CN116875820A - Recovering lithium silicon aluminum glass powder and co-producing carbon material and SiO 2 Is a method of (2) - Google Patents
Recovering lithium silicon aluminum glass powder and co-producing carbon material and SiO 2 Is a method of (2) Download PDFInfo
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- CN116875820A CN116875820A CN202310851397.4A CN202310851397A CN116875820A CN 116875820 A CN116875820 A CN 116875820A CN 202310851397 A CN202310851397 A CN 202310851397A CN 116875820 A CN116875820 A CN 116875820A
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- 239000011521 glass Substances 0.000 title claims abstract description 60
- 239000000843 powder Substances 0.000 title claims abstract description 50
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- -1 lithium silicon aluminum Chemical compound 0.000 title claims abstract description 29
- 229910004298 SiO 2 Inorganic materials 0.000 title claims description 10
- 238000002386 leaching Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000006104 solid solution Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000005188 flotation Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000001721 carbon Chemical class 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 239000006018 Li-aluminosilicate Substances 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 235000021110 pickles Nutrition 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- 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
- C22B7/001—Dry processes
-
- 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
-
- 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
- C22B7/007—Wet processes by acid leaching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to the field of waste treatment, and particularly relates to a recovery method of lithium silicon aluminum glass powder, which comprises the steps of roasting lithium silicon aluminum glass powder and a carbonaceous material at a temperature of more than 500 ℃ under negative pressure to obtain a roasted material; carrying out water leaching treatment on the roasting material to obtain lithium liquid and water leaching slag; and carrying out acid leaching treatment on the water leaching slag to obtain acid leaching liquid enriched with other metal elements in the glass and acid leaching slag. The method can effectively recycle the metal in the material, and can co-produce the carbon material with high electrochemical activity and the fine-grained silicon dioxide.
Description
Technical Field
The invention belongs to the field of waste recycling, and particularly relates to the field of glass powder recycling.
Background
The lithium aluminum silicon glass powder mainly comprises silicon dioxide, aluminum oxide and Li 2 Waste glass powder containing solid solution components such as O, and further, magnesium oxide, calcium oxide, transition metals such as Mn and Sr, and the like are often contained. The glass is highly solid due to lithium silicon aluminum oxideThe content of trace elements in the glass powder is low, the difficulty of recovering metal elements from the glass powder is high, and the recovery process for glass powder in the industry is low.
The Chinese patent publication No. CN115595445A discloses a method for recovering lithium from lithium-containing glass powder, and specifically discloses a method for recovering lithium from lithium-containing glass powder by adopting a method comprising the steps of 2 SO 4 Acid leaching treatment with 30vt% hydrochloric acid. The recovery effect of the metal of the process is not ideal, and the recovery and utilization of the components of all elements are difficult to realize.
Disclosure of Invention
Aiming at the problems that the glass powder treatment process is deficient, the complete element recovery is difficult to realize in a few processes, and the like, the invention provides the lithium silicon aluminum glass powder for recovery and co-production of carbon materials and SiO 2 Is aimed at achieving an efficient recovery of all elements, and in addition to this, preferably co-production of high-performance carbon materials and SiO 2 。
For Li in lithium silicon aluminum glass powder 2 O-A1 2 O 3 -SiO 2 The invention provides the following solutions for solving the problem that components are difficult to separate and utilize efficiently due to high solid solution of the components:
a recovery method of lithium silicon aluminum glass powder comprises the steps of roasting lithium silicon aluminum glass powder and carbonaceous materials at a temperature of more than 500 ℃ under negative pressure to obtain a roasted material;
carrying out water leaching treatment on the roasting material to obtain lithium liquid and water leaching slag;
and carrying out acid leaching treatment on the water leaching slag to obtain acid leaching liquid enriched with other metal elements in the glass and acid leaching slag.
Aiming at the problem that the lithium silicon aluminum glass powder is difficult to recycle due to solid solution of the components of the lithium silicon aluminum glass powder, the invention innovatively calcines and modifies the lithium silicon aluminum glass powder and the carbonaceous material under negative pressure, so that the solid solution structure can be transformed and modified, thereby realizing water leaching and lithium pre-extraction and acid leaching and extraction of other elements. The process can effectively improve the recovery of lithium, silicon, al and other components in the glass.
In the invention, the lithium silicon aluminum glass powder comprises waste Li 2 O-A1 2 O 3 -SiO 2 Powder of solid solution glass. In addition, other similar glass powder waste materials are allowed to exist.
In the present invention, the lithium silica alumina glass powder may further include at least one of solid-solution magnesium oxide, calcium oxide, potassium oxide, and the like. The lithium silicon aluminum glass powder also allows at least one of Mn, sr and Ni.
In the present invention, the particle size of the lithium silica alumina glass powder is not particularly required, and may be, for example, 100 μm or less; preferably 5 to 100 microns.
In the invention, the carbonaceous material is at least one of graphite, lignite and asphalt.
In the invention, the weight ratio of the lithium silicon aluminum glass powder to the carbonaceous material is 1:2 to 5, and further may be 1:2 to 3.
In the present invention, the negative pressure is 0.5atm or less, and may be 0.05 to 0.5atm in view of the treatment cost.
In the invention, the roasting temperature is 500-1000 ℃, preferably 500-800 ℃;
preferably, the calcination time is 1 hour or more, preferably 1 to 6 hours, and more preferably 2 to 4 hours.
Preferably, the roasting process comprises a first heat preservation section and a second heat preservation section;
preferably, the temperature of the first heat preservation section is 530-560 ℃, and the temperature of the second heat preservation section is 600-700 ℃;
preferably, the time of the first heat preservation period and the second heat preservation period is respectively 0.5-1.5 h.
In the invention, the temperature of the roasting material is subjected to air cooling treatment; the air-cooled atmosphere is preferably air.
In the invention, after the roasting material is air-cooled to 150-250 ℃, the roasting material is directly contacted with water with the temperature of less than 40 ℃ to be subjected to water quenching treatment, and then water leaching treatment is carried out;
preferably, the liquid-solid ratio in the water leaching stage is 10-50 mL/g.
Preferably, the temperature of the water immersion stage is below 40 ℃; further preferably 4 to 30℃and more preferably 10 to 15 ℃.
In the invention, the acid solution in the acid leaching treatment stage is an inorganic strong acid solution with the concentration of 0.5-2M. The inorganic strong acid is at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
the temperature of the acid leaching stage is 60 ℃ or less, and may be further 20 to 45 ℃ in consideration of the treatment cost and effect. The acid leaching process is carried out for 1-4 hours;
the invention also provides a method for recovering the lithium silicon aluminum glass powder and co-producing the carbon material and the SiO 2 The acid leaching slag is obtained by adopting the treatment method of the lithium silicon aluminum glass, and then the modified carbon material and SiO are separated from the acid leaching slag based on the known process such as flotation 2 ；
In the present invention, the modified carbon material and silica may be separated based on a known method, for example, separation may be achieved by a flotation method.
According to the invention, through the treatment, the electrochemical performance of the recