CN115974105A - Comprehensive utilization method of lithium-containing gypsum slag - Google Patents
Comprehensive utilization method of lithium-containing gypsum slag Download PDFInfo
- Publication number
- CN115974105A CN115974105A CN202211543324.0A CN202211543324A CN115974105A CN 115974105 A CN115974105 A CN 115974105A CN 202211543324 A CN202211543324 A CN 202211543324A CN 115974105 A CN115974105 A CN 115974105A
- Authority
- CN
- China
- Prior art keywords
- lithium
- slag
- washing
- leaching
- iron
- 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.)
- Pending
Links
- 239000002893 slag Substances 0.000 title claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 47
- 239000010440 gypsum Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005406 washing Methods 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002386 leaching Methods 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 1
- 235000011941 Tilia x europaea Nutrition 0.000 claims 1
- 239000004571 lime Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 4
- 239000010970 precious metal Substances 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- RDNYEBBIOKDIBV-UHFFFAOYSA-N [Mn].[Co].[Ni].[Cu] Chemical compound [Mn].[Co].[Ni].[Cu] RDNYEBBIOKDIBV-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
Images
Classifications
-
- 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
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a comprehensive utilization method of lithium-containing gypsum slag, which comprises the following steps: adding water into the lithium-containing gypsum slag, stirring and mixing the mixture, adding hydrogen peroxide and sulfuric acid to adjust the pH value of the slurry, filtering the mixture after reaction to obtain a leaching solution and leaching slag, adjusting the pH value to be subacidity, filtering the mixture after precipitation reaction to adjust the pH value to be alkalescence, filtering the mixture after precipitation reaction to obtain a lithium-containing filtrate, washing the lithium-containing filtrate and filter residues containing nickel, cobalt, manganese and copper to obtain a second washing solution, and performing MVR (mechanical vapor recompression) to obtain anhydrous sodium sulphate and crude lithium carbonate. Leaching by adopting sulfuric acid-hydrogen peroxide, wherein the leaching rate of the precious metal is up to more than 95 percent, realizing the high-efficiency separation of valuable metal and gypsum slag, and producing and selling separated products such as gypsum slag, iron slag, nickel slag, cobalt slag, manganese slag, copper slag and the like; the metal is precipitated by adjusting the pH step by step to realize the separation of base metal Fe and precious metal, and the precipitated filtrate is subjected to calcium carbonate decalcification treatment and returned to the MVR procedure of a workshop, so that sodium sulfate and Li in the filtrate can be recovered.
Description
Technical Field
The invention belongs to the technical field of comprehensive recycling of waste residues, and particularly relates to a comprehensive recycling method of lithium-containing gypsum residues generated in a lithium carbonate production process.
Background
In the waste lithium iron phosphate battery recovery process, in order to improve the recovery efficiency and shorten the process flow, a selective leaching lithium extraction method is adopted to recover lithium, and the process flow is as follows: LFP waste → oxidation acid leaching → purification and impurity removal of filtrate → lithium deposition → water washing → lithium carbonate product. Since the LFP waste contains heavy metals such as Ni, co, mn, cu and the like, the heavy metals enter the filtrate during oxidation acid leaching, and the filtrate is purified and purified by quicklime/carbide slag, so that a certain amount of lithium-containing gypsum slag is generated. Heavy metals such as Ni, co, mn, cu and the like exist in the lithium-containing gypsum slag in a hydroxide precipitation mode. The lithium-containing gypsum slag not only contains a plurality of valuable heavy metal elements, but also contains a certain lithium element, and if the lithium-containing gypsum slag is directly sold for building materials without being processed, the lithium-containing gypsum slag not only causes resource waste, but also pollutes the environment.
Therefore, valuable elements in the lithium-containing gypsum slag are recovered by adopting an effective way, the harm of the lithium-containing gypsum slag is reduced to the maximum extent, and the method is very necessary for a lithium carbonate production process by recovering lithium iron phosphate.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and defects in the background technology, and provides a comprehensive recycling method for lithium-containing gypsum slag generated in the process of purifying a waste lithium iron phosphate selective lithium extraction solution.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a comprehensive utilization method of lithium-containing gypsum slag comprises the following steps:
(1) Adding water into the lithium-containing gypsum slag, stirring and mixing, adding hydrogen peroxide and sulfuric acid to adjust the pH value of the slurry, heating, keeping the temperature, stirring, reacting, and filtering to obtain a leaching solution and leaching slag;
(2) Adding alkali liquor into the leachate obtained in the step (1) to adjust the pH value to be weakly acidic, carrying out precipitation reaction, filtering to obtain a liquid after iron removal and iron slag, and washing the iron slag to obtain a washing solution I;
(3) Mixing the iron-removed liquid obtained in the step (2) with the washing liquid I, adding an alkaline solution to regulate the pH value to be alkaline, carrying out precipitation reaction, filtering to obtain a lithium-containing filtrate and filter residues containing nickel, cobalt, manganese and copper, and washing the filter residues containing nickel, cobalt, manganese and copper to obtain a washing liquid II;
(4) And (4) mixing the lithium-containing filtrate obtained in the step (3) with the washing solution II, adding sodium carbonate, and performing MVR (mechanical vapor recompression) to obtain anhydrous sodium sulfate and crude lithium carbonate.
The following reaction occurs in step (1):
1. adding carbide slag to the pickle liquor of the workshop for impurity precipitation: mn 2+ +OH - →Mn(OH) 2
2. Oxidizing the manganese hydroxide: 2Mn (OH) 2 +O 2 →2MnO(OH) 2
3、MnO(OH) 2 Dissolved (insoluble in sulfuric acid, but soluble in acidified hydrogen peroxide):
MnO(OH) 2 +2H + +H 2 O 2 ＝Mn 2+ +3H 2 O+O 2 ↑
therefore, the leaching effect can be improved by adding hydrogen peroxide in the sulfuric acid leaching process.
The pH value of the step 1 is less than 1.2, and the purpose is to leach Li, ni, co, mn, cu and Fe in the slag through the strong acid oxidation condition of sulfuric acid and hydrogen peroxide; step 2, adding alkali to adjust the pH value to 3.5-4.0, so as to precipitate the Fe leached in the step 1 into ferric hydroxide precipitate; and 3, adjusting the pH value to 10.0-10.5 to precipitate valuable elements such as Ni, co, mn, cu and the like in the leachate. The purpose of the steps 2 and 3 is to remove most Fe by adjusting the pH according to different precipitation pH of Ni, co, mn, cu and Fe, so that the valuable element content of the Ni, co, mn and Cu slag enriched in the step 3 is higher.
Preferably, the lithium-containing gypsum residue in the step (1) is a lithium sulfate acid leaching solution obtained by adding sulfuric acid to a waste lithium iron phosphate battery for acid leaching, and then adding carbide slag or precipitated slag formed by precipitating metal with quicklime.
Preferably, the lithium-containing gypsum slag in the step (1) contains 1.0wt% of lithium, 0.2-4.0 wt% of nickel, 2.0wt% of cobalt, 0.5-4.0 wt% of manganese, 2.0wt% of copper and 1.0-6.0 wt% of iron.
Preferably, the stirring and size mixing time in the step (1) is 10-60 min, and the solid-liquid ratio of stirring and size mixing is 1: 2-4.
Preferably, in the step (1), the mass percentage concentration of the hydrogen peroxide is 25-50%, the addition amount of the hydrogen peroxide is 0.6-3.0 times of the mass of manganese in the lithium-containing gypsum slag, the mass percentage concentration of the sulfuric acid is 70-98%, and the addition amount of the sulfuric acid is 0.25-0.5 times of the mass of the lithium-containing gypsum slag. A sulfuric acid and hydrogen peroxide system is adopted to reduce manganese oxyhydroxide (insoluble in acid) to enable manganese to enter a solution in an ionic state.
