CN118223041A - Method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder - Google Patents
Method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 67
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 63
- 239000000843 powder Substances 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 title claims abstract description 50
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 title claims abstract description 50
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 171
- 239000012528 membrane Substances 0.000 claims abstract description 60
- 238000002386 leaching Methods 0.000 claims abstract description 39
- 239000012466 permeate Substances 0.000 claims abstract description 39
- 238000000909 electrodialysis Methods 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 238000001728 nano-filtration Methods 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000012530 fluid Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000012141 concentrate Substances 0.000 claims abstract description 21
- 230000000149 penetrating effect Effects 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 129
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims description 21
- 159000000002 lithium salts Chemical class 0.000 claims description 21
- 239000012266 salt solution Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 238000005341 cation exchange Methods 0.000 claims description 12
- 239000003011 anion exchange membrane Substances 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 11
- 239000007853 buffer solution Substances 0.000 claims description 8
- 239000010413 mother solution Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000001698 pyrogenic effect Effects 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000012527 feed solution Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 Ca 2+ Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 102000015863 Nuclear Factor 90 Proteins Human genes 0.000 description 1
- 108010010424 Nuclear Factor 90 Proteins Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder, which comprises the following steps: mixing lithium iron phosphate waste powder, an oxidant and water, and adding a leaching agent to obtain a leaching solution; introducing leaching liquid into the nanofiltration device to obtain a first permeate and a first concentrate, diluting the first concentrate, introducing the diluted first concentrate into the nanofiltration device to obtain a second permeate and a second concentrate, and mixing the second permeate and the first permeate to obtain a mixed permeate; providing a bipolar membrane electrodialysis device, respectively introducing mixed penetrating fluid and second concentrated solution into a salt chamber, and respectively obtaining a first lithium hydroxide solution and a second lithium hydroxide solution in an alkali chamber after electrodialysis; mixing and filtering the first lithium hydroxide solution and the second lithium hydroxide solution to obtain a lithium hydroxide solution, evaporating, concentrating, crystallizing, centrifuging, drying and crushing the crystallized product to obtain the lithium hydroxide monohydrate. The method solves the problems of high energy consumption and high impurity content of products in the traditional pyrogenic and wet lithium extraction process.
Description
Technical Field
The invention belongs to the technical field of battery waste recovery, and particularly relates to a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder.
Background
With the rapid development of the electric automobile industry, the demand of power batteries is increasing. The lithium iron phosphate serving as a common anode material has the advantages of high safety performance, long cycle life, environmental protection and the like, and is widely applied to the fields of electric automobiles, energy storage and the like. However, as the decommissioning of lithium iron phosphate power cells continues to increase, how to effectively recycle and dispose of these spent cells becomes a technical hotspot in the current industry.
The current recovery of waste lithium iron phosphate batteries is divided into two types, namely a fire method and a wet method. The traditional pyrogenic recovery is generally to burn the electrode slice at high temperature, burn off carbon and organic matters in the electrode slice, and finally screen the residual ash which cannot be burnt off to obtain the fine powdery material containing metal and metal oxide. The method has simple process, but long treatment flow and lower comprehensive recovery rate of valuable metals. The improved fire recovery technology is that the organic binder is removed by calcination, the lithium iron phosphate powder is separated from the aluminum foil sheet, the lithium iron phosphate material is obtained, then a proper amount of raw materials are added into the material to obtain the required molar ratio of lithium, iron and phosphorus, and a high-temperature solid-phase method is used for synthesizing new lithium iron phosphate, so that the method can not realize the selective recovery of valuable metals, has high impurity content and high energy consumption, and is easy to cause secondary pollution to the environment; the wet recovery is mainly realized by leaching metal ions in the lithium iron phosphate battery recovery powder through an acid solution, and then removing impurities, precipitating target ions and the like to recover valuable metal ions, especially lithium ions, of the recovery powder.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing lithium hydroxide monohydrate by using lithium iron phosphate waste powder, which aims to solve the technical problems of high energy consumption, easy secondary pollution to the environment and high impurity content of the prepared product in the prior art by the traditional technology of extracting lithium by a fire method and a wet method.
The invention is realized by the following technical scheme: a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder, the method comprising:
Uniformly mixing lithium iron phosphate waste powder, an oxidant and water according to a preset solid-to-liquid ratio, adding a leaching agent with a preset concentration to adjust the pH value to a preset pH value, heating for a preset time at a preset temperature, and filtering to obtain leaching liquid and filter residues;
Introducing the leaching solution into a nanofiltration device to obtain a first permeate and a first concentrate, diluting the first concentrate, and then introducing the first concentrate into the nanofiltration device again to obtain a second permeate and a second concentrate, wherein the second permeate is mixed with the first permeate to obtain a mixed permeate;
Providing a bipolar membrane electrodialysis device, wherein the bipolar membrane electrodialysis device comprises an anode electrode chamber, an acid chamber, a base chamber, a salt chamber and a cathode electrode chamber, the mixed permeate and the second concentrated solution are respectively introduced into the salt chamber, direct current is introduced to carry out electrodialysis, a first lithium hydroxide solution and a second lithium hydroxide solution are respectively obtained in the base chamber, and a hydrochloric acid solution and a phosphoric acid solution are respectively obtained in the acid chamber;
Mixing the first lithium hydroxide solution and the second lithium hydroxide solution, filtering to obtain a lithium hydroxide solution, evaporating, concentrating, crystallizing and centrifuging the lithium hydroxide solution to obtain a crystallization mother solution and a crystallization product, and drying and crushing the crystallization product to obtain lithium hydroxide monohydrate.
Compared with the prior art, the invention has the beneficial effects that: according to the method for preparing the lithium hydroxide monohydrate from the lithium iron phosphate waste powder, provided by the invention, the nanofiltration device and the bipolar membrane electrodialysis device are adopted to treat the lithium-containing leaching solution of the lithium iron phosphate waste powder, other reagents are not required to be added in the operation after leaching reaction, and a high-purity lithium hydroxide monohydrate product can be obtained under relatively low energy consumption and mild conditions; the method comprises the following steps: performing membrane separation treatment on the lithium-containing leaching solution of the lithium iron phosphate waste powder by a nanofiltration device to obtain a mixed penetrating fluid and a second concentrated solution, and performing electrodialysis treatment on the mixed penetrating fluid and the second concentrated solution by a bipolar membrane electrodialysis device to obtain a lithium hydroxide solution, a hydrochloric acid solution and a phosphoric acid solution, wherein the hydrochloric acid solution can be recycled and used as a leaching agent of the lithium iron phosphate waste powder, thereby being beneficial to recycling and high-efficiency utilization of resources and realizing the aim of low energy consumption of a reaction system; in addition, the bipolar membrane electrodialysis device is internally provided with the anode electrode chamber and the cathode electrode chamber, and buffer solution is filled in the two electrode chambers, so that a certain protection effect is achieved on the electrodes, and long-term stable operation of the device is facilitated.
Optionally, the oxidant comprises any one of hydrogen peroxide and sodium chlorate, and the preset solid-to-liquid ratio is 1g (8-12) mL.
Optionally, the leaching agent is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 5-15mol/L, the preset pH value is 0.1-2, the preset temperature is 60-80 ℃, and the preset time is 0.5-2 h.
Optionally, the operating pressure of the nanofiltration device is controlled between 0.1MPa and 0.5MPa.
Optionally, the permeate water rate of the nanofiltration device is 20% -80%, and the volume ratio of the mixed permeate liquid to the second concentrated liquid is 1 by controlling the permeate water rate of the nanofiltration device: 1.
Optionally, the bipolar membrane electrodialysis device comprises an anode plate, a cathode plate, a bipolar membrane, a cation exchange membrane and an anion exchange membrane, wherein the arrangement mode is that the anode plate, the bipolar membrane, the cation exchange membrane, the anion exchange membrane, the bipolar membrane and the cathode plate are ruthenium iridium coating titanium electrode plates;
The anode plate is matched with the positive surface of the bipolar membrane to form the anode electrode chamber, the negative surface of the bipolar membrane is matched with the cation exchange membrane to form the acid chamber, the cation exchange membrane is matched with the anion exchange membrane to form the salt chamber, the anion exchange membrane is matched with the positive surface of the bipolar membrane to form the alkali chamber, and the negative surface of the bipolar membrane is matched with the cathode plate to form the cathode electrode chamber.
Optionally, the anode electrode chamber and the cathode electrode chamber are filled with buffer solution, the buffer solution is sodium sulfate solution, and the concentration of the sodium sulfate solution is 0.2mol/L-0.5mol/L;
before the mixed penetrating fluid is introduced into the salt chamber, a first lithium salt solution is filled in the salt chamber, the solute of the first lithium salt solution is consistent with that of the mixed penetrating fluid, and the initial concentration of the first lithium salt solution is controlled to be 0.1 mol/L-0.5 mol/L;
before the second concentrated solution is introduced into the salt chamber, a second lithium salt solution is filled in the salt chamber, the solute of the second lithium salt solution is consistent with that of the second concentrated solution, and the initial concentration of the second lithium salt solution is controlled to be 0.1 mol/L-0.5 mol/L.
Optionally, the current density of the electrodialysis is controlled at 10mA/cm 2-50 mA/cm2.
Optionally, after the evaporation concentration process is completed, the volume ratio of the lithium hydroxide solution before and after concentration is (15-20): 1.
Optionally, the crystallization mother liquor is returned to the lithium hydroxide solution obtained by the bipolar membrane electrodialysis device for mixed recycling.
Drawings
FIG. 1 is a process flow diagram of a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder according to the present invention;
FIG. 2 is a process schematic diagram of a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder according to the present invention;
Fig. 3 is a schematic diagram of a bipolar membrane electrodialysis apparatus of the invention in use.
The invention will be further described in the following detailed description in conjunction with the above-described figures.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Several embodiments of the invention are presented in the figures. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "mounted" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only.
Unless defined otherwise, 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 in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1 to 3, a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder according to the present invention is shown, and the method comprises steps S10-S13:
Step S10: mixing lithium iron phosphate waste powder, an oxidant and water uniformly according to a preset solid-to-liquid ratio, adding a leaching agent with a preset concentration, adjusting to a preset pH value, heating at a preset temperature for a preset time, and filtering to obtain leaching liquid and filter residues.
The method comprises the following steps: the preset solid-to-liquid ratio of the mixture obtained by uniformly mixing the lithium iron phosphate waste powder, the oxidant and the water is 1g (8-12) mL.
The oxidant comprises any one of hydrogen peroxide and sodium chlorate, and the purpose of the oxidant is to oxidize leached Fe 2+ ions into Fe 3+ ions, so that Fe (OH) 3 sediment with relatively lower solubility can be generated later. In the experiment, in order to reduce the introduction of impurity elements as much as possible, the oxidant is preferably hydrogen peroxide.
The leaching agent is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 5mol/L-15mol/L, the preset pH value is 0.1-2, the preset temperature is 60-80 ℃, and the preset time is 0.5-2 h. The leaching is carried out by dripping hydrochloric acid solution, and the pH value is regulated to be less than or equal to 2, so as to ensure the leaching effect.
After the leaching reaction is finished, filtering to obtain a leaching solution containing lithium and iron phosphate filter residues, testing the lithium content m 1、m2 in the leaching solution and filter residues, and calculating a lithium leaching rate C according to the lithium content m 1、m2, which is defined as
Step S11: and introducing the leaching solution into a nanofiltration device to obtain a first penetrating fluid and a first concentrated solution, diluting the first concentrated solution, introducing the diluted first concentrated solution into the nanofiltration device again to obtain a second penetrating fluid and a second concentrated solution, and mixing the second penetrating fluid with the first penetrating fluid to obtain a mixed penetrating fluid.
Specific: the NF90 nanofiltration membrane is arranged in the nanofiltration device, the osmotic water yield of the nanofiltration device is controlled to be about 20% -80% in the experimental process, the operating pressure is controlled to be 0.1MPa-0.5MPa, for the membrane element, the larger the pressure is, the larger the osmotic quantity is, but the pressure resistance of the membrane element is limited, and the membrane element can be damaged to influence the service life beyond a certain pressure, so that the rated pressure of the membrane element is not suitable to be exceeded, and the operating pressure is preferably 0.5MPa.
Introducing a lithium-containing leaching solution into a nanofiltration device, separating two lithium salts by utilizing the molecular weight difference of lithium dihydrogen phosphate and lithium chloride, regulating and controlling the permeation water yield of the nanofiltration device to be about 50%, obtaining a first permeation solution and a first concentrated solution, adding pure water which is equal to the liquid in the mixture in the step S10 in a concentrated water tank to dilute the first concentrated solution, then introducing the diluted solution into the nanofiltration device again for separation, regulating the permeation water yield of the nanofiltration device to be about 33%, obtaining a second permeation solution and a second concentrated solution, discharging the second permeation solution into the permeation water tank, mixing the second permeation solution with the first permeation solution to obtain a mixed permeation solution, and regulating and controlling the permeation water yield of the nanofiltration device for two times, so that the volume ratio of the mixed permeation solution to the second concentrated solution is 1:1. wherein the main component in the mixed permeate is lithium chloride, and the main component of the second concentrated solution is lithium dihydrogen phosphate.
Step S12: the bipolar membrane electrodialysis device comprises an anode electrode chamber, an acid chamber, a base chamber, a salt chamber and a cathode electrode chamber, wherein the mixed permeate and the second concentrated solution are respectively introduced into the salt chamber, direct current is introduced into the salt chamber for electrodialysis, a first lithium hydroxide solution and a second lithium hydroxide solution are respectively obtained in the base chamber, and a hydrochloric acid solution and a phosphoric acid solution are respectively obtained in the acid chamber.
Specific: the Bipolar Membrane Electrodialysis Device (BMED) is a self-made membrane stacking device in a laboratory, a schematic diagram of the device is shown in fig. 3, the device consists of two Anion Exchange Membranes (AEMs), two Cation Exchange Membranes (CEMs), three bipolar membranes (BPMs) and two electrode plates, the two electrode plates are combined together to form two repeating units, and a specific arrangement mode is anode plate-bipolar membrane-cation exchange membrane-anion exchange membrane-bipolar membrane-cathode plate.
Wherein, the two electrode plates are made of titanium and are coated with an oxide coating such as ruthenium iridium. And the compartments between two adjacent films are separated by a 10mm spacer and the effective area of each film is 2033mm 2.
The device comprises two electrode chambers (an anode electrode chamber and a cathode electrode chamber), two acid chambers, two alkali chambers and two salt chambers, and specifically, an anode plate is matched with the anode surface of a bipolar membrane to form the anode electrode chamber, a cathode surface of the bipolar membrane is matched with a cation exchange membrane to form the acid chamber, a cation exchange membrane is matched with an anion exchange membrane to form the salt chamber, an anion exchange membrane is matched with the anode surface of the bipolar membrane to form the alkali chamber, and a cathode surface of the bipolar membrane is matched with a cathode plate to form the cathode electrode chamber. Each chamber had a volume of 200mL and during the experiment 4 peristaltic pumps were used to pump different feed materials into the corresponding chamber and back through the return line into the feed solution container to form 4 circulation loops at a feed rate of 200mL/min.
Wherein, the anode electrode chamber and the cathode electrode chamber are filled with buffer solution, the buffer solution is sodium sulfate solution with the concentration of 0.2mol/L-0.5mol/L, and the purpose of filling the buffer solution is to ensure stable operation of the bipolar membrane electrodialysis device. Before the mixed penetrating fluid and the second concentrated fluid obtained in the step S11 are respectively introduced into the salt chamber in the experimental process, the salt chamber is correspondingly filled with a first lithium salt solution and a second lithium salt solution respectively, the solute of the first lithium salt solution is consistent with that of the mixed penetrating fluid, the solute of the second lithium salt solution is consistent with that of the second concentrated fluid, and the initial concentration of the first lithium salt solution and the initial concentration of the second lithium salt solution are controlled to be 0.1mol/L-0.5mol/L.
The direct current power supply is used for connecting the two electrode plates, the maximum voltage of the power supply can be 40V, the current density is controlled to be unchanged, the current density range is controlled to be 10mA/cm 2-50 mA/cm2, and before the two electrode plates are formally electrified, the circulation of four feed liquids is started in advance until visible bubbles are eliminated and a steady flow state is achieved.
The whole operation process is carried out at room temperature (26 ℃), the voltage is suddenly reduced after the power is supplied, the area resistance is increased along with ion transfer consumption of a salt chamber for a period of time, the voltage is gradually increased to be recovered to the initial voltage (40V), then the power is cut off to stop the operation, circulating solutions of an acid chamber and an alkali chamber are collected, fe 3+ and trace impurity ions such as Ca 2+、Mg2+、Cu2+ in alkali solution form precipitation in an alkaline environment, after the filtering operation, a first lithium hydroxide solution and a second lithium hydroxide solution are respectively obtained in the alkali chamber, an inorganic acid solution can be obtained in the acid chamber, the inorganic acid solution comprises a hydrochloric acid solution and a phosphoric acid solution, and the hydrochloric acid solution can be used as a leaching agent in the step S10 after the hydrochloric acid solution is treated.
The current efficiency of the bipolar membrane electrodialysis device was calculated as follows:
In the above formula (2), ct (mol/L) and Vt (mL) are the concentration and volume of LiOH in the base chamber at time node t, and similarly C 0 and V 0 are the initial concentration and volume of LiOH in the base chamber, Z is the absolute valence of the ion (for LiOH, z=1), F is faraday constant (96485C/mol), N is the number of repeating units of the device (n=2), I (a) is the applied current, and t (h) is the test time.
Step S13: mixing the first lithium hydroxide solution and the second lithium hydroxide solution, filtering to obtain a lithium hydroxide solution, evaporating, concentrating, crystallizing and centrifuging the lithium hydroxide solution to obtain a crystallization mother solution and a crystallization product, and drying and crushing the crystallization product to obtain lithium hydroxide monohydrate.
Specific: mixing the first lithium hydroxide solution and the second lithium hydroxide solution obtained in the step S12, and filtering to obtain a lithium hydroxide solution, wherein the volume ratio of the solution before and after evaporation concentration is (15-20): 1. and then cooling and crystallizing the concentrated solution by utilizing the solubility difference to obtain a crystallized product and crystallized mother solution, wherein the crystallized mother solution is returned to the lithium hydroxide solution for mixed circulation and evaporation for use, the crystallized product is dried for 1-4 hours in a drying oven at 100-140 ℃ after being washed, and then crushed by an airflow crusher to obtain the lithium hydroxide monohydrate product.
According to the method, the nanofiltration device is adopted for multiple membrane separation, so that the second concentrated solution enriched with the dihydrogen phosphate is obtained, and is conveniently distinguished from the mixed penetrating fluid mainly containing lithium chloride, so that the use of reagents in the treatment process of lithium iron phosphate waste powder is effectively reduced, the phase change is not involved in the separation process of the two materials, and the method is a pure physical process and low in whole-process energy consumption; and then the mixed permeate and the second concentrated solution obtained by membrane separation for a plurality of times through a nanofiltration device are respectively treated through a bipolar membrane electrodialysis device to generate a high-purity lithium hydroxide solution, and finally the obtained lithium hydroxide monohydrate product has higher content. That is, the method adopts the nanofiltration device and the bipolar membrane electrodialysis device to treat the lithium-containing leaching solution of the lithium iron phosphate waste powder, no other reagent is required to be added in the operation after leaching reaction, the high-purity lithium hydroxide monohydrate product can be obtained under relatively low energy consumption and mild conditions, the whole process is simple, the control is easy, the environmental pollution is small, the cost is low, the recovery rate of lithium in the recovered lithium iron phosphate waste powder is high, and the utilization value and the economic benefit of the recovered lithium iron phosphate waste powder can be greatly improved.
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder provided by the first embodiment of the invention comprises the following steps of S10-S13:
Step S10: mixing lithium iron phosphate waste powder, an oxidant and water uniformly according to a preset solid-to-liquid ratio, adding a leaching agent with a preset concentration, adjusting to a preset pH value, heating at a preset temperature for a preset time, and filtering to obtain leaching liquid and filter residues.
In the embodiment, the oxidant is preferably hydrogen peroxide, the concentration of the hydrogen peroxide is 5%, the hydrogen peroxide consumption is 220mL, 100g of lithium iron phosphate waste powder is taken, and pure water is added to adjust the solid-liquid ratio to 1g:10mL; then 10mL of 10mol/L hydrochloric acid solution is slowly added, and the leaching solution and the ferric phosphate filter residue containing lithium are obtained by filtering through mechanical stirring for 1h at the constant temperature of a water bath of 60 ℃, and the leaching rate C of the embodiment is calculated to be 94.3% through the formula (1).
Step S11: and introducing the leaching solution into a nanofiltration device to obtain a first penetrating fluid and a first concentrated solution, diluting the first concentrated solution, introducing the diluted first concentrated solution into the nanofiltration device again to obtain a second penetrating fluid and a second concentrated solution, and mixing the second penetrating fluid with the first penetrating fluid to obtain a mixed penetrating fluid.
In this embodiment, the operation pressure of the nanofiltration device is 0.1MPa, the permeate water rate of the nanofiltration device is adjusted to be about 50%, a first permeate liquid and a first concentrate are obtained, 1000mL of pure water is added into the first concentrate to dilute the first concentrate, then the first concentrate is separated by the nanofiltration device, at this time, the permeate water rate of the nanofiltration device is adjusted to be about 33%, a second permeate liquid and a second concentrate are obtained, the first permeate liquid and the second permeate liquid are mixed to obtain a mixed permeate liquid, and the volume ratio of the finally obtained mixed permeate liquid to the second concentrate is about 1:1 through twice adjustment of the permeate water rate of the nanofiltration device.
Step S12: the bipolar membrane electrodialysis device comprises an anode electrode chamber, an acid chamber, a base chamber, a salt chamber and a cathode electrode chamber, wherein the mixed permeate and the second concentrated solution are respectively introduced into the salt chamber, direct current is introduced into the salt chamber for electrodialysis, a first lithium hydroxide solution and a second lithium hydroxide solution are respectively obtained in the base chamber, and a hydrochloric acid solution and a phosphoric acid solution are respectively obtained in the acid chamber.
In this example, the mixed permeate and the second concentrate obtained in step S11 were pumped as feed solutions into the salt chambers of the BMED apparatus shown in fig. 2, respectively, and the initial concentrations of the first lithium salt solution and the second lithium salt solution in the salt chambers were controlled to be 0.3mol/L, respectively, and the circulation feed rate was fixed at 200ml/min, consistent with the other feed liquids. After 10min of pre-circulation, a direct current power supply is connected, the current density is controlled to be 30mA/cm 2, voltage reading (V) on the power supply is observed, the power-off stopping operation is carried out when the voltage is slowly increased to 40V after the voltage is rapidly reduced, and the time (t) and the concentration and the volume of the first lithium hydroxide solution and the second lithium hydroxide solution in the alkaline chamber before and after the power-on are respectively recorded.
And then, after electrodialysis of the two feed solutions, mixing the first lithium hydroxide solution and the second lithium hydroxide solution which are obtained in the alkali chamber, and filtering to obtain the lithium hydroxide solution for the next operation. Separately collecting the hydrochloric acid solution and the phosphoric acid solution obtained in the acid chamber, and calculating the current efficiencies of the electrodialysis mixed permeate and the second concentrate respectively by the formula (2); 89.76% and 84.28%, respectively, and in addition, the Li transfer rate during electrodialysis is defined as the ratio of the Li content in the base compartment to the Li content in the initial salt compartment after the end of electrodialysis, under which conditions the two feed solutions electrodialysis Li transfer rates were 99.53% and 99.47%, respectively.
Step S13: mixing the first lithium hydroxide solution and the second lithium hydroxide solution, filtering to obtain a lithium hydroxide solution, evaporating, concentrating, crystallizing and centrifuging the lithium hydroxide solution to obtain a crystallization mother solution and a crystallization product, and drying and crushing the crystallization product to obtain lithium hydroxide monohydrate.
In this embodiment, the first lithium hydroxide solution and the second lithium hydroxide solution obtained in the step S12 are mixed to obtain a lithium hydroxide solution, the lithium hydroxide solution is filtered and then transferred into a rotary evaporator, the evaporation concentration ratio is 15:1, the concentrated solution is transferred into a beaker to be cooled to room temperature, the crystallized mother solution and the crystallized product are obtained after centrifugal separation, the crystallized mother solution is collected and returned to the lithium hydroxide solution obtained by mixing for recycling, the crystallized product is washed and then is dried in an oven at 120 ℃ for 2.5 hours, and then the product lithium hydroxide monohydrate (lioh·h 2 O) is obtained after crushing by a jet mill.
The pure content of lithium hydroxide in a product prepared by the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder is 57.0%, and the content of other impurities is compared with national standard LiOH.H2O-D1 as shown in the following table 1:
TABLE 1 comparison Table of lithium hydroxide monohydrate prepared by the invention and national Standard LiOH H2O-D1
As can be seen from Table 1, the impurity content of the lithium hydroxide monohydrate product prepared by the method is smaller than that of the national standard LiOH H2O-D1, and the purity of the lithium hydroxide in the product is higher.
Example two
The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder provided by the second embodiment of the invention is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
In the step S10, 100g of lithium iron phosphate waste powder is taken, 220mL of 5% hydrogen peroxide is added for mixing, and then pure water is added for regulating the solid-liquid ratio to 1g to 8mL.
Example III
The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder provided by the third embodiment of the invention is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
In the step S10, 100g of lithium iron phosphate waste powder is taken, 220mL of 5% hydrogen peroxide is added for mixing, and then pure water is added for regulating the solid-liquid ratio to 1 g/9 mL.
Example IV
The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder provided by the fourth embodiment of the invention is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
In the step S10, 100g of lithium iron phosphate waste powder is taken, 220mL of 5% hydrogen peroxide is added for mixing, and then pure water is added for regulating the solid-liquid ratio to 1g to 11mL.
Example five
The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder provided by the fifth embodiment of the invention is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
in the step S10, 100g of lithium iron phosphate waste powder is taken, 220mL of 5% hydrogen peroxide is added for mixing, and then pure water is added for regulating the solid-liquid ratio to 1g to 12mL.
Example six
The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder provided by the sixth embodiment of the invention is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
In step S12, the current density of the direct current power supply for switching on the bipolar membrane electrodialysis device is set to 10mA/cm 2.
Example seven
The seventh embodiment of the present invention provides a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder, which is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
In step S12, the current density of the direct current power supply for switching on the bipolar membrane electrodialysis device is set to 20mA/cm 2.
Example eight
The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder provided by the eighth embodiment of the invention is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
In step S12, the current density of the direct current power supply for switching on the bipolar membrane electrodialysis device is set to 40mA/cm 2.
Example nine
The ninth embodiment of the present invention provides a method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder, which is different from the method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder in the first embodiment in that:
In step S12, the current density of the direct current power supply for switching on the bipolar membrane electrodialysis device is set to be 50mA/cm 2.
Referring to table 2, parameters corresponding to the first to fifth embodiments of the present invention are shown.
Table 2 solid-to-liquid ratio-leaching ratio data table in examples one to five
| Project | Example 1 | Example two | Example III | Example IV | Example five |
| Solid to liquid ratio (g: mL) | 1:10 | 1:8 | 1:9 | 1:11 | 1:12 |
| Leaching rate C (%) | 94.3 | 85.4 | 90.8 | 94.7 | 94.6 |
As can be seen from the comparison of examples one to three in table 2 above: in the step S10, the leaching rate of lithium is affected by the small amount of pure water added in the solid-liquid ratio adjusting process; as can be seen from the comparison of example one, example four and example five in table 2 above: when the amount of pure water added in the process of adjusting the solid-liquid ratio in the step S10 is large, the leaching rate of lithium is not large, but the amount of liquid is large, so that the cost of subsequent separation and evaporation concentration can be greatly increased, and the solid-liquid ratio in the step S10 is preferably 1g:10mL.
Referring to table 3, parameters corresponding to the first embodiment, the sixth embodiment and the ninth embodiment of the present invention are shown.
Table 3 current efficiency and Li transfer rate data tables for example one, example six to example nine
As can be seen from the comparison of the data in examples one, six to nine of table 3, the current efficiency in the electrodialysis of the two feed solutions, i.e. the mixed permeate and the second concentrate, gradually decreased with increasing current density, and the Li transfer rate was not significantly changed and was maintained at a high level (> 99%).
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder, which is characterized by comprising the following steps:
Uniformly mixing lithium iron phosphate waste powder, an oxidant and water according to a preset solid-to-liquid ratio, adding a leaching agent with a preset concentration to adjust the pH value to a preset pH value, heating for a preset time at a preset temperature, and filtering to obtain leaching liquid and filter residues;
Introducing the leaching solution into a nanofiltration device to obtain a first permeate and a first concentrate, diluting the first concentrate, and then introducing the first concentrate into the nanofiltration device again to obtain a second permeate and a second concentrate, wherein the second permeate is mixed with the first permeate to obtain a mixed permeate;
Providing a bipolar membrane electrodialysis device, wherein the bipolar membrane electrodialysis device comprises an anode electrode chamber, an acid chamber, a base chamber, a salt chamber and a cathode electrode chamber, the mixed permeate and the second concentrated solution are respectively introduced into the salt chamber, direct current is introduced to carry out electrodialysis, a first lithium hydroxide solution and a second lithium hydroxide solution are respectively obtained in the base chamber, and a hydrochloric acid solution and a phosphoric acid solution are respectively obtained in the acid chamber;
Mixing the first lithium hydroxide solution and the second lithium hydroxide solution, filtering to obtain a lithium hydroxide solution, evaporating, concentrating, crystallizing and centrifuging the lithium hydroxide solution to obtain a crystallization mother solution and a crystallization product, and drying and crushing the crystallization product to obtain lithium hydroxide monohydrate.
2. The method for preparing lithium iron phosphate waste powder into lithium hydroxide monohydrate according to claim 1, wherein the oxidant comprises any one of hydrogen peroxide and sodium chlorate, and the preset solid-to-liquid ratio is 1g (8-12) mL.
3. The method for preparing lithium iron phosphate waste powder into lithium hydroxide monohydrate according to claim 1, wherein the leaching agent is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 5-15mol/L, the preset pH value is 0.1-2, the preset temperature is 60-80 ℃, and the preset time is 0.5-2 h.
4. The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder according to claim 1, wherein the operating pressure of the nanofiltration device is controlled between 0.1MPa and 0.5MPa.
5. The method for preparing lithium iron phosphate waste powder into lithium hydroxide monohydrate according to claim 1, wherein the permeate water rate of the nanofiltration device is 20% -80%, and the volume ratio of the mixed permeate and the second concentrated solution is 1 by controlling the permeate water rate of the nanofiltration device: 1.
6. The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder according to claim 1, wherein the bipolar membrane electrodialysis device comprises an anode plate, a cathode plate, a bipolar membrane, a cation exchange membrane and an anion exchange membrane, which are arranged in a manner of anode plate-bipolar membrane-cation exchange membrane-anion exchange membrane-bipolar membrane-cathode plate, and the anode plate and the cathode plate are ruthenium iridium coated titanium electrode plates;
The anode plate is matched with the positive surface of the bipolar membrane to form the anode electrode chamber, the negative surface of the bipolar membrane is matched with the cation exchange membrane to form the acid chamber, the cation exchange membrane is matched with the anion exchange membrane to form the salt chamber, the anion exchange membrane is matched with the positive surface of the bipolar membrane to form the alkali chamber, and the negative surface of the bipolar membrane is matched with the cathode plate to form the cathode electrode chamber.
7. The method for preparing lithium iron phosphate waste powder into lithium hydroxide monohydrate according to claim 1, wherein the anode electrode chamber and the cathode electrode chamber are filled with buffer solution, the buffer solution is sodium sulfate solution, and the concentration of the sodium sulfate solution is 0.2mol/L-0.5mol/L;
before the mixed penetrating fluid is introduced into the salt chamber, a first lithium salt solution is filled in the salt chamber, the solute of the first lithium salt solution is consistent with that of the mixed penetrating fluid, and the initial concentration of the first lithium salt solution is controlled to be 0.1 mol/L-0.5 mol/L;
before the second concentrated solution is introduced into the salt chamber, a second lithium salt solution is filled in the salt chamber, the solute of the second lithium salt solution is consistent with that of the second concentrated solution, and the initial concentration of the second lithium salt solution is controlled to be 0.1 mol/L-0.5 mol/L.
8. The method for preparing lithium iron phosphate waste powder into lithium hydroxide monohydrate according to claim 1, wherein the current density of the electrodialysis is controlled to be 10mA/cm 2-50 mA/cm2.
9. The method for preparing lithium iron phosphate waste powder into lithium hydroxide monohydrate according to claim 1, wherein after the evaporation and concentration process is completed, the volume ratio of the lithium hydroxide solution before and after concentration is (15-20): 1.
10. The method for preparing lithium hydroxide monohydrate from lithium iron phosphate waste powder according to claim 1, wherein the crystallization mother liquor is returned to the lithium hydroxide solution obtained by the bipolar membrane electrodialysis device for mixed recycling.
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