CN113929061A - Method for recovering lithium nitride waste - Google Patents
Method for recovering lithium nitride waste Download PDFInfo
- Publication number
- CN113929061A CN113929061A CN202111191392.0A CN202111191392A CN113929061A CN 113929061 A CN113929061 A CN 113929061A CN 202111191392 A CN202111191392 A CN 202111191392A CN 113929061 A CN113929061 A CN 113929061A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulfide
- reaction
- methyl pyrrolidone
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 28
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 title claims abstract 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 56
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 40
- HXQGSILMFTUKHI-UHFFFAOYSA-M lithium;sulfanide Chemical compound S[Li] HXQGSILMFTUKHI-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000013058 crude material Substances 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000007769 metal material Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 4
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012066 reaction slurry Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- SQEAYXHOPFSDBX-UHFFFAOYSA-N 4-(hydroxymethylamino)butanoic acid Chemical compound [H]C([H])(NCO)C([H])([H])C([H])([H])C(O)=O SQEAYXHOPFSDBX-UHFFFAOYSA-N 0.000 description 1
- AOKCDAVWJLOAHG-UHFFFAOYSA-N 4-(methylamino)butyric acid Chemical compound C[NH2+]CCCC([O-])=O AOKCDAVWJLOAHG-UHFFFAOYSA-N 0.000 description 1
- QKAIIJHXZDNKMY-UHFFFAOYSA-N 4-hydroxy-2-(methylamino)butanoic acid Chemical compound CNC(C(O)=O)CCO QKAIIJHXZDNKMY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of battery material recovery, and discloses a method for recovering lithium nitride waste. The recovery method comprises the following steps: s1, mixing the lithium nitride waste material with N-methyl pyrrolidone, heating, and introducing hydrogen sulfide for reaction to obtain a metal lithium crude material and an N-methyl pyrrolidone solution containing lithium hydrosulfide; s2, heating the N-methyl pyrrolidone solution containing lithium hydrosulfide to obtain a lithium sulfide crude material; and S3, washing and drying the crude lithium metal material and the crude lithium sulfide material respectively to obtain the lithium metal and the lithium sulfide. According to the invention, the lithium nitride waste material and hydrogen sulfide react in N-methyl pyrrolidone, and the N-methyl pyrrolidone solution containing lithium hydrosulfide is heated to finally obtain the lithium metal and the lithium sulfide, wherein the yield of the obtained lithium sulfide and lithium metal is high, the recovery rate is more than 95% by lithium, the quality of the lithium sulfide and lithium metal is good, the impurity content is low, and the purity is more than 99%.
Description
Technical Field
The invention belongs to the technical field of battery material recovery, and particularly relates to a method for recovering lithium nitride waste.
Background
Lithium nitride is a fast ionic conductor and has higher conductivity than other inorganic lithium salts, and therefore, is widely used as a solid electrode material for lithium ion batteries. At present, the main preparation method of lithium nitride is to use lithium to react in nitrogen, but the yield of high-purity lithium nitride (mass content > 99.5%) is lower, and the unqualified products are more. The unqualified lithium nitride waste mainly contains more unreacted metal lithium, and the recycling of the unqualified lithium nitride waste is a difficult problem. The traditional treatment method is to expose the lithium nitride waste material in the air to change the lithium nitride waste material into lithium carbonate, but the lithium carbonate has lower value compared with metal lithium and lithium sulfide, and how to recover the unreacted metal lithium from the lithium nitride waste material and convert the lithium nitride waste material into lithium sulfide with higher value is a problem to be solved in the field.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for recovering lithium nitride waste, which can recover and obtain high-value lithium metal and lithium sulfide from the lithium nitride waste.
The invention provides a method for recovering lithium nitride waste, which comprises the following steps:
s1, mixing the lithium nitride waste material with N-methyl pyrrolidone, introducing hydrogen sulfide for heating reaction, and filtering to obtain a metal lithium coarse material and an N-methyl pyrrolidone solution containing lithium hydrosulfide;
s2, heating the N-methyl pyrrolidone solution containing the lithium hydrosulfide, and filtering to obtain a lithium sulfide crude material;
s3, respectively purifying the crude lithium metal material and the crude lithium sulfide material to obtain lithium metal and lithium sulfide.