Preferably, the pH value of the slurry in the step (1) is adjusted to be less than 1.2, the heating is carried out to 60-90 ℃, and the heat preservation and stirring time is 1-3 h.
Preferably, the leached residues in the step (1) are washed to obtain gypsum residues and washing water, and the washing water is used as acid leaching feeding water for producing the lithium-containing gypsum residues.
Preferably, the alkali liquor in the step (2) and the step (3) is a sodium hydroxide solution, and the mass concentration of the sodium hydroxide solution is 20-40%.
Preferably, the pH adjusted in step (2) is weakly acidic and is 3.5 to 4.0, and the pH adjusted in step (3) is alkaline and is 10.0 to 10.5.
Preferably, in the step (4), the addition amount of the sodium carbonate in the mixed solution of the lithium-containing filtrate and the washing solution is 20 to 60mg/L. Sodium carbonate is added to remove calcium from the solution, and the filtrate is returned to MVR treatment.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the comprehensive recycling method for the lithium-containing gypsum slag in the selective lithium extraction production of the waste lithium iron phosphate, sulfuric acid-hydrogen peroxide is adopted for leaching, the leaching rate of Ni, co, mn, cu and Li is up to more than 95%, the efficient separation of valuable metals and the gypsum slag is realized, and the products of the separated gypsum slag, iron slag, nickel slag, cobalt slag, manganese slag, copper slag and the like are produced for sale, so that economic benefits are obtained; more than 98% of iron in the pickle liquor can enter the iron slag by gradually adjusting the pH to precipitate the metal, so that the separation of base metal Fe and precious metals Ni, co, mn and Cu is realized, the recovery rate of the Ni, co, mn and Cu precipitate reaches more than 90%, the filtrate after precipitation is subjected to calcium carbonate decalcification treatment and returned to the MVR process of a workshop, and sodium sulfate and Li in the filtrate can be recovered.
2. According to the invention, a two-stage impurity removal process is adopted, ni, co, mn and Cu in secondary impurity removal can be enriched and recovered, the first impurity removal slag and the secondary slag are avoided together, the contents of Ni, co, mn and Cu in the secondary slag are reduced, pH leaching is adjusted in multiple stages, and the pH value in step 1 is less than 1.2, so that the aim of leaching Li, ni, co, mn, cu and Fe in the slag through the strong acid oxidation condition of sulfuric acid and hydrogen peroxide is achieved; step 2, adding alkali to adjust the pH value to 3.5-4.0 so as to precipitate Fe leached in the step 1 into ferric hydroxide precipitate; and 3, adjusting the pH value to 10.0-10.5 to precipitate valuable elements such as Ni, co, mn, cu and the like in the leaching solution, and adjusting the pH value to remove most Fe in the step 2 and the step 3 according to different precipitation pH values of Ni, co, mn, cu and Fe so as to ensure that the valuable element content of the Ni, co, mn and Cu slag enriched in the step 3 is higher.
3. The comprehensive recycling method of the lithium-containing gypsum slag in the production of the waste lithium iron phosphate selective lithium extraction lithium carbonate has simple operation, can comprehensively recycle various elements in the lithium-containing gypsum slag, and the washing liquid in the production process can also be used as acid leaching feeding water for producing the lithium-containing gypsum slag or a reactant in the subsequent step, thereby achieving the effect of harmless discharge and having very important significance for saving resources and lightening environmental pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram for the comprehensive recycling of the lithium-containing gypsum slag of the present invention.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a method for comprehensively utilizing lithium-containing gypsum slag is shown in figure 1, and the content of each metal in a product is tested by the following steps:
in this example, the composition of the lithium-containing gypsum slag is: 0.13wt% of Li, 0.22wt% of Ni, 0.07wt% of Co, 0.73wt% of Mn, 0.25wt% of Cu, and 1.95wt% of Fe.
(1) Adding 400g of lithium-containing gypsum slag into 800g of water, stirring for 10min, mixing, adding 6.48g of 50% hydrogen peroxide water with concentration and 112.00g of 98% sulfuric acid with concentration until the pH value of the slurry is 1.08, heating to 60 ℃, stirring for 1h under heat preservation, and filtering after the reaction is finished to obtain leachate and leaching slag; washing the leached slag to obtain the lithium-containing gypsum slag, and using the washing water as acid leaching feeding water.
(2) Adding sodium hydroxide solution into the leachate to adjust the pH value to 4.0, precipitating and reacting for 0.5h, and filtering to obtain iron-removed liquid and iron slag; washing the iron slag to obtain washing liquid I and washed iron slag.
(3) Mixing the deironing solution and the washing solution I, adding a sodium hydroxide solution with the mass concentration of 40% to adjust the pH value to 10.0, precipitating and reacting for 0.5h, and filtering to obtain a filtrate containing Li and filter residues containing Ni, co, mn and Cu; washing the filter residue to obtain washing liquid II and the washed nickel-cobalt-manganese-copper slag.
(4) And mixing the Li-containing filtrate and the washing liquid II per liter, adding 60mg of sodium carbonate to remove calcium, and performing MVR (mechanical vapor recompression) to prepare anhydrous sodium sulfate and crude lithium carbonate.
Table 1 metal content in the product obtained in example 1
Example 2:
a method for comprehensively utilizing lithium-containing gypsum slag is disclosed, the process flow is shown in figure 1, the content of each metal in a product is tested, and the steps are as follows:
in this example, the composition of the lithium-containing gypsum slag is: li 0.20wt%, ni 2.01wt%, co 0.76wt%, mn 1.42wt%, cu 0.67wt%, fe 2.33wt%.
(1) Adding 250g of lithium-containing gypsum slag into 1000g of water, stirring for 60min, mixing, adding 28.81g of 27% hydrogen peroxide water with concentration and 90.88g of 98% sulfuric acid with concentration until the pH value of the slurry is 0.88, heating to 90 ℃, keeping the temperature, stirring for 3h, and filtering after the reaction is finished to obtain leachate and leaching slag; washing the leached slag to obtain gypsum slag, and using the washing water as acid leaching feeding water.
(2) Adding sodium hydroxide solution into the leachate to adjust the pH value to 3.5, precipitating and reacting for 0.5h, and filtering to obtain iron-removed liquid and iron slag; washing the iron slag to obtain washing liquid I and washed iron slag.
(3) Mixing the iron-removed solution and the washing solution I, adding a sodium hydroxide solution with the mass concentration of 20% to adjust the pH value to 10.5, precipitating and reacting for 0.5h, and filtering to obtain a Li-containing filtrate and filter residues containing Ni, co, mn and Cu; washing the filter residue to obtain washing liquid II and the washed nickel-cobalt-manganese-copper slag.
(4) And mixing the Li-containing filtrate and the washing liquid II per liter, adding 20mg of sodium carbonate to remove calcium, and performing an MVR (mechanical vapor recompression) process to prepare anhydrous sodium sulfate and crude lithium carbonate.
Table 2 metal content in the product obtained in example 2
As can be seen from tables 1 and 2, valuable elements in the metal can be efficiently precipitated and recovered by adjusting the pH value after acid leaching, and the recovery rates of Ni, co, mn and Cu are up to more than 90%; the gypsum residue after the leaching residue is washed can be sold outside for building materials without harm; and (4) removing calcium from the precipitated filtrate, returning the filtrate to the MVR procedure of a workshop, and recovering sodium sulfate and Li in the filtrate. Therefore, the effects of comprehensive recycling and harmless discharge are achieved, and the method has very important significance for saving resources and reducing environmental pollution.
