CN110498433B - Method, equipment and application for preparing lithium ion-containing solution - Google Patents
Method, equipment and application for preparing lithium ion-containing solution Download PDFInfo
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- CN110498433B CN110498433B CN201810471158.5A CN201810471158A CN110498433B CN 110498433 B CN110498433 B CN 110498433B CN 201810471158 A CN201810471158 A CN 201810471158A CN 110498433 B CN110498433 B CN 110498433B
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- solution
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- 238000000034 method Methods 0.000 title claims abstract description 98
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 95
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 159
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 156
- 239000002994 raw material Substances 0.000 claims abstract description 66
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 59
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 59
- 238000011084 recovery Methods 0.000 claims abstract description 51
- 238000002386 leaching Methods 0.000 claims description 212
- 239000007788 liquid Substances 0.000 claims description 187
- 239000007787 solid Substances 0.000 claims description 165
- 239000000243 solution Substances 0.000 claims description 140
- 238000005406 washing Methods 0.000 claims description 108
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 78
- 239000011575 calcium Substances 0.000 claims description 78
- 229910052791 calcium Inorganic materials 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 63
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 63
- 239000002893 slag Substances 0.000 claims description 51
- 238000000926 separation method Methods 0.000 claims description 50
- 239000003929 acidic solution Substances 0.000 claims description 45
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 31
- 239000001110 calcium chloride Substances 0.000 claims description 31
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 31
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 31
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 31
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 30
- 235000017550 sodium carbonate Nutrition 0.000 claims description 30
- 239000012535 impurity Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 22
- 239000001488 sodium phosphate Substances 0.000 claims description 19
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 19
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 19
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 18
- 239000002699 waste material Substances 0.000 claims description 15
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910001424 calcium ion Inorganic materials 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 12
- 239000010802 sludge Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000012047 saturated solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- 238000010936 aqueous wash Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 22
- 239000000203 mixture Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 9
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 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 description 8
- 238000010977 unit operation Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 3
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 leached residues Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D25/00—Filters formed by clamping together several filtering elements or parts of such elements
- B01D25/12—Filter presses, i.e. of the plate or plate and frame type
- B01D25/21—Plate and frame presses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application provides a method for preparing a solution containing lithium ions, and lithium carbonate is prepared by using the prepared solution containing lithium ions. In the method for preparing the solution containing lithium ions, the used raw materials can be various lithium-containing recovery raw materials, the recovery rate of lithium reaches over 94 percent, precious lithium resources are saved, and the vigorous market demands of domestic electric vehicle batteries and large energy storage batteries can be met by further preparing lithium carbonate.
Description
Technical Field
The invention relates to the technical field of lithium recovery and lithium carbonate preparation, in particular to a method and equipment for preparing a solution containing lithium ions by using various lithium-containing recovery raw materials.
Background
The important role played by lithium materials in human life is self-evident, especially in recent years, the demand of lithium electricity has been increased at a rate of more than 20% for five years continuously, the global consumption of lithium carbonate in 2009 is 8 ten thousand tons, and the demand of lithium carbonate is estimated to reach 20 ten thousand tons by 2020 due to the vigorous market demands of domestic electric vehicle batteries and large energy storage batteries. With the tight supply of upstream cobalt, lithium and other resources and the continuous increase of market demand, how to prepare lithium carbonate by various lithium-containing recovery raw materials is significant. The existing lithium-containing recovery raw materials are lithium-containing solutions in the state of low-concentration lithium chloride and lithium sulfate, and the existing lithium-containing recovery raw materials are various lithium-containing recovery raw materials in the state of lithium carbonate, lithium fluoride, lithium chloride, lithium sulfate or lithium phosphate, so that the materials are large in storage quantity, and if the materials can be effectively utilized, precious lithium resources are saved, and huge economic benefits can be created.
Disclosure of Invention
The application relates to a multistage countercurrent solid-liquid contact device, which provides a method for preparing a solution containing lithium ions by using various lithium-containing recovery raw materials, and provides a method for preparing lithium carbonate by using the solution containing lithium ions, so as to solve the problem of effective utilization of lithium resources in the background technology.
Embodiment 1. A method of preparing a solution containing lithium ions, comprising:
and carrying out multistage countercurrent leaching on the lithium-containing solid raw material by adopting a calcium-containing acidic solution to obtain a solution containing lithium ions and leaching residues.
Embodiment 2. The method according to embodiment 1, wherein the solution containing lithium ions is a solution containing lithium chloride or lithium sulfate.
Embodiment 3. The method according to embodiment 1, wherein the calcium-containing acidic solution is a solution containing an acid and calcium ions, the acid including at least one selected from hydrochloric acid and sulfuric acid.
Embodiment 4. The method according to embodiment 1, wherein the lithium-containing solid raw material contains at least one selected from the group consisting of lithium phosphate, lithium fluoride, lithium chloride, lithium carbonate, and lithium sulfate.
Embodiment 5. The method of embodiment 1, wherein the multi-stage countercurrent leaching comprises two or more stages of countercurrent leaching steps.
Embodiment 6. The method according to embodiment 1 or 5, characterized by comprising washing the leaching residue with water, for example, in a multistage countercurrent water washing comprising two or more stages of countercurrent water washing.
Embodiment 7. The method according to embodiment 1, characterized in that the PH of the calcium-containing acidic solution is less than 6, preferably less than 5, optionally the PH of the calcium-containing acidic solution is greater than 3.
Embodiment 8. The method according to embodiment 1, characterized in that the molar ratio of calcium in the calcium-containing acidic solution to lithium in the lithium-containing solid raw material is 1:0.1 to 0.3:1, preferably 1:0.1 to 1:1, preferably 1:0.2 to 1:0.5, preferably 1:0.3 to 1:0.4.
Embodiment 9. The method of embodiment 1, wherein the single stage of the multistage countercurrent leaching is performed for a reaction time of 0.3 to 4 hours, such as 1 to 3 hours, and a reaction temperature of 50 to 95 degrees celsius, such as 60 to 80 degrees celsius.
Embodiment 10. The method of embodiment 6, wherein the single stage of the multistage countercurrent water wash is performed for a period of 0.3 to 4 hours, such as 1 to 3 hours, at a temperature of 50 to 95 degrees celsius, such as 60 to 80 degrees celsius.
Embodiment 11. The method of embodiment 5 or 6, wherein the multi-stage countercurrent leaching comprises a three-stage countercurrent leaching comprising the steps of:
(1) A primary leaching step, wherein the secondary leaching solid is contacted with a primary calcium-containing acidic solution to obtain a primary leaching solid and a primary leaching liquid, and the primary leaching solid is leaching slag;
(2) A secondary leaching step, wherein the tertiary leaching solids are contacted with a secondary calcium-containing acidic solution to obtain secondary leaching solids and a secondary leaching liquid;
(3) And a third leaching step, wherein the lithium-containing solid raw material is contacted with a third calcium-containing acidic solution to obtain a third leached solid and a third leaching solution, and the third leaching solution is the lithium ion-containing solution.
Embodiment 12. The method of embodiment 6 or 11, wherein the multi-stage countercurrent water wash comprises a two-stage countercurrent water wash comprising the steps of:
(1) The first-stage countercurrent washing, wherein the second-stage washing slag is contacted with water-containing liquid to obtain first-stage washing slag, namely waste slag and first-stage washing liquid;
(2) And (3) carrying out secondary countercurrent washing, wherein leaching residues are contacted with the primary washing liquid to obtain secondary washing liquid and secondary washing residues.
Embodiment 13. The method according to embodiment 12, characterized in that the primary calcium-containing acidic solution is formulated from the secondary aqueous wash with the addition of hydrochloric acid and calcium chloride, the secondary calcium-containing acidic solution is formulated from the primary leach solution optionally with the addition of hydrochloric acid and calcium chloride, and the tertiary calcium-containing acidic solution is formulated from the secondary leach solution optionally with the addition of hydrochloric acid and calcium chloride.
Embodiment 14. A method of preparing lithium carbonate, comprising: the method of any one of embodiments 1-13, wherein the solution comprising lithium ions is prepared.