The method comprises the steps of reacting lithium nitride waste materials with hydrogen sulfide in N-methyl pyrrolidone, reacting the lithium nitride waste materials with the hydrogen sulfide in the N-methyl pyrrolidone at a certain temperature to generate lithium hydrosulfide which is soluble in the N-methyl pyrrolidone, wherein the lithium hydrosulfide is acidic, when the reaction is completed, the whole slurry is strongly acidic, the lithium metal does not react, filtering to obtain a crude lithium metal material, heating and filtering an N-methyl pyrrolidone solution containing the lithium hydrosulfide to obtain a crude lithium sulfide material, and finally purifying to obtain the lithium metal and the lithium sulfide. The reaction principle of the invention is as follows:
Li3N+3H2S→3LiHS+NH3；2LiHS→2Li2S+H2S。
because no water molecule is introduced in the whole reaction process, the reaction of lithium sulfide and water can be avoided, and the amidation reaction of NMP can be avoided. Mainly under alkaline environment or high temperature, three adjacent C in NMP are likely to be activated, wherein the C in C ═ O can directly cause NMP ring-opening hydrolysis after being activated to generate N-methyl-4-aminobutyric acid; if the methylene adjacent to N and the C of the methyl are activated, oxidation reaction can occur firstly to generate peroxide, and hydroxyl is easy to generate due to instability of the peroxide, namely 5-HNMP and NHMP are generated; in addition, 5-HNMP and NHMP are easy to open loop and hydrolyze in an alkaline environment to generate N-methyl-4-hydroxy aminobutyric acid and N-hydroxymethyl-4-aminobutyric acid, and finally, the three NMP hydrolysis products can be subjected to polymerization reaction to generate the amide polymer. According to the reaction, water molecules are not introduced, NMP does not undergo hydrolysis reaction at high temperature, impurities are prevented from being introduced into a lithium sulfide product, unreacted metal lithium in the lithium nitride waste material is recovered, and ammonia gas generated in the reaction process can be volatilized. The lithium sulfide and metal lithium obtained by the recovery method have high yield, good quality, low impurity and purity of more than 99 percent.
Preferably, in step S1, the lithium nitride waste material and the N-methyl pyrrolidone are mixed according to a material-liquid ratio of 1kg (6-8) L.
Preferably, in step S1, the reaction temperature is 70 to 130 ℃, and the reaction pressure is 50 to 150.
Preferably, in step S1, the particles D50 of the lithium nitride waste material are less than 3 um.
Preferably, the specific process of step S2 is: and under the condition of inert gas and pressure of-50 to-150 Pa, heating the N-methylpyrrolidone solution containing the lithium hydrosulfide to 170 to 190 ℃, stirring for 6 to 8 hours, and filtering to obtain a lithium sulfide coarse material.
Preferably, the inert gas comprises argon or nitrogen.
Preferably, in step S3, the purification includes washing and drying.
Preferably, the specific process of washing is as follows: the washing is carried out by adopting the mixture of alkane solvent and ether solvent as washing liquid.
Preferably, the alkane solvent comprises n-hexane or cyclohexane; the ether solvent comprises 1, 3-dioxolane or acetone.
Preferably, the volume ratio of the alkane solvent to the ether solvent is 1 (1-5).
Preferably, in step S3, the purity of the metallic lithium is greater than 99%; the purity of the lithium sulfide is more than 99%.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the lithium nitride waste material and hydrogen sulfide react in N-methyl pyrrolidone, and the N-methyl pyrrolidone solution containing lithium hydrosulfide is heated to finally obtain metal lithium and lithium sulfide. The lithium sulfide and metal lithium obtained by the recovery method have high yield, the recovery rate is over 95 percent based on lithium, the quality of the lithium sulfide and the metal lithium is good, the impurity is low, and the purity is over 99 percent.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A method for recycling lithium nitride waste comprises the following steps:
s1, loading 10kg of lithium nitride waste (containing 31.6% of metallic lithium) and 80L N-methyl pyrrolidone into a 200L sealed reaction kettle, uniformly stirring, heating to 70 ℃, introducing hydrogen sulfide gas into a reaction system through a submerged tube for reaction, keeping the air pressure in the reaction kettle at 50Pa, keeping the reaction temperature at 70 ℃, and filtering after complete reaction to respectively obtain metallic lithium coarse material and N-methyl pyrrolidone solution containing lithium hydrosulfide; in the reaction process, a small amount of reaction slurry can be added into the methyl orange solution, and the reaction can be judged to be complete if the reaction slurry turns red;
s2, adding an N-methyl pyrrolidone solution containing lithium hydrosulfide into a sealed reaction kettle, introducing argon gas to enable the pressure in the reaction kettle to be-50 Pa, heating to 170 ℃, keeping the temperature at 170 ℃ for reacting for 6 hours, continuously stirring the solution in the reaction process, and filtering after the reaction is completed to obtain a lithium sulfide crude material;
s3, mixing n-hexane and 1, 3-dioxolane according to the volume ratio of 1:1 to obtain a washing solution, washing the obtained lithium sulfide crude material and the obtained metal lithium crude material respectively in a closed environment for three times by using the washing solution, filtering, then respectively placing in a vacuum oven, and carrying out vacuum drying treatment for 1 hour at 450 ℃ to obtain 13.18kg of lithium sulfide and 3.14kg of metal lithium.
Example 2
A method for recycling lithium nitride waste comprises the following steps:
s1, filling 15kg of lithium nitride waste (containing 21.6% of metallic lithium) and 100L N-methyl pyrrolidone into a 200L sealed reaction kettle, uniformly stirring, heating to 100 ℃, introducing hydrogen sulfide gas into a reaction system through a submerged pipe for reaction, keeping the air pressure in the reaction kettle at 100Pa, keeping the reaction temperature at 100 ℃, and filtering after complete reaction to respectively obtain metallic lithium coarse material and N-methyl pyrrolidone solution containing lithium hydrosulfide; in the reaction process, a small amount of reaction slurry can be added into the methyl orange solution, and the reaction can be judged to be complete if the reaction slurry turns red;
s2, adding an N-methyl pyrrolidone solution containing lithium hydrosulfide into a sealed reaction kettle, introducing nitrogen to enable the pressure in the reaction kettle to be-100 Pa, heating to 180 ℃, keeping the temperature at 180 ℃ for reaction for 7 hours, continuously stirring the solution in the reaction process, and filtering after the reaction is completed to obtain a lithium sulfide crude material;
s3, mixing cyclohexane and acetone according to the volume ratio of 1:1 to obtain washing liquid, washing the obtained lithium sulfide crude material and metal lithium crude material respectively in a closed environment for three times by using the washing liquid, filtering, then respectively placing in a vacuum oven, and carrying out vacuum drying treatment for 2 hours at the temperature of 450 ℃ to obtain 22.08kg of lithium sulfide and 3.23kg of metal lithium.
Example 3
A method for recycling lithium nitride waste comprises the following steps:
s1, 20kg of lithium nitride waste (containing 18.16% of metallic lithium) and 120L N-methyl pyrrolidone are filled into a 200L sealed reaction kettle, the mixture is uniformly stirred and heated to 130 ℃, hydrogen sulfide gas is introduced into a reaction system through a submerged tube for reaction, the air pressure in the reaction kettle is kept at 150Pa, the reaction temperature is kept at 130 ℃, and after the reaction is completed, the mixture is filtered to respectively obtain metallic lithium coarse material and N-methyl pyrrolidone solution containing lithium hydrosulfide; in the reaction process, a small amount of reaction slurry can be added into the methyl orange solution, and the reaction can be judged to be complete if the reaction slurry turns red;
s2, adding an N-methyl pyrrolidone solution containing lithium hydrosulfide into a sealed reaction kettle, introducing argon gas to ensure that the pressure in the reaction kettle is-150 Pa, heating to 190 ℃, keeping the reaction at 190 ℃ for 8 hours, continuously stirring the solution in the reaction process, and filtering after the reaction is completed to obtain a lithium sulfide crude material;
s3, mixing cyclohexane and 1, 3-dioxolane according to the volume ratio of 1:1 to obtain a washing solution, washing the obtained lithium sulfide crude material and the obtained metal lithium crude material respectively in a closed environment for three times by using the washing solution, filtering, then respectively placing in a vacuum oven, and carrying out vacuum drying treatment for 3 hours at 450 ℃ to obtain 31.35kg of lithium sulfide and 3.63kg of metal lithium.