Claims (10)
1. A comprehensive utilization method of lithium-containing gypsum slag is characterized by comprising the following steps:
(1) Adding water into the lithium-containing gypsum slag, stirring and mixing, adding hydrogen peroxide and sulfuric acid to adjust the pH value of the slurry, heating, keeping the temperature, stirring, reacting, and filtering to obtain leachate and leaching slag;
(2) Adding alkali liquor into the leachate obtained in the step (1) to adjust the pH value to be weakly acidic, carrying out precipitation reaction, filtering to obtain a liquid after iron removal and iron slag, and washing the iron slag to obtain a washing solution I;
(3) Mixing the iron-removed liquid obtained in the step (2) with the washing liquid I, adding an alkaline solution to regulate the pH value to be alkaline, carrying out precipitation reaction, filtering to obtain a lithium-containing filtrate and filter residues containing nickel, cobalt, manganese and copper, and washing the filter residues containing nickel, cobalt, manganese and copper to obtain a washing liquid II;
(4) And (4) mixing the lithium-containing filtrate obtained in the step (3) with the washing solution II, adding sodium carbonate, and performing MVR (mechanical vapor recompression) to obtain anhydrous sodium sulfate and crude lithium carbonate.
2. The method as claimed in claim 1, wherein the lithium-containing gypsum residue in step (1) is a precipitation residue formed by adding carbide slag or calcium lime to precipitate metals, wherein the precipitation residue is obtained by adding sulfuric acid to a lithium sulfate acid leaching solution obtained by adding sulfuric acid to a waste lithium iron phosphate battery for acid leaching.
3. The method of claim 1, wherein the gypsum slag containing lithium in step (1) contains less than 1.0wt% of lithium, 0.2-4.0 wt% of nickel, less than 2.0wt% of cobalt, 0.5-4.0 wt% of manganese, less than 2.0wt% of copper, and 1.0-6.0 wt% of iron.
4. The method as claimed in claim 1, wherein the stirring and size mixing time in the step (1) is 10-60 min, and the solid-liquid ratio of the stirring and size mixing is 1: 2-4.
5. The method according to claim 1, characterized in that in the step (1), the mass percentage concentration of the hydrogen peroxide is 25-50%, the addition amount of the hydrogen peroxide is 0.6-3.0 times of the mass of manganese in the lithium-containing gypsum slag, the mass percentage concentration of the sulfuric acid is 70-98%, and the addition amount of the sulfuric acid is 0.25-0.5 times of the mass of the lithium-containing gypsum slag.
6. The method according to claim 1, wherein the pH of the slurry is adjusted to be less than 1.2 in the step (1), the heating is carried out to be 60-90 ℃, and the heat preservation and stirring time is 1-3 h.
7. The method according to claim 1, characterized in that the leaching residue in step (1) is washed to obtain gypsum residue and washing water, and the washing water is used as acid leaching feeding water for producing the lithium-containing gypsum residue.
8. The method according to claim 1, wherein the alkali liquor in the steps (2) and (3) is sodium hydroxide solution, and the mass concentration of the sodium hydroxide solution is 20-40%.
9. The method according to claim 1, wherein the adjusted pH in step (2) is a weakly acidic pH of 3.5 to 4.0, and the adjusted pH in step (3) is a basic pH of 10.0 to 10.5.
