step S6, and continuously supplementing the ammonia solution after heating and stirring to maintain the pH value of the solution in the filter residue to be 8-9 in the stirring and heating process; along with the heating process, ammonia gas and water vapor are continuously evaporated to cause the fluctuation of the pH value of the solution, in order to maintain the reaction condition, the ammonia water solution is required to be continuously supplemented, and the concentration of the ammonia water solution is regulated in the process of supplementing the ammonia water according to the pH value change in the solution.
The heating and stirring process of the step S62 is performed in a closed container, the closed container comprises a device for automatically displaying the pH value of the solution in the container, the closed container comprises a one-way liquid supplementing port, the one-way liquid supplementing port is used for supplementing the ammonia solution, the closed container further comprises an exhaust channel, the exhaust channel is closed in the heating and stirring process, and after the heating and stirring process of the step S62 is completed, ammonia in the closed container is led into an ammonia recovery device outside the closed container through the exhaust channel, because the ammonia solution is huge in the whole step S62 process, and the recovery device can recycle the ammonia without polluting the environment.
Performing heating evaporation crystallization on the filtrate filtered in the step S62, wherein the heating evaporation crystallization comprises a primary crystallization process and a secondary crystallization process, and a large amount of ammonia generated in the primary crystallization process is introduced into the ammonia recovery device, and meanwhile, ammonium tungstate crystals containing crystal water are obtained; and (3) carrying out the secondary crystallization process on the ammonium tungstate crystal containing the crystallization water, wherein the heating temperature in the secondary crystallization process is 100-150 ℃, and obtaining the anhydrous ammonium tungstate crystal after the secondary crystallization process. Because the dehydration temperature of the ammonium tungstate crystal is 100 ℃, the heating temperature in the secondary crystallization process is higher than 100 ℃, but in consideration of economic cost, the excessive heating temperature is unnecessary, and the dehydration requirement of the ammonium tungstate can be met through measuring and calculating 150 ℃.
In the step S7, the filtrate obtained in the step S6 is introduced into the bottom of a container containing weak base aqueous solution, and stirring is continued until no sediment is generated; in the step S8, the mixed solution after the stirring in the step S7 is subjected to secondary filtration to obtain hydroxide filter residues and filtrate.
The step S82 is to add ethanol into the filtrate obtained in the step S8, stir and filter the filtrate until no sediment is generated, filter the filtrate and crystallize the filter residue to obtain lithium hydroxide crystals
The method disclosed by the application has the following advantages:
according to the method, the characteristics that the tungsten-tin tailings contain a plurality of lithium-containing minerals with different lithium contents and the tungsten content is high are combined, the step S3 of flotation and extraction of lepidolite and other lithium resource extraction steps are combined, and the other lithium resource extraction steps exist, so that the main point of the step S3 of flotation is to extract the purity of lepidolite, a flotation procedure with stronger pertinence is adopted, the purity of lepidolite in the flotation process can be improved, high-purity lithium carbonate is further obtained, and meanwhile, the lithium extraction rate of the whole tungsten-tin tailings resource is ensured due to the existence of the other lithium resource extraction steps. Meanwhile, precious tungsten resources in the process are effectively recovered;
since a metal hydroxide such as tin hydroxide is precipitated with a weak base in advance before precipitating lithium hydroxide with ethanol. Since the metal hydroxide impurities have been removed, a large amount of cations in the solution are alkali metal ions before the start of step S82. While lithium hydroxide is insoluble in ethanol, the solution is subjected to step S82, and then the solution is filtered to obtain high-purity lithium hydroxide.
The method combines the characteristics of various lithium-containing minerals with different lithium contents in the tungsten tin tailings and high tungsten content, and the overall design realizes gradient utilization, so that not only is lithium resources recovered, but also valuable tungsten resources are recovered, and meanwhile, the high-performance ceramic raw material is obtained, the formation of waste residues is greatly reduced, meanwhile, ammonia is absorbed in a closed loop and is recycled, and the cost is saved.