Comparative example 1
S1, charging 10kg of lithium nitride waste (containing 31.6 percent of metallic lithium), 80L N-methyl pyrrolidone and 36.11kg of sodium hydrosulfide into a 200L sealed reaction kettle, uniformly stirring, heating to 70 ℃ under the condition of nitrogen, keeping the air pressure in the reaction kettle at 50Pa, and keeping the reaction temperatureMaintaining the temperature at 70 ℃, and filtering after complete reaction to respectively obtain a metal lithium crude material, sodium sulfide and an N-methylpyrrolidone solution containing lithium hydrosulfide; in the reaction process, a small amount of reaction slurry can be added into the methyl orange solution, and the reaction can be judged to be complete if the reaction slurry turns red; the reaction formula is as follows: 2Li3N+6NaHS→3L2S+3Na2S+2NH3；
S2, adding an N-methyl pyrrolidone solution containing lithium hydrosulfide into a sealed reaction kettle, introducing argon gas to enable the pressure in the reaction kettle to be-50 Pa, heating to 170 ℃, keeping the temperature at 170 ℃ for reacting for 6 hours, continuously stirring the solution in the reaction process, and filtering after the reaction is completed to obtain a lithium sulfide crude material;
s3, filling the crude lithium metal material obtained in the step S1 and sodium sulfide into an 80L N-methyl pyrrolidone sealing device, introducing hydrogen sulfide gas, stirring uniformly, heating to 70 ℃, keeping the air pressure in a reaction kettle at 50Pa, keeping the reaction temperature at 70 ℃, and filtering after complete reaction to respectively obtain the crude lithium metal material and an N-methyl pyrrolidone solution containing sodium hydrosulfide;
s4, mixing n-hexane and 1, 3-dioxolane according to the volume ratio of 1:1 to obtain a washing solution, washing the obtained lithium sulfide crude material and the obtained metal lithium crude material respectively in a closed environment for three times by using the washing solution, filtering, then respectively placing in a vacuum oven, and carrying out vacuum drying treatment for 1 hour at 450 ℃ to obtain 7.84kg of lithium sulfide and 3.01kg of metal lithium.
The quality of lithium sulfide and lithium metal recovered in examples 1 to 3 was measured by ICP (inductively coupled plasma atomic emission spectrometry) and the results are shown in tables 1 and 2. Meanwhile, the recovery rate was calculated, and the results of the recovery rate in terms of lithium are shown in Table 3.
TABLE 1
Wherein Li in Table 12S is a reduced value.
TABLE 2
TABLE 3
| Quality of lithium sulfide | Purity of lithium sulfide | Quality of metallic lithium | Purity of metallic lithium | Recovery (in lithium) | |
| Example 1 | 13.18kg | 99.98％ | 3.14kg | 99.9％ | 98.07％ |
| Example 2 | 22.8kg | 99.98％ | 3.23kg | 99.9％ | 95.07％ |
| Example 3 | 31.35kg | 99.98％ | 3.63kg | 99.9％ | 97.46％ |
| Comparative example 1 | 17.84kg | 52.42％ | 2.57kg | 98.04％ | 65.45％ |
As can be seen from tables 1, 2 and 3, the purity of the lithium sulfide and the metal lithium obtained by the recovery method of the invention is very high, reaching 99.9 percent, and the recovery rate (calculated by lithium) is also more than 95 percent; in contrast, comparative example 1, in which hydrogen sulfide was replaced with sodium hydrosulfide, resulted in significant decrease in the purity of lithium sulfide and metallic lithium and recovery rate (in terms of lithium).
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions without departing from the spirit of the invention as set forth in the claims appended hereto.
Claims (10)
1. The method for recycling the lithium nitride waste is characterized by comprising the following steps of:
s1, mixing the lithium nitride waste material with N-methyl pyrrolidone, and introducing hydrogen sulfide for reaction to obtain a metal lithium coarse material and an N-methyl pyrrolidone solution containing lithium hydrosulfide;
s2, heating the N-methyl pyrrolidone solution containing the lithium hydrosulfide to obtain a lithium sulfide crude material;
s3, respectively purifying the crude lithium metal material and the crude lithium sulfide material to obtain lithium metal and lithium sulfide.
2. The recycling method according to claim 1, wherein in step S1, the lithium nitride waste material and N-methylpyrrolidone are mixed in a feed-to-liquid ratio of 1kg (6-8) L.
3. The recycling method according to claim 1, wherein in step S1, the temperature of the reaction is 70 to 130 ℃, and the pressure of the reaction is 50 to 150 ℃.
4. The recycling method according to claim 1, wherein in step S1, the particles D50 of the lithium nitride waste material are less than 3 um.
5. The recycling method according to claim 1, wherein the step S2 includes the following steps: and under the condition of inert gas and pressure of-50 to-150 Pa, heating the N-methylpyrrolidone solution containing the lithium hydrosulfide to 170 to 190 ℃, stirring for 6 to 8 hours, and filtering to obtain a lithium sulfide coarse material.
6. The recovery method according to claim 1, wherein the purification in step S3 includes washing and drying.
7. The recovery method according to claim 6, wherein the specific washing process comprises: the washing is carried out by adopting the mixture of alkane solvent and ether solvent as washing liquid.
8. The recovery method according to claim 7, wherein the alkane solvent comprises n-hexane or cyclohexane; the ether solvent comprises 1, 3-dioxolane or acetone.
9. The recovery method according to claim 7, wherein the volume ratio of the alkane solvent to the ether solvent is 1 (1-5).
10. The recycling method according to claim 1, wherein in step S3, the purity of the metallic lithium is greater than 99%; the purity of the lithium sulfide is more than 99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111191392.0A CN113929061A (en) | 2021-10-12 | 2021-10-12 | Method for recovering lithium nitride waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111191392.0A CN113929061A (en) | 2021-10-12 | 2021-10-12 | Method for recovering lithium nitride waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113929061A true CN113929061A (en) | 2022-01-14 |
Family
ID=79279080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111191392.0A Pending CN113929061A (en) | 2021-10-12 | 2021-10-12 | Method for recovering lithium nitride waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929061A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07330312A (en) * | 1994-06-03 | 1995-12-19 | Idemitsu Petrochem Co Ltd | Production of lithium sulfide |
| JP2002293515A (en) * | 2001-03-30 | 2002-10-09 | Idemitsu Petrochem Co Ltd | Production method of lithium hydrosulfide |
| CN103304837A (en) * | 2013-07-03 | 2013-09-18 | 四川宝利丰科技有限公司 | Lithium salt recovery method |
| CN103552990A (en) * | 2013-10-15 | 2014-02-05 | 四川宝利丰科技有限公司 | Production method of high-purity lithium sulfide |
| CN105016310A (en) * | 2015-07-30 | 2015-11-04 | 广东先导稀材股份有限公司 | Preparation method and device of high-purity lithium sulfide |
| CN109346679A (en) * | 2018-09-21 | 2019-02-15 | 合肥国轩高科动力能源有限公司 | A method of cycle life of lithium ion battery is promoted using lithium nitride |
| US10221075B1 (en) * | 2018-01-25 | 2019-03-05 | Benjamin Fannin Bachman | Synthesis of ammonia from hydrogen sulfide |
| CN112786313A (en) * | 2019-11-04 | 2021-05-11 | 中国科学院大连化学物理研究所 | Electrode slurry containing lithium nitride and preparation and application thereof |
| CN113415812A (en) * | 2021-06-23 | 2021-09-21 | 高能时代(佛山)新能源科技有限公司 | Preparation method and application of high-purity lithium sulfide |
-
2021
- 2021-10-12 CN CN202111191392.0A patent/CN113929061A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07330312A (en) * | 1994-06-03 | 1995-12-19 | Idemitsu Petrochem Co Ltd | Production of lithium sulfide |
| JP2002293515A (en) * | 2001-03-30 | 2002-10-09 | Idemitsu Petrochem Co Ltd | Production method of lithium hydrosulfide |
| CN103304837A (en) * | 2013-07-03 | 2013-09-18 | 四川宝利丰科技有限公司 | Lithium salt recovery method |
| CN103552990A (en) * | 2013-10-15 | 2014-02-05 | 四川宝利丰科技有限公司 | Production method of high-purity lithium sulfide |
| CN105016310A (en) * | 2015-07-30 | 2015-11-04 | 广东先导稀材股份有限公司 | Preparation method and device of high-purity lithium sulfide |
| US10221075B1 (en) * | 2018-01-25 | 2019-03-05 | Benjamin Fannin Bachman | Synthesis of ammonia from hydrogen sulfide |
| CN109346679A (en) * | 2018-09-21 | 2019-02-15 | 合肥国轩高科动力能源有限公司 | A method of cycle life of lithium ion battery is promoted using lithium nitride |
| CN112786313A (en) * | 2019-11-04 | 2021-05-11 | 中国科学院大连化学物理研究所 | Electrode slurry containing lithium nitride and preparation and application thereof |
| CN113415812A (en) * | 2021-06-23 | 2021-09-21 | 高能时代(佛山)新能源科技有限公司 | Preparation method and application of high-purity lithium sulfide |
Non-Patent Citations (1)
| Title |
|---|
| 刘翠连等: "N,N-二甲基甲酰胺对氮化锂的稳定性机理及其在锂离子超级电容器预锂化中的应用（英文）", 《SCIENCE BULLETIN》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109775732B (en) | Preparation method of high-purity lithium carbonate with well-adjusted particle size, particle size distribution and shape | |
| CN112520703B (en) | Green preparation method of lithium sulfide | |
| CN107863530B (en) | Method for preparing high-density lithium iron phosphate by adopting siderite | |
| US20180237314A1 (en) | Synthesis of deep eutectic solvent chemical precursors and their use in the production of metal oxides | |
| CN103626208A (en) | Preparation method for high-purity lithium fluoride by taking lithium hexafluorophosphate as raw material | |
| CN109809440B (en) | Method for preparing high-purity lithium chloride, high-purity lithium formate and high-purity lithium carbonate | |
| CN101838017A (en) | Method for preparing hydrated manganese sulfate | |
| CN101857270A (en) | Method for synthesizing high-purity arsine | |
| CN111039282A (en) | Preparation method of graphene material and application of graphene material in preparation of lithium ion battery | |
| CN111137869A (en) | Preparation method of lithium iron phosphate | |
| CN113929061A (en) | Method for recovering lithium nitride waste | |
| WO2024008206A1 (en) | Preparation method for lithium difluorophosphate | |
| KR101316620B1 (en) | Method of manufacturing high-purity and nano-sacle manganese dioxide | |
| GB2617006A (en) | Expanded graphite and preparation method therefor | |
| CN108328592A (en) | A kind of technique for using phosphoric acid by wet process to produce magnesium monohydrogen phosphate for raw material | |
| CN108190858B (en) | Preparation method of graphite fluoride | |
| CN112573592A (en) | Preparation method of high-purity nickel protoxide | |
| CN112745341A (en) | Preparation method of high-purity lithium bis (fluorooxalato) borate | |
| CN113512651B (en) | Method for respectively recovering indium and gallium from IGZO target material | |
| CN113979417B (en) | Preparation method of low-sulfur high-purity ferric phosphate in sulfuric acid system | |
| CN116282186B (en) | Battery-grade ferromanganese oxide based on nitrogen oxide recycling and preparation method thereof | |
| EP3424625A1 (en) | Nickel powder production method | |
| CN112062109B (en) | Preparation of S by using dielectric barrier discharge low-temperature plasma4N4Method (2) | |
| CN115286020B (en) | Preparation method of lithium salt or positive electrode material of lithium ion battery and lithium ion battery | |
| KR101498971B1 (en) | Novel method for preparing olivine type electrode material using formic acid derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 528299 floor 1 and 2, building 2, No. 6, Jinyuan 1st Road, Tangjiawan Town, high tech Zone, Zhuhai, Guangdong Applicant after: High energy era (Zhuhai) New Energy Technology Co.,Ltd. Address before: 518100 1003, building 8, Xinyi Lingyu R & D center, No. 26, Honglang North Second Road, Xingdong community, Xin'an street, Bao'an District, Shenzhen, Guangdong Province Applicant before: Shenzhen high energy times Technology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220114 |
|
| RJ01 | Rejection of invention patent application after publication |