10. The method according to claim 1, wherein the sodium carbonate is added to the mixture of the lithium-containing filtrate and the washing solution in the step (4) in an amount of 20 to 60mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211543324.0A CN115974105A (en) | 2022-12-02 | 2022-12-02 | Comprehensive utilization method of lithium-containing gypsum slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211543324.0A CN115974105A (en) | 2022-12-02 | 2022-12-02 | Comprehensive utilization method of lithium-containing gypsum slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115974105A true CN115974105A (en) | 2023-04-18 |
Family
ID=85972923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211543324.0A Pending CN115974105A (en) | 2022-12-02 | 2022-12-02 | Comprehensive utilization method of lithium-containing gypsum slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115974105A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024141117A1 (en) * | 2023-09-19 | 2024-07-04 | 天齐锂业股份有限公司 | Method for extracting lithium from spodumene while recovering low-iron and low-sulfur silicon-aluminum micro powder, high-purity gypsum, tantalum-niobium concentrate and lithium-rich iron material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| KR102154599B1 (en) * | 2019-04-30 | 2020-09-10 | 코스모에코켐(주) | Method for Separation and Recovery of Valuable Metals from Cathode Active Material |
| WO2022105463A1 (en) * | 2020-11-23 | 2022-05-27 | 湖南金源新材料股份有限公司 | Comprehensive recycling method for waste lithium iron phosphate batteries |
-
2022
- 2022-12-02 CN CN202211543324.0A patent/CN115974105A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| KR102154599B1 (en) * | 2019-04-30 | 2020-09-10 | 코스모에코켐(주) | Method for Separation and Recovery of Valuable Metals from Cathode Active Material |
| WO2022105463A1 (en) * | 2020-11-23 | 2022-05-27 | 湖南金源新材料股份有限公司 | Comprehensive recycling method for waste lithium iron phosphate batteries |
Non-Patent Citations (2)
| Title |
|---|
| 刘庆杰;贾玲;李广海;: "从湿法炼锌锑盐净化钴渣中回收钴、锌、镉、铜", 资源再生, no. 09, 15 September 2010 (2010-09-15) * |
| 陈欢;张银亮;谭群英;唐红辉;李强;: "废旧电池回收过程中硫酸镍钴锰溶液除铁铝工艺研究", 湿法冶金, no. 06, 2 November 2018 (2018-11-02) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024141117A1 (en) * | 2023-09-19 | 2024-07-04 | 天齐锂业股份有限公司 | Method for extracting lithium from spodumene while recovering low-iron and low-sulfur silicon-aluminum micro powder, high-purity gypsum, tantalum-niobium concentrate and lithium-rich iron material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112357899A (en) | Comprehensive recycling method of waste lithium iron phosphate batteries | |
| CN112662877B (en) | Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag | |
| CN110835683B (en) | Method for selectively extracting lithium from waste lithium ion battery material | |
| CN111334664B (en) | Method for comprehensively recycling valuable metals from ternary lithium battery positive electrode material based on magnesium salt circulation | |
| CN108408745B (en) | Method for preparing battery-grade lithium carbonate from waste lithium batteries | |
| CN110983045A (en) | Method for removing iron and aluminum from nickel-cobalt-manganese solution | |
| CN112779419B (en) | Method for removing iron, aluminum and silicon from nickel, cobalt, manganese and copper solution under normal pressure | |
| CN111826523B (en) | Method for refining nickel hydroxide cobalt | |
| US11981976B2 (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| WO2023000847A1 (en) | Nickel-iron wet treatment method and application thereof | |
| CN113088705A (en) | Method for preparing cobalt salt by low-cost resource treatment of cobalt intermediate and waste battery materials | |
| CN115505754B (en) | Leaching method of crude nickel hydroxide | |
| CN113502394A (en) | Method for recovering cobalt or nickel intermediate product | |
| CN115974105A (en) | Comprehensive utilization method of lithium-containing gypsum slag | |
| CN116377243A (en) | Method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw material | |
| CN112609090B (en) | Separation method of copper-cobalt oxide ore | |
| CN111573736B (en) | Method for preparing industrial manganese carbonate by using copper-manganese chloride solution | |
| CN108977672B (en) | Method for preparing iron molybdate by taking molybdenum-removing slag as raw material | |
| CN108441649B (en) | Method for extracting nickel from chemical precipitation nickel sulfide material | |
| CN115109943A (en) | Method for extracting and recovering copper, zinc, cobalt and manganese metals from copper chloride manganese zinc cobalt solution step by step | |
| CN113943019A (en) | Method for separating ferrochrome from chromium-and iron-containing solution | |
| CN113582252A (en) | Preparation method of nickel-cobalt-manganese ternary precursor material and lithium ion battery | |
| CN110092423B (en) | Method for producing nickel sulfate solution by quickly dissolving nickel oxide and deacidifying and removing impurities with nickel soap | |
| CN114645143A (en) | Separation method of nickel, cobalt, copper and manganese in laterite-nickel ore | |
| CN111172392A (en) | Environment-friendly iron removal method without impurity in laterite-nickel ore leaching solution |
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 |