Claims (9)
1. A method for echelon recovery of lithium hydroxide by using tungsten tin tailings, which is characterized by comprising the following steps:
step S1, collecting tungsten tin tailings;
step S2, performing primary ball milling, and performing ball milling on the tungsten tin tailings collected in the step S1;
s3, floating, namely floating the tungsten-tin tailing powder subjected to primary ball milling, and separating to obtain lepidolite powder and other powder mixed liquid;
s4, performing secondary ball milling, namely adding sulfate and calcium sucrose into the other powder mixed solution obtained by flotation to perform wet ball milling to obtain mixed slurry;
s5, roasting the mixed slurry with concentrated sulfuric acid after evaporating part of the solvent;
s6, filtering for the first time, and filtering the slurry after roasting the concentrated sulfuric acid to obtain filtrate and filter residues;
step S62, neutralizing filter residues with alkali liquor and filtering again, adding ammonia water solution into the filter residues obtained in the step S6, stirring and heating, filtering again, drying the filter residues after filtering again to obtain ceramic raw materials, and crystallizing the filtrate after filtering again to obtain ammonium tungstate crystals;
step S7, adding alkali to stir the filtrate, and mixing and stirring the weak alkali solution and the filtrate obtained in the step S6;
s8, performing secondary filtration, and filtering the mixed solution stirred in the step S7 to obtain hydroxide filter residues and filtrate;
and S82, adding alcohol, stirring the filtrate, adding alcohol into the filtrate obtained in the step S8, stirring and filtering to obtain filter residues containing lithium hydroxide precipitates, and crystallizing the filter residues containing the lithium hydroxide precipitates to obtain lithium hydroxide crystals.
2. The method for echelon recovery of lithium hydroxide by using tungsten-tin tailings according to claim 1, wherein the tungsten-tin tailings in the step S1 contain tungsten, tin, lepidolite and quartz, and the mass percentage of tungsten in the tungsten-tin tailings is 0.5% -1%.
3. The method for echelon recovery of lithium hydroxide by using tungsten-tin tailings according to claim 2, wherein the size fraction of the powder material obtained by ball milling in the step S2 is 0.1-0.15mm;
and (3) performing flotation in the step (S3) to obtain lepidolite, wherein the activating agent used in the flotation is sulfuric acid, and the collecting agent is dodecyl amine.
4. The method for echelon recovery of lithium hydroxide by using tungsten-tin tailings according to claim 3, wherein in the step S4, the sulfate and the calcium sucrose powder are directly added into other powder mixed liquid after flotation in the step S3 for secondary ball milling; the sulfate includes sodium sulfate and calcium sulfate.
5. The method for echelon recovery of lithium hydroxide by using tungsten-tin tailings according to claim 4, wherein the mixed slurry obtained by wet ball milling in the step S4 is evaporated with partial solvent so that the water content in the evaporated mixed slurry is not more than 10% by mass; in the step S5, the concentrated sulfuric acid is 98% by mass, and the roasting temperature is 700-1000 ℃.
6. The method for echelon recovery of lithium hydroxide by using tungsten tin tailings according to claim 5, wherein in the step S5, the mixing sequence of the mixed slurry and the concentrated sulfuric acid is as follows: the concentrated sulfuric acid is added to the mixed slurry in multiple portions and stirring is continued.
7. The method for echelon recovery of lithium hydroxide by using tungsten tin tailings according to claim 6, wherein in the step S62, the weak base solution is a weak base solution of ammonia water, and the heating temperature is 60-100 ℃;
adding the ammonia weak base solution into the filter residue in the step S6, and continuously supplementing the ammonia solution after heating and stirring to maintain the pH value of the solution in the filter residue to be 8-9 in the stirring and heating process;
the heating and stirring process of the step S62 is performed in a closed container, the closed container comprises a device for automatically displaying the pH value of the solution in the container, the closed container comprises a one-way liquid supplementing port, the one-way liquid supplementing port is used for supplementing the ammonia water solution, the closed container further comprises an exhaust channel, the exhaust channel is closed in the heating and stirring process, and after the heating and stirring process of the step S62 is completed, ammonia in the closed container is led into an ammonia recovery device outside the closed container through the exhaust channel.
8. The method for echelon recovery of lithium hydroxide by using tungsten tin tailings according to claim 7, wherein the filtrate filtered in the step S62 is subjected to heating evaporation crystallization, the heating evaporation crystallization comprises a primary crystallization process and a secondary crystallization process, and a large amount of ammonia generated in the primary crystallization process is led into the ammonia recovery device, and ammonium tungstate crystals containing crystal water are obtained; and (3) carrying out the secondary crystallization process on the ammonium tungstate crystal containing the crystallization water, wherein the heating temperature in the secondary crystallization process is 100-150 ℃, and obtaining the anhydrous ammonium tungstate crystal after the secondary crystallization process.
9. The method for echelon recovery of lithium hydroxide by using tungsten tin tailings according to claim 8, wherein in the step S7, the filtrate obtained in the step S6 is introduced into the bottom of a container containing weak base aqueous solution, and stirring is continued until no precipitate is generated; in the step S8, the mixed solution after the stirring in the step S7 is subjected to secondary filtration to obtain hydroxide filter residues and filtrate.
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