Embodiment 15. The method of preparing lithium carbonate according to embodiment 14, characterized in that the lithium-containing solid feedstock is obtained from a pretreatment of a lithium-containing recycle feedstock, the pretreatment comprising at least one of the following steps:
(1) When the lithium-containing recovery raw material comprises liquid, enabling trisodium phosphate to react with the liquid, and carrying out solid-liquid separation to obtain the lithium-containing solid raw material; and
(2) When the lithium-containing recovery raw material contains a solid, the solid is prepared into a proper particle size, and impurities are removed.
Embodiment 16. The method of producing lithium carbonate according to embodiment 15, characterized in that the molar ratio of trisodium phosphate to lithium in the lithium-containing recovery feedstock is from 0.3:1 to 0.4:1.
Embodiment 17. The method for producing lithium carbonate according to embodiment 15, characterized in that the method comprises adjusting the PH (e.g., PH 10 or more, e.g., 11 or more) of the solution containing lithium ions with a base such as a hydroxide, and adding soda ash, and performing liquid-solid separation to obtain a solution containing lithium ions and a residue (the residue is used as the solid raw material containing lithium) after removal.
Embodiment 18. The method of embodiment 17 wherein the molar ratio of the sodium carbonate to the calcium in the purified lithium ion-containing solution is from 0.8:1 to 1.2:1, such as from 1.0:1 to 1.1:1.
Embodiment 19. The method of preparing lithium carbonate according to embodiment 18, characterized in that the alkaline pH is 10 or more, for example 11 or more.
Embodiment 20. The method for producing lithium carbonate according to embodiment 17, characterized by comprising reacting the purified lithium ion-containing solution with a saturated solution of soda, and performing liquid-solid separation to obtain lithium carbonate solid and a mother liquor.
Embodiment 21. The method of preparing lithium carbonate according to embodiment 20, characterized in that the amount of soda is such that the molar ratio of soda to lithium in the solution containing lithium ions is 0.3:1 to 0.8:1, for example 0.5:1 to 0.55:1.
Embodiment 22. The method for producing lithium carbonate according to embodiment 20, characterized by comprising reacting a mother liquor with trisodium phosphate and performing liquid-solid separation to obtain lithium phosphate sludge.
Embodiment 23. The method of producing lithium carbonate according to embodiment 22, characterized by comprising returning the lithium phosphate sludge to the pretreatment step as a lithium-containing recovery raw material.
Embodiment 24. A multistage countercurrent solid-liquid contacting apparatus comprising N solid-liquid contacting units, wherein the ith solid-liquid contacting unit comprises: contacting means (3), separating means (6),
Wherein the contact device (3) is provided with a contact device feed port (12) and a contact device discharge port (5), the separation device is provided with a separation device feed port (11), a separation device liquid discharge port (9) and a separation device solid discharge port (13),
The discharge port (5) of the contact equipment is connected with the feed port (11) of the separation equipment,
Wherein, for the ith solid-liquid contact unit,
When N is more than i and more than 1 (i and N are integers and N is an integer more than or equal to 3), the contact equipment feed inlet (12) is connected with the separation equipment liquid discharge port of the i-1 solid-liquid contact unit and the separation equipment solid discharge port of the i+1 solid-liquid contact unit,
When i=1, the contact device feed port (12) is connected with the separation device solid discharge port of the (i+1) th solid-liquid contact unit and with an external liquid feed device;
When i=n, the contacting device feed port is connected to the separating device liquid discharge port of the i-1 th solid-liquid contacting unit and to the external solid feed device, optionally the separating device liquid discharge port is connected to the external liquid treatment device. In the present application, when referring to the solid-liquid contacting unit, "a" and "a" are used to define the same meaning, such that the 2 nd solid-liquid contacting unit and the 2 nd solid-liquid contacting unit have the same meaning, and thus, "a" and "a" are used interchangeably at this time.
Embodiment 25. The multistage countercurrent solid-liquid contacting apparatus according to embodiment 24, characterized in that the contacting apparatus is provided with stirring apparatus (4).
Embodiment 26. The multistage countercurrent solid-liquid contacting apparatus according to embodiment 24, wherein for the j-th solid-liquid contacting unit, where j > 1, the solid-liquid contacting unit further comprises a solid treatment apparatus (8), the separation apparatus solid discharge port (13) is connected to the solid treatment apparatus (8);
the solid treatment equipment (8) is provided with a stirring equipment (7);
the solid treatment device (8) is provided with a solid treatment device discharge port (10);
and the discharge port (10) of the solid treatment device is connected with the feed port of the contact device of the upper-stage solid-liquid contact unit.
Embodiment 27. The multistage countercurrent solid-liquid contacting apparatus according to any one of embodiments 24 to 26, characterized in that the separation apparatus is a filter press.
Embodiment 28. The multistage countercurrent solid-liquid contact apparatus according to embodiment 27, wherein the filter press is a plate-and-frame filter press.
Embodiment 29. The multistage countercurrent solid-liquid contacting apparatus according to any one of embodiments 24 to 26, wherein the contacting apparatus (3) is a reaction vessel.
Embodiment 30. The multistage countercurrent solid-liquid contacting apparatus of embodiment 26, wherein the solid treatment apparatus is a slurrying tank.
The invention has simple process route, easy operation and low cost; the lithium metal in various lithium-containing recovery raw materials can be effectively recovered, the comprehensive utilization rate of lithium can reach more than 94%, and the social benefit is obvious; the lithium carbonate product produced by the method can reach battery level, and has remarkable economic benefit.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following brief description of the drawings of the embodiments will make it apparent that the drawings in the following description relate only to some embodiments of the present disclosure, not to limit the present disclosure.
Figure 1 shows a schematic diagram of a single countercurrent contacting unit of a multistage countercurrent solid-liquid contacting apparatus according to one embodiment of the present application.
Figure 2 illustrates a three stage countercurrent leaching, two stage countercurrent water wash procedure according to one embodiment of the present application.
Reference numerals:
1. A liquid supply pipeline connected with the liquid discharge port of the primary solid-liquid contact unit or the discharge port of the external liquid treatment equipment
2. A solid supply pipeline connected with the solid discharge port of the next-stage solid-liquid contact unit or the discharge port of the external solid supply device
3.4 Parts of a reaction kettle, 5 parts of a stirrer, 6 parts of a discharge hole of the reaction kettle, 7 parts of a plate-and-frame filter press and 7 parts of the stirrer
8. Slurrying kettle 9, a liquid discharge hole 10 of a plate-and-frame filter press, and a discharge hole of the slurrying kettle
11. Plate-and-frame filter press feed inlet 12, reaction kettle feed inlet 13, plate-and-frame filter press solid discharge outlet
Detailed Description
Terms used in the present application have meanings commonly understood by those skilled in the art unless explicitly indicated to the contrary or contradicted by context. The term "solution containing lithium ions" according to the present application refers to a state in which lithium is dissolved in a solvent in an ionic form, wherein the solvent is generally an aqueous solvent, and the solution does not exclude other components from the solution. "lithium-containing solid feedstock" refers to solid feedstock containing lithium elements, including various lithium-containing recovery feedstock containing lithium carbonate, lithium fluoride, or lithium phosphate. "calcium-containing acidic solution" means a solution containing calcium ions under acidic conditions, i.e., at a pH of less than 7, without excluding the inclusion of other ions at the same time. The term "aqueous liquid" in the present application refers to a liquid whose main component is water, such as a liquid having a water content of more than 50wt%, for example a liquid having a water content of more than 60wt%, for example a liquid having a water content of more than 70wt%, for example a liquid having a water content of more than 80wt%, for example a liquid having a water content of more than 90wt%, for example a liquid having a water content of more than 95 wt%.
In one aspect, the present application provides a method of preparing a solution containing lithium ions, comprising: and carrying out multistage countercurrent leaching on the lithium-containing solid raw material by adopting a calcium-containing acidic solution to obtain a solution containing lithium ions and leaching residues. Fractional countercurrent leaching is a batch operation. By performing multistage countercurrent leaching of a lithium-containing solid raw material with a calcium-containing acidic solution, lithium leaching can be performed with high efficiency, and a solution containing lithium ions with high lithium recovery rate and high concentration can be obtained.
In the present application, the composition of the lithium ion-containing solution is not particularly limited, and it mainly varies depending on the operation method, and for example, a lithium chloride solution is obtained by leaching with acid calcium chloride, and a lithium sulfate solution is obtained by leaching with acid calcium sulfate solution. In some embodiments, the lithium ion-containing solution is a lithium chloride-containing solution, and in other embodiments, the lithium ion-containing solution is a lithium sulfate-containing solution.
In the present application, the acid in the calcium-containing acidic solution is not particularly limited as long as leaching of lithium can be achieved, and may be any acid that a person skilled in the art has proven to be viable through ordinary experiments. In some embodiments, the calcium-containing acidic solution is a solution containing an acid and calcium ions, the acid including at least one selected from hydrochloric acid and sulfuric acid.
In the present application, the lithium-containing solid raw material is not particularly limited as long as it contains lithium suitable for leaching, which may be present in any suitable compound state. In some embodiments, the lithium-containing solid feedstock includes a feedstock containing one or more selected from lithium phosphate, lithium fluoride, lithium chloride, lithium carbonate, and lithium sulfate. Lithium phosphate and lithium fluoride are the most readily available raw materials in practice, and they often originate from discarded batteries and the like.
In the present application, there is no limitation on how many stages of countercurrent leaching are employed, as long as the purpose of leaching can be achieved. But in general, a minimum of two-stage leaching is used, three-stage leaching enables a higher leaching rate, and more than four-stage leaching is economically unsuitable. In some embodiments, the multi-stage countercurrent leaching comprises two or more stages of countercurrent leaching steps.
In the present application, there is no limitation on how many stages of countercurrent water washing are used, as long as lithium ions in the solid can be washed out. Generally, in order to clean lithium ions in solids, a minimum of two water wash steps are used. In some embodiments, the multistage countercurrent water wash comprises two or more stages of countercurrent water wash steps.
In the countercurrent leaching procedure, since lithium-containing solid materials such as lithium phosphate, lithium fluoride, lithium carbonate, etc. are not readily soluble in water, an acidic solution is usually added for adequate leaching, and thus the PH during the leaching reaction is usually less than 6, preferably less than 5. Specifically, in some embodiments, the more acidic the lithium-containing solid feedstock contains lithium phosphate, the more favorable the leaching of lithium ions, but for proper use of the acid, the PH is typically controlled to about 3; in other embodiments, where the lithium-containing solid feedstock is lithium fluoride, the pH is generally not less than 3 and is typically in the range of 4 to 5, because leaching lithium ions from the lithium fluoride solids produces hydrogen fluoride, which is more corrosive.
In the countercurrent leaching procedure, when calcium ions in the calcium-containing acidic solution completely replace lithium ions to form calcium phosphate precipitates, the molar ratio of the required calcium ions to lithium is 1:2, but under acidic conditions, a large proportion of calcium hydrophosphate precipitates occur, and the molar ratio of the calcium ions to the lithium ions is 1:3 under such chemical reactions. In actual production, the dosage of calcium ions is directly related to cost, excessive calcium can cause the increase of subsequent impurity removal cost, insufficient calcium can not sufficiently leach lithium ions, and the recovery rate of lithium is reduced. In practice the molar ratio of calcium ions to lithium ions is from 1:0.1 to 0.3:1, for example from 1:0.1 to 1:1, preferably from 1:0.2 to 1:0.5, preferably from 1:0.3 to 1:0.4.
In the countercurrent leaching process and countercurrent washing process, the temperature is not particularly limited, and 50 to 95 degrees celsius (e.g., 60 to 80 degrees, for example, about 70 degrees) is usually selected for both efficiency and ease of operation, and the corresponding time is 0.3 to 4 hours (e.g., 1 to 3 hours, for example, about 2 hours), and of course, the time required for both processes is reduced with the increase in temperature.
In the present application, the countercurrent leaching procedure and countercurrent washing procedure may include the cases of concurrent leaching and concurrent washing, as long as countercurrent leaching and/or countercurrent washing steps are used as a whole, which are the cases disclosed in the present application. In some countercurrent leaching unit operations, it is possible that one unit operation may not be able to perform the purpose of the leaching reaction in that unit operation, and thus a further leaching step may be performed, i.e. a concurrent leaching step, in which both liquid and solids come from the separated product of the previous stage of leaching, before the unit operation proceeds to the next countercurrent leaching. Similarly, in some unit operations of some countercurrent water washes, it is possible that one unit operation may not be able to accomplish the purpose of the water wash in that unit operation, and thus may be subjected to a further solid-liquid contact, i.e., a concurrent water wash step in which both liquid and solids come from the separated product of the previous water wash, before the unit operation proceeds to the next countercurrent water wash.
In multi-stage countercurrent leaching and multi-stage countercurrent water washing procedures, the leached solids, leached residues, and water washing residues are not limited to being present in solid form, including being present as a slurry and entering another reaction unit as a slurry.
The specific step of countercurrent leaching adopted in the application is not limited, and 2-stage countercurrent leaching can be adopted, or 3-stage or more countercurrent leaching can be adopted, so long as the preset leaching purpose can be achieved, but countercurrent leaching is not suitable for a plurality of stages, the cost of too many stages of countercurrent leaching can be increased, and generally, the multistage countercurrent leaching is not more than 5 stages. In some embodiments, the multi-stage countercurrent leaching comprises a three-stage countercurrent leaching comprising the steps of:
(1) A primary leaching step, wherein the secondary leaching solids are contacted with a primary calcium-containing acidic solution to obtain primary leaching solids, namely leaching slag and primary leaching liquid;
(2) A secondary leaching step, wherein the tertiary leaching solids are contacted with a secondary calcium-containing acidic solution to obtain secondary leaching solids and a secondary leaching liquid;
(3) And a third leaching step, wherein the lithium-containing solid raw material is contacted with a third calcium-containing acidic solution to obtain a third leached solid and a third leaching solution, and the third leaching solution is the solution containing lithium ions.
In some embodiments, the multi-stage counter-current water wash comprises a two-stage counter-current water wash comprising the steps of:
(1) The first-stage countercurrent washing, wherein the second-stage washing slag is contacted with water-containing liquid to obtain first-stage washing slag, namely waste slag and first-stage washing liquid;
(2) And (3) carrying out secondary countercurrent washing, wherein leaching residues are contacted with the primary washing liquid to obtain secondary washing liquid and secondary washing residues.
The primary calcium-containing acidic solution is prepared by adding hydrochloric acid and calcium chloride into the secondary water washing liquid. The secondary calcium-containing acidic solution is prepared from the primary leach solution optionally with the addition of hydrochloric acid and calcium chloride. The tertiary calcium-containing acidic solution is formulated from the secondary leach solution optionally with the addition of hydrochloric acid and optionally calcium chloride. The particular method of preparing the calcium-containing acidic solution is not limited and may be carried out prior to entering the leaching operation or during the leaching operation.
In the application, only a multi-stage countercurrent leaching procedure can be adopted, and countercurrent leaching can extract as much lithium as possible from raw material solids and obtain a solution containing lithium ions with higher concentration; the process of combining multi-stage countercurrent leaching and multi-stage countercurrent washing can also be adopted, and the washing process can enable lithium ions mixed in leaching slag to enter aqueous solution to form aqueous washing solution, namely solution containing a small amount of lithium ions, so that the recovery rate of lithium is improved.
The present application provides a method for preparing lithium carbonate using the above-described lithium ion-containing solution, and thus the method for preparing lithium carbonate of the present application includes the above-described step of preparing a lithium ion-containing solution. In some embodiments, the method of preparing lithium carbonate includes: the lithium-containing solid raw material is obtained by pretreating the lithium-containing recovered raw material before preparing the solution containing lithium ions. For liquid lithium-containing recovery raw materials such as a solution containing lithium chloride, lithium sulfate and the like, the liquid lithium-containing recovery raw materials are firstly converted into solid lithium-containing raw materials through chemical reaction, and the step is mainly used for reducing impurities and improving the recovery purity of lithium, but is not an indispensable step in the process of preparing lithium carbonate; for the solid lithium-containing recovery raw materials, foreign matters such as stones, plastics, fabrics and the like are screened and separated by a steel screen or similar equipment, and the obviously agglomerated raw materials are crushed and then screened so as to avoid blocking a pipeline in the subsequent step, wherein the step is for the smooth proceeding of the subsequent reaction, and in the actual operation, the method can be omitted if no obvious sundries or agglomeration phenomenon exists. Thus, in some embodiments, the lithium-containing solid feedstock is obtained from a pretreatment of a lithium-containing recycle feedstock, the pretreatment comprising at least one of the following steps: (1) When the lithium-containing recovery raw material comprises liquid, enabling trisodium phosphate to react with the liquid, and carrying out solid-liquid separation to obtain the lithium-containing solid raw material; and (2) when the lithium-containing recovery feedstock comprises a solid, the solid is prepared to a suitable particle size, and impurities are removed.
For the liquid lithium-containing recovery raw material, trisodium phosphate is used for precipitating lithium ions to generate lithium phosphate precipitation, if the reaction is completed, the molar ratio of trisodium phosphate to lithium ions is 1:3, and in actual practice, in order to completely precipitate lithium ions, excessive trisodium phosphate is often added, but is usually 0.3:1-0.4:1.
Liquid lithium-containing recovery feedstock obtained from the market generally has a lithium content of less than 20g/L and solid lithium-containing recovery feedstock generally has a lithium content (natural basis) of less than 20%.
In the application, the method for preparing lithium carbonate by using the solution containing lithium ions comprises a step of removing impurities, namely removing calcium, iron, magnesium, copper, aluminum and other ions in the calcium-containing acidic solution, wherein sodium hydroxide and sodium carbonate are added, the solution is made to reach higher alkalinity, usually more than 10, the ions of iron, magnesium, copper, aluminum and the like form a precipitate under the action of hydroxide radicals, and the calcium ions and the carbonate radicals form calcium carbonate precipitates. Since carbonate and lithium also undergo a precipitation reaction, the amount of carbonate is controlled. If carbonate reacts completely with calcium to form calcium carbonate, the molar ratio is 1:1, and considering that carbonate will react with water to form calcium bicarbonate and hydroxide, a small excess of carbonate is allowed, typically the molar ratio of the soda ash to the calcium in the purified lithium ion-containing solution is from 0.8:1 to 1.2:1, e.g., from 1.0:1 to 1.1:1. In the impurity removal step, since sodium carbonate is added, lithium carbonate precipitation is inevitably generated and enters impurity removal slag, and in order to further recover lithium ions, the impurity removal slag can be returned to the multistage countercurrent leaching step, but the step is not a necessary step for preparing lithium carbonate in order to improve the recovery rate of lithium.
In some embodiments, the method for preparing lithium carbonate comprises a lithium precipitation step, wherein the lithium precipitation step is that the solution containing lithium ions after impurity removal is reacted with a saturated solution of sodium carbonate, and liquid-solid separation is carried out, so as to obtain lithium carbonate solid and mother liquor. In general, for the purpose of sufficient reaction, the molar ratio of the sodium carbonate to lithium in the lithium ion-containing solution is 0.3:1 to 0.8:1, for example, 0.5:1 to 0.55:1, and in practice, the amount of sodium carbonate may be increased.
In the lithium precipitation step, lithium ions enter the mother liquor because no lithium precipitation reaction occurs, so that lithium can be further recovered from the mother liquor, namely, the mother liquor reacts with trisodium phosphate, liquid-solid separation is carried out to obtain lithium phosphate sludge, and the lithium phosphate sludge is returned to the pretreatment step to be recovered as a lithium-containing recovery raw material. This step of recovering the mother liquor is also for improving the recovery rate of lithium, and is not an essential step for producing lithium carbonate.
The application also includes a multistage countercurrent solid-liquid contacting apparatus comprising N solid-liquid contacting units, wherein the ith solid-liquid contacting unit comprises: contacting means (3), separating means (6),
Wherein the contact device (3) is provided with a contact device feed port (12) and a contact device discharge port (5), the separation device is provided with a separation device feed port (11), a separation device liquid discharge port (9) and a separation device solid discharge port (13),
The discharge port (5) of the contact equipment is connected with the feed port (11) of the separation equipment,
Wherein, for the ith stage of solid-liquid contact unit,
When N > i >1 (i, N are integers, and N is an integer greater than or equal to 3, for example an integer greater than or equal to 4, for example an integer greater than or equal to 5, for example an integer greater than or equal to 6, for example an integer greater than or equal to 7, for example an integer greater than or equal to 8), the contacting device feed inlet (12) is connected to the separating device liquid discharge port of the i-1 th solid-liquid contacting unit and the separating device solid discharge port of the i+1 th solid-liquid contacting unit;
When i=1, the contact device feed port (12) is connected with the separation device solid discharge port of the (i+1) th solid-liquid contact unit and with an external liquid feed port;
when i=n, the contact device feed port is connected with the separation device liquid discharge port of the i-1 th solid-liquid contact unit and with the external solid feed device, and the separation device liquid discharge port is connected with the external liquid treatment device.
In some embodiments, for the j-th stage solid-liquid contact unit, where j > 1, the solid-liquid contact unit further comprises a solid treatment device (8), and the separation device solid discharge port is connected to the solid treatment device (8);
the solid treatment equipment (8) is provided with a stirring equipment (7);
the solid treatment device (8) is provided with a solid treatment device discharge port (10);
the discharge port (10) of the solid treatment device is connected with the feed port of the contact device of the solid-liquid contact unit of the upper stage (i.e. the j-1 stage).
The solid treatment device (8) is intended to facilitate the transfer to the next solid-liquid contacting unit by further processing of the solids produced by the separation device, and is not an essential feature of a multistage countercurrent contacting device. The solids processing apparatus may be a slurrying tank.
The specific type of the separation apparatus is not limited as long as solid-liquid separation can be solved. In some embodiments, the separation device is a filter press;
in some embodiments, the filter press is at least one selected from the group consisting of: plate and frame filter press, chamber filter press, vertical filter press, and belt filter press.
The specific type of the contacting apparatus (3) is not limited as long as the purpose of solid-liquid contact can be achieved, and it may be various reactors such as a tubular reactor, a tank reactor, etc.
The numerical ranges recited herein can be used alone or in combination.
Examples
Example 1
The embodiment firstly provides a multistage countercurrent solid-liquid contact device, which comprises more than two solid-liquid contact units, wherein the embodiment adopts 5 solid-liquid contact units, and the structure of each solid-liquid contact unit is shown in fig. 1. Wherein each solid-liquid contact unit mainly comprises a reaction kettle (3) (i.e. contact equipment) and a plate-and-frame filter press (6) (i.e. separation equipment);
The reaction kettle (3) is provided with a stirrer (4), the reaction kettle (3) is provided with a reaction kettle feed inlet (12) and a reaction kettle discharge outlet (5), the plate-and-frame filter press (6) is provided with a plate-and-frame filter press feed inlet (11), a plate-and-frame filter press liquid discharge outlet (9) and a plate-and-frame filter press solid discharge outlet (13), and the reaction kettle discharge outlet (5) is connected with the plate-and-frame filter press feed inlet (11) through a pipeline;
For the 2-5-level solid-liquid contact unit, a solid discharge port (13) of the plate-and-frame filter press is connected with a slurrying kettle (8) (namely solid treatment equipment), the slurrying kettle (8) is provided with a stirrer (7), and the slurrying kettle is provided with a discharge port (10).
For the second to fourth-stage solid-liquid contact units, the feed inlet (12) of the reaction kettle is connected with the liquid discharge port of the plate-and-frame filter press of the upper-stage solid-liquid contact unit and is connected with the solid discharge port of the plate-and-frame filter press of the lower-stage solid-liquid contact unit,
For the first-stage solid-liquid contact unit, a feed inlet (12) of the reaction kettle is connected with a solid discharge port of a plate-and-frame filter press of the second-stage solid-liquid contact unit and is connected with a discharge port of external liquid feed equipment;
For the fifth-stage solid-liquid contact unit, the feeding hole (12) of the reaction kettle is connected with the liquid discharging hole of the plate-and-frame filter press of the fourth-stage solid-liquid contact unit and is connected with external solid feeding equipment, and the liquid discharging hole of the plate-and-frame filter press is connected with external liquid treatment equipment for further producing lithium carbonate. Reference numerals (1) and (2) in fig. 1 are a solid supply pipe and a liquid supply pipe, respectively.
The present example provides a process for preparing lithium carbonate from a lithium-containing recovery feedstock comprising liquid by means of a multistage countercurrent solid-liquid contacting apparatus by:
1. pretreatment: introducing a low-concentration lithium-containing solution (namely a liquid lithium-containing recovery raw material with the lithium content of about 8 g/L) into a reaction kettle, adding trisodium phosphate according to the molar ratio of trisodium phosphate to lithium ions in the solution of 0.35:1, reacting at the reaction temperature of 70 ℃ for 2 hours, and filtering to obtain a lithium-containing solid raw material;
the reaction equation: PO 4 3-+3Li+＝Li3PO4 ∈
2. Preparation of lithium ion-containing solutions (three stage countercurrent leaching, two stage countercurrent washing procedure)
In this embodiment, the preparation of the solution containing lithium ions is mainly completed through a three-stage countercurrent leaching step and a two-stage countercurrent washing step, and the two steps, namely, the three-stage countercurrent leaching and the two-stage countercurrent washing procedures, are completed by adopting different solid-liquid contact units of one solid-liquid contact device, as shown in fig. 2, and the method is simple to operate and high in efficiency, and the embodiment is implemented in this way.
(1) Three stage countercurrent leaching
In the first to third stage leaching process, a countercurrent leaching operation is employed, the reaction equation of which is as follows.
The reaction equation: 3CaCl 2+2Li3PO4＝6LiCL+Ca3(PO4)2 ∈
CaCl2+HCl+Li3PO4＝3LiCL+CaHPO4↓
① Primary countercurrent leaching operation
The primary calcium-containing acidic solution is prepared from a secondary water washing solution, calcium chloride and hydrochloric acid, wherein the addition amount of the hydrochloric acid is used for keeping the pH value of the solution to be lower than 4, and the addition amount of the calcium chloride is used for enabling the molar ratio of the calcium to the lithium in the secondary leached solid to be 0.35:1. Leaching the secondary leaching solid and the primary calcium-containing acid solution in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture through a plate-and-frame filter press to obtain a primary leaching liquid and leaching residues; the primary leaching liquid enters a reaction kettle of the secondary leaching unit through a pipeline, leaching slag enters a slurrying kettle, becomes slurry under the action of a stirrer in the slurrying kettle, and enters a secondary water washing device under the action of a pump.
② Two stage countercurrent leaching operation
The secondary calcium-containing acid solution is prepared from primary leaching solution, calcium chloride and hydrochloric acid, wherein the addition amount of the hydrochloric acid is used for keeping the pH value of the solution to be lower than 4, and the addition amount of the calcium chloride is used for enabling the molar ratio of calcium in the secondary calcium-containing acid solution to lithium in the tertiary leaching solid to be 0.35:1. Leaching the three-stage leached solids and the two-stage calcium-containing acid solution in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture through a plate-and-frame filter press to obtain two-stage leached liquid and two-stage leached solids; the secondary leaching liquid enters a reaction kettle of the third leaching step through a pipeline, and the secondary leaching solid enters a slurrying kettle, becomes slurry under the action of a stirrer in the slurrying kettle and is pumped into the reaction kettle of the first leaching unit.
③ Three stage countercurrent leaching operation
The three-stage calcium-containing acidic solution is prepared from a second-stage leaching solution, calcium chloride and hydrochloric acid, wherein the addition amount of the hydrochloric acid is used for keeping the pH value of the solution to be lower than 4, and the addition amount of the calcium chloride is used for enabling the molar ratio of calcium in the three-stage calcium-containing acidic solution to lithium in the lithium-containing solid raw material to be 0.35:1. Leaching a lithium-containing solid raw material and a three-stage calcium-containing acidic solution in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture through a plate-and-frame filter press to obtain a three-stage leaching solution, namely a solution containing lithium ions and three-stage leaching solids, wherein the three-stage leaching solids enter a slurrying kettle, become slurry under the action of the slurrying kettle, and are pumped into the reaction kettle of a two-stage leaching unit.
(2) Two-stage countercurrent water washing
① Primary countercurrent water washing operation
The second-level washing slag is contacted with water, washing is carried out in a reaction kettle, after washing is carried out for 2 hours at 70 ℃, the solid-liquid mixture is separated through a plate-and-frame filter press, and the first-level washing slag, namely waste slag and first-level washing liquid, is obtained, the waste slag can be directly discarded after the environment protection standard is confirmed, and the first-level washing liquid enters the reaction kettle of the second-level countercurrent washing unit through a pipeline. The lithium content in the waste slag obtained in this step is less than 0.5%.
② Two-stage countercurrent water washing operation
The leaching slag obtained by three-stage countercurrent leaching is contacted with primary water washing liquid, after water washing is carried out for 2 hours at 70 ℃, a solid-liquid mixture is separated through a plate-and-frame filter press to obtain secondary water washing liquid and secondary water washing slag, the secondary water washing liquid is used for the primary countercurrent leaching step, and the secondary water washing slag enters a slurrying kettle and is pumped into a reaction kettle of a primary countercurrent water washing unit.
3. Removing impurities: adding a solution containing lithium ions into a reaction kettle, adding sodium hydroxide to adjust the pH to be in a range of 11-12, adding sodium carbonate according to a molar ratio of 1.05:1 of sodium carbonate to calcium in the solution containing lithium ions, reacting for 2 hours, filtering to obtain filtrate, namely the solution containing lithium ions after impurity removal, entering a step 4, and allowing filter residues (namely impurity removal residues) to enter a step 2 for continuous use;
Impurity removal reaction equation:
Fe3++3OH-＝Fe(OH)3↓
Ni2++2OH-＝Ni(OH)2↓
Mg2++2OH-＝Mg(OH)2↓
Cu2++2OH-＝Cu(OH)2↓
Al3++3OH-＝Al(OH)3↓
Ca2++CO3 2-＝CaCO3↓
4. Precipitating lithium: adding sodium carbonate saturated solution into the solution containing lithium ions after impurity removal according to the molar ratio of sodium carbonate to lithium of 0.53:1 for precipitating lithium, controlling the temperature at 60 ℃, reacting for 2 hours, and obtaining a lithium carbonate product after liquid-solid separation, wherein mother liquor enters step 5.
Lithium precipitation reaction equation: 2LiCl+Na 2CO3＝Li2CO3 ∈
5. And (3) recycling: transferring the mother solution generated in the step 4 into a reaction kettle, adding trisodium phosphate according to the mole ratio of trisodium phosphate to lithium ions in the solution of 0.35:1, reacting for 2 hours at the temperature of 70 ℃, separating liquid from solid to obtain lithium phosphate sludge, returning the lithium phosphate sludge to the step2 for continuous use, and discharging the wastewater after treatment. In this step, the lithium content of the wastewater is less than 0.2g/l.
Recovery step reaction equation: PO 4 3-+3Li+＝Li3PO4 ∈
Comprehensive calculation shows that the lithium content in the wastewater and the lithium content in the waste slag are lower than 6% of the lithium content in the liquid-containing lithium recovery raw material, namely, the recovery rate of lithium reaches more than 94%. The method is particularly suitable for the situation that the content of lithium in the liquid recovery raw material is in the range of 0.5g/l to 10g/l, if the content of lithium is smaller than 0.5g/l, the recovery cost is too high, and if the content of lithium is larger than 10g/l, sodium carbonate can be added for precipitating lithium to improve the efficiency, crude lithium carbonate and the recovery raw material containing lithium with the content of lithium in the range of 0.5g/l to 10g/l can be obtained, and then the method of the embodiment is adopted for preparing the lithium carbonate.
Example 2
In this example, the same apparatus and method as in example 1 was used, except that: this example uses a solid recovery feedstock containing lithium phosphate, the natural radical lithium content of which is about 8%, to produce lithium carbonate. The specific implementation is as follows:
1. Pretreatment: the raw materials are solid recovery raw materials containing lithium phosphate, the raw materials are screened by a 20-mesh steel screen, foreign matters such as stones, plastics, fabrics and the like are removed, and the agglomerated raw materials are crushed and then are screened by the screen. The screened foreign matters are treated as solid waste, and the screened raw materials enter step 2.
2. Preparation of lithium ion-containing solutions
The preparation of the lithium ion-containing solution was carried out in the same manner as the method and operation of the lithium ion-containing solution of example 1, i.e., mainly by a three-stage countercurrent leaching, a two-stage countercurrent washing procedure, as shown in fig. 2.
(1) Three-stage countercurrent leaching:
in the first to third stage leaching process, a countercurrent leaching operation is employed, the reaction equation of which is as follows.
The reaction equation: 3CaCl 2+2Li3PO4＝6LiCL+Ca3(PO4)2 ∈
CaCl2+HCl+Li3PO4＝3LiCL+CaHPO4↓
① Primary countercurrent leaching operation
Leaching the secondary leached solid and a primary calcium-containing acidic solution (which is prepared from a secondary water washing liquid, calcium chloride and hydrochloric acid, wherein the addition amount of the hydrochloric acid is such that the pH value of the solution is kept below 4, and the addition amount of the calcium chloride is such that the molar ratio of the calcium to lithium in the secondary leached solid is 0.35:1.) in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture by a plate-and-frame filter press to obtain a primary leaching liquid and leaching residues; the primary leaching liquid enters a reaction kettle of the secondary leaching unit through a pipeline, leaching slag enters a slurrying kettle, becomes slurry under the action of a stirrer in the slurrying kettle, and enters a secondary water washing device under the action of a pump.
② Two stage countercurrent leaching operation
Leaching the three-stage leached solid and a two-stage calcium-containing acid solution (which is prepared from a first-stage leaching solution, calcium chloride and hydrochloric acid, wherein the addition amount of the hydrochloric acid is such that the pH value of the solution is kept below 4, and the addition amount of the calcium chloride is such that the molar ratio of the calcium in the two-stage calcium-containing acid solution to the lithium in the three-stage leached solid is 0.35:1.) in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture by a plate-and-frame filter press to obtain a two-stage leaching solution and a two-stage leached solid; the secondary leaching liquid enters a reaction kettle of the third leaching step through a pipeline, and the secondary leaching solid enters a slurrying kettle, becomes slurry under the action of a stirrer in the slurrying kettle and is pumped into the reaction kettle of the first leaching unit.
③ Three stage countercurrent leaching operation
Leaching the lithium-containing solid raw material obtained in pretreatment and a three-stage calcium-containing acidic solution (which is prepared from a secondary leaching solution, calcium chloride and hydrochloric acid), wherein the addition amount of the hydrochloric acid is such that the pH value of the solution is kept below 4, the addition amount of the calcium chloride is such that the molar ratio of calcium in the three-stage calcium-containing acidic solution to lithium in the lithium-containing solid raw material is 0.35:1.) in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture through a plate-and-frame filter press to obtain a three-stage leaching solution, namely a solution containing lithium ions and three-stage leaching solids, wherein the three-stage leaching solids enter a slurrying kettle, become slurry under the action of the slurrying kettle and are pumped into the reaction kettle of a secondary leaching unit. The lithium content in the waste slag obtained in this step is less than 0.5%.
(2) Two-stage countercurrent water washing
① Primary countercurrent water washing operation
The second-level washing slag is contacted with water-containing liquid, water washing is carried out in a reaction kettle, after water washing is carried out at 70 ℃ for 2 hours, the solid-liquid mixture is separated through a plate-and-frame filter press, so that first-level washing slag, namely waste slag and first-level washing liquid, is obtained, the waste slag can be directly discarded after the environment protection standard is confirmed, and the first-level washing liquid enters the water washing kettle of the second-level countercurrent washing unit through a pipeline.
② Two-stage countercurrent water washing operation
The leaching slag obtained by three-stage countercurrent leaching is contacted with primary washing liquid, after washing for 2 hours at 70 ℃, the solid-liquid mixture is separated by a plate-and-frame filter press to obtain secondary washing liquid and secondary washing slag, the secondary washing liquid is used for the primary countercurrent leaching step, and the secondary washing slag enters a slurrying kettle and is pumped into a washing kettle of a primary countercurrent washing unit.
3. Removing impurities: adding a solution containing lithium ions into a reaction kettle, adding sodium hydroxide to adjust the pH to be in a range of 11-12, adding sodium carbonate according to a molar ratio of 1.05:1 of sodium carbonate to calcium in the solution containing lithium ions, reacting for 2 hours, filtering to obtain filtrate, namely the solution containing lithium ions after impurity removal, entering a step 4, and allowing filter residues (impurity removal residues) to enter a step 2 for continuous use;
Impurity removal reaction equation:
Fe3++3OH-＝Fe(OH)3↓
Ni2++2OH-＝Ni(OH)2↓
Mg2++2OH-＝Mg(OH)2↓
Cu2++2OH-＝Cu(OH)2↓
Al3++3OH-＝Al(OH)3↓
Ca2++CO3 2-＝CaCO3↓
4. Precipitating lithium: adding sodium carbonate saturated solution into the solution containing lithium ions after impurity removal according to the molar ratio of sodium carbonate to lithium of 0.53:1 for precipitating lithium, controlling the temperature at 60 ℃, reacting for 2 hours, and obtaining a lithium carbonate product after liquid-solid separation, wherein mother liquor enters step 5.
Lithium precipitation reaction equation: 2LiCl+Na 2CO3＝Li2CO3 ∈
5. And (3) recycling: transferring the mother solution generated in the step 4 into a reaction kettle, adding trisodium phosphate according to the mole ratio of trisodium phosphate to lithium ions in the solution of 0.35:1, reacting for 2 hours at the temperature of 70 ℃, separating liquid from solid to obtain lithium phosphate sludge, returning the lithium phosphate sludge to the step 2 for continuous use, and discharging the wastewater after treatment. In this step, the lithium content in the wastewater is less than 0.2g/L.
Recovery step reaction equation: PO 4 3-+3Li+＝Li3PO4 ∈
And comprehensively calculating that the lithium content in the wastewater and the lithium content in the waste slag are lower than 6% of the lithium content in the solid lithium phosphate recovery raw material, namely, the recovery rate of lithium reaches over 94%.
Example 3
In this example, the same apparatus and method as in example 2 was used, except that: this example uses a solid recovery feedstock containing lithium fluoride, the natural radical lithium content of which is about 11%, to produce lithium carbonate. The specific implementation is as follows:
1. Pretreatment: the raw materials are solid recovery raw materials containing lithium fluoride, the raw materials are screened by a 20-mesh steel screen, foreign matters such as stones, plastics, fabrics and the like are removed, and the agglomerated raw materials are crushed and then are screened by the screen. The screened foreign matters are treated as solid waste, and the screened raw materials enter step 2.
2. Preparation of lithium ion-containing solutions
The preparation of the lithium ion-containing solution was carried out in the same manner as the method and operation of the lithium ion-containing solution of example 1, mainly by a three-stage countercurrent leaching, two-stage countercurrent washing procedure, as shown in fig. 2. (1) three-stage countercurrent leaching:
in the first to third stage leaching process, a countercurrent leaching operation is employed, the reaction equation of which is as follows.
The reaction equation: caCl 2+2LiF＝2LiCl+CaF2 ∈
① Primary countercurrent leaching operation
Leaching the secondary leached solid and the primary calcium-containing acid solution (which is prepared from a secondary water washing liquid, calcium chloride and hydrochloric acid, wherein the addition amount of the hydrochloric acid is that the pH value of the solution is kept to be 4-5, and the addition amount of the calcium chloride is that the molar ratio of the calcium in the secondary calcium-containing acid solution to the lithium in the tertiary leached solid is 0.53:1.) in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture through a plate-and-frame filter press to obtain a primary leaching liquid and leaching residues; the primary leaching liquid enters a reaction kettle of the secondary leaching unit through a pipeline, leaching slag enters a slurrying kettle, becomes slurry under the action of a stirrer in the slurrying kettle, and enters a secondary water washing device under the action of a pump.
② Two stage countercurrent leaching operation
Leaching the three-stage leached solid and a two-stage calcium-containing acid solution (which is prepared from a first-stage leaching solution, calcium chloride and hydrochloric acid, wherein the addition amount of the hydrochloric acid is used for keeping the pH value of the solution to be 4-5, and the addition amount of the calcium chloride is used for keeping the molar ratio of the calcium in the two-stage calcium-containing acid solution to the lithium in the three-stage leached solid to be 0.53:1.) in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture through a plate-and-frame filter press to obtain a two-stage leaching solution and a two-stage leached solid; the secondary leaching liquid enters a reaction kettle of the three-stage leaching unit through a pipeline, the secondary leaching solid enters a slurrying kettle, becomes slurry under the action of a stirrer in the slurrying kettle, and is pumped into the reaction kettle of the first-stage leaching unit.
③ Three stage countercurrent leaching operation
Leaching the lithium-containing solid raw material obtained in pretreatment and a three-stage calcium-containing acidic solution (which is prepared from a secondary leaching solution, calcium chloride and hydrochloric acid), wherein the addition amount of the hydrochloric acid is such that the pH value of the solution is kept at 4-5, the addition amount of the calcium chloride is such that the molar ratio of calcium in the three-stage calcium-containing acidic solution to lithium in the lithium-containing solid raw material is 0.53:1.) in a reaction kettle, leaching for 2 hours at the temperature of 70 ℃, and separating a solid-liquid mixture through a plate-frame filter press to obtain a three-stage leaching solution, namely a solution containing lithium ions and three-stage leaching solids, wherein the three-stage leaching solids enter a slurrying kettle, become slurry under the action of the slurrying kettle and are pumped into the reaction kettle of a secondary leaching unit.
(2) Two-stage countercurrent water washing
① Primary countercurrent water washing operation
The second-level washing slag is contacted with water-containing liquid, water washing is carried out in a reaction kettle, after water washing is carried out at 70 ℃ for 2 hours, the solid-liquid mixture is separated through a plate-and-frame filter press, so that first-level washing slag, namely waste slag and first-level washing liquid, is obtained, the waste slag can be directly discarded after the environment protection standard is confirmed, and the first-level washing liquid enters the water washing kettle of the second-level countercurrent washing unit through a pipeline. The lithium content in the waste slag obtained in this step is less than 0.5%.
② Two-stage countercurrent water washing operation
The leaching slag obtained by three-stage countercurrent leaching is contacted with primary washing liquid, after washing for 2 hours at 70 ℃, the solid-liquid mixture is separated by a plate-and-frame filter press to obtain secondary washing liquid and secondary washing slag, the secondary washing liquid is used for the primary countercurrent leaching step, and the secondary washing slag enters a slurrying kettle and is pumped into a washing kettle of a primary countercurrent washing unit.
3. Removing impurities: adding a solution containing lithium ions into a reaction kettle, adding sodium hydroxide to adjust the pH to be in a range of 11-12, adding sodium carbonate according to a molar ratio of 1.05:1 of sodium carbonate to calcium in the solution containing lithium ions, reacting for 2 hours, filtering to obtain filtrate, namely the solution containing lithium ions after impurity removal, entering a step 4, and allowing filter residues (impurity removal residues) to enter a step 2 for continuous use;
Impurity removal reaction equation:
Fe3++3OH-＝Fe(OH)3↓
Ni2++2OH-＝Ni(OH)2↓
Mg2++2OH-＝Mg(OH)2↓
Cu2++2OH-＝Cu(OH)2↓
Al3++3OH-＝Al(OH)3↓
Ca2++CO3 2-＝CaCO3↓
4. Precipitating lithium: adding sodium carbonate saturated solution into the solution containing lithium ions after impurity removal according to the molar ratio of sodium carbonate to lithium of 0.53:1 for precipitating lithium, controlling the temperature at 60 ℃, reacting for 2 hours, and obtaining a lithium carbonate product after liquid-solid separation, wherein mother liquor enters step 5.
Lithium precipitation reaction equation: 2LiCl+Na 2CO3＝Li2CO3 ∈
5. And (3) recycling: transferring the mother solution generated in the step 4 into a reaction kettle, adding trisodium phosphate according to the mole ratio of trisodium phosphate to lithium ions in the solution of 0.35:1, reacting for 2 hours at the temperature of 70 ℃, separating liquid from solid to obtain lithium phosphate sludge, returning the lithium phosphate sludge to the step 2 for continuous use, and discharging the wastewater after treatment. In this step, the lithium content in the wastewater is less than 0.2g/L.
Recovery step reaction equation: PO 4 3-+3Li+＝Li3PO4 ∈
And comprehensively calculating that the lithium content in the wastewater and the lithium content in the waste slag are lower than 6% of the lithium content in the solid lithium fluoride recovery raw material, namely, the recovery rate of lithium reaches over 94%.
The foregoing is merely exemplary embodiments of the present disclosure and is not intended to limit the scope of the disclosure, which is defined by the appended claims.
Claims (32)
1. A method of preparing a solution containing lithium ions, comprising:
Carrying out multistage countercurrent leaching on a lithium-containing solid raw material by adopting a calcium-containing acidic solution to obtain a solution containing lithium ions and leaching residues, wherein the molar ratio of calcium in the calcium-containing acidic solution to lithium in the lithium-containing solid raw material is 1:0.3 to 1:0.5, the pH value of the calcium-containing acidic solution is 3 or more and less than 4, the multistage countercurrent leaching comprises two or more stages of countercurrent leaching steps, and in the countercurrent operation, the reaction equation is as follows:
3CaCl2+2Li3PO4＝6LiCl+Ca3(PO4)2↓
CaCl2+HCl+Li3PO4＝3LiCl+CaHPO4↓
The multi-stage countercurrent leaching comprises two or more than three stages of countercurrent leaching steps, wherein in each stage of countercurrent leaching step, leached solids are leached by using calcium-containing acid solution, the single-stage reaction time is 0.3-4 hours, and the reaction temperature is 50-95 ℃ to obtain leaching liquid and leaching slag.
2. The method of claim 1, wherein the lithium ion-containing solution is a lithium chloride-containing solution.
3. The method according to claim 1, wherein the calcium-containing acidic solution is a solution containing an acid and calcium ions, the acid comprising hydrochloric acid.
4. The method of claim 1, wherein the lithium-containing solid feedstock comprises lithium phosphate.
5. The method of claim 1, comprising washing the leach residue with water.
6. The method of claim 1, comprising subjecting the leach residue to a multi-stage countercurrent water wash comprising two or more stages of countercurrent water wash.
7. The method of claim 1, wherein the single stage reaction time of the multistage countercurrent leaching is 1-3 hours and the reaction temperature is 60-80 degrees celsius.
8. The method of claim 6, wherein the single stage water wash time of the multistage countercurrent water wash is 0.3 to 4 hours and the temperature is 50 to 95 degrees celsius.
9. The method of claim 6, wherein the single stage water wash time of the multistage countercurrent water wash is 1-3 hours and the temperature is 60-80 degrees celsius.
10. The method of claim 1 or 6, wherein the multi-stage countercurrent leaching comprises a three-stage countercurrent leaching comprising the steps of:
(1) A primary leaching step, wherein the secondary leaching solid is contacted with a primary calcium-containing acidic solution to obtain a primary leaching solid and a primary leaching liquid, and the primary leaching solid is leaching slag;
(2) A secondary leaching step, wherein the tertiary leaching solids are contacted with a secondary calcium-containing acidic solution to obtain secondary leaching solids and a secondary leaching liquid;
(3) And a third leaching step, wherein the lithium-containing solid raw material is contacted with a third calcium-containing acidic solution to obtain a third leached solid and a third leaching solution, and the third leaching solution is the solution containing lithium ions.
11. The method of claim 10, wherein the multi-stage counter-current water wash comprises a two-stage counter-current water wash comprising the steps of:
(1) The first-stage countercurrent washing, wherein the second-stage washing slag is contacted with water-containing liquid to obtain first-stage washing slag, namely waste slag and first-stage washing liquid;
(2) And (3) carrying out secondary countercurrent washing, wherein the leaching slag is contacted with the primary washing liquid to obtain secondary washing liquid and secondary washing slag.
12. The method according to claim 11, wherein the primary calcium-containing acidic solution is formulated from the secondary aqueous wash with the addition of hydrochloric acid and calcium chloride, the secondary calcium-containing acidic solution is formulated from the primary leach solution optionally with the addition of hydrochloric acid and calcium chloride, and the tertiary calcium-containing acidic solution is formulated from the secondary leach solution optionally with the addition of hydrochloric acid and calcium chloride.
13. A process for preparing lithium carbonate, which comprises preparing a solution containing lithium ions by the process according to any one of claims 1 to 12.
14. The method of preparing lithium carbonate according to claim 13, wherein the lithium-containing solid feedstock is obtained from a pretreatment of a lithium-containing recycle feedstock, the pretreatment comprising at least one of the following steps:
(1) When the lithium-containing recovery raw material comprises liquid, enabling trisodium phosphate to react with the liquid, and carrying out solid-liquid separation to obtain the lithium-containing solid raw material; and
(2) When the lithium-containing recovery raw material contains a solid, the solid is prepared into a proper particle size, and impurities are removed.
15. The method of preparing lithium carbonate of claim 14, wherein the molar ratio of trisodium phosphate to lithium in the lithium-containing recycle feedstock is 0.3:1 to 0.4:1.
16. The method for preparing lithium carbonate according to claim 14, wherein the method comprises adjusting the pH value of the solution containing lithium ions to 10 or more with a base, adding soda ash, and performing liquid-solid separation to obtain the solution containing lithium ions after impurity removal and impurity removal slag.
17. The method for preparing lithium carbonate according to claim 14, wherein the method comprises adjusting the pH value of the solution containing lithium ions to 11 or more with a base, adding soda ash, and performing liquid-solid separation to obtain the solution containing lithium ions and the impurity-removed slag.
18. The method of preparing lithium carbonate of claim 16, wherein the molar ratio of the sodium carbonate to the calcium in the purified lithium ion-containing solution is from 0.8:1 to 1.2:1.
19. The method of preparing lithium carbonate of claim 16, wherein the molar ratio of the sodium carbonate to the calcium in the purified lithium ion-containing solution is 1.0:1 to 1.1:1.
20. The method for producing lithium carbonate according to claim 16, wherein the impurity-removed slag is used as the lithium-containing solid raw material.
21. The method for preparing lithium carbonate according to claim 16, comprising reacting the solution containing lithium ions after the impurity removal with a saturated solution of soda ash, and performing liquid-solid separation to obtain lithium carbonate solid and mother liquor.
22. The method of preparing lithium carbonate according to claim 21, wherein the amount of the sodium carbonate is such that the molar ratio of the sodium carbonate to lithium in the solution containing lithium ions is 0.3:1 to 0.8:1.
23. The method of preparing lithium carbonate according to claim 22, wherein the amount of the sodium carbonate is such that the molar ratio of the sodium carbonate to lithium in the solution containing lithium ions is 0.5:1 to 0.55:1.
24. The method for preparing lithium carbonate according to claim 21, comprising reacting the mother liquor with trisodium phosphate and performing liquid-solid separation to obtain lithium phosphate sludge.
25. The method of producing lithium carbonate according to claim 24, comprising returning the lithium phosphate sludge to the pretreatment step as a lithium-containing recovery raw material.
26. A method of preparing a solution containing lithium ions according to claim 1, wherein the multistage countercurrent leaching step is accomplished with a multistage countercurrent solid-liquid contacting apparatus comprising N solid-liquid contacting units, wherein the ith solid-liquid contacting unit comprises: contacting means (3), separating means (6),
Wherein the contact device (3) is provided with a contact device feed port (12) and a contact device discharge port (5), the separation device is provided with a separation device feed port (11), a separation device liquid discharge port (9) and a separation device solid discharge port (13),
The discharge port (5) of the contact equipment is connected with the feed port (11) of the separation equipment,
Wherein, for the ith solid-liquid contact unit,
When N is more than i and is more than 1, i and N are integers, N is an integer greater than or equal to 3, and the contact equipment feed inlet (12) is connected with the separation equipment liquid discharge port of the i-1 solid-liquid contact unit and is connected with the separation equipment solid discharge port of the i+1 solid-liquid contact unit;
When i=1, the contact device feed port (12) is connected with the separation device solid discharge port of the (i+1) th solid-liquid contact unit and with an external liquid feed device;
when i=n, the contact device feed port is connected to the separation device liquid discharge port of the i-1 th solid-liquid contact unit and to an external solid feed device.
27. A method for preparing a solution containing lithium ions according to claim 26, characterized in that the contacting device (3) is provided with a stirring device (4).
28. A method for preparing a solution containing lithium ions according to claim 26, characterized in that for a j-th solid-liquid contacting unit, where j >1, the solid-liquid contacting unit further comprises a solids handling device (8), the separation device solids outlet (13) being connected to the solids handling device (8);
the solid treatment equipment (8) is provided with a stirring equipment (7);
the solid treatment device (8) is provided with a solid treatment device discharge port (10);
the discharge port (10) of the solid treatment device is connected with the feed port of the contact device of the solid-liquid contact unit of the upper stage, namely the j-1 stage.
29. A method of preparing a solution containing lithium ions according to claim 26, wherein the separation device is a filter press.
30. The method of claim 29, wherein the filter press is a plate and frame filter press.
31. A method for preparing a solution containing lithium ions according to claim 26, characterized in that the contacting means (3) is a reaction vessel.
32. The method of claim 27, wherein the solid handling device is a slurrying tank.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189389A (en) * | 1997-01-26 | 1998-08-05 | 杨时英 | Multi-stage counterflow leaching process |
| JP2011168461A (en) * | 2010-02-22 | 2011-09-01 | Eco-System Recycling Co Ltd | Method for producing high-concentration lithium liquid from lithium-containing liquid and method for producing lithium carbonate |
| CN103168107A (en) * | 2010-10-12 | 2013-06-19 | Ls-日光铜制炼株式会社 | Method for recovering valuable metals from lithium secondary battery wastes |
| CN208493380U (en) * | 2018-05-17 | 2019-02-15 | 江西迈特循环科技有限公司 | A kind of multistage countercurrent solid-liquid contact arrangement |
-
2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189389A (en) * | 1997-01-26 | 1998-08-05 | 杨时英 | Multi-stage counterflow leaching process |
| JP2011168461A (en) * | 2010-02-22 | 2011-09-01 | Eco-System Recycling Co Ltd | Method for producing high-concentration lithium liquid from lithium-containing liquid and method for producing lithium carbonate |
| CN103168107A (en) * | 2010-10-12 | 2013-06-19 | Ls-日光铜制炼株式会社 | Method for recovering valuable metals from lithium secondary battery wastes |
| CN208493380U (en) * | 2018-05-17 | 2019-02-15 | 江西迈特循环科技有限公司 | A kind of multistage countercurrent solid-liquid contact arrangement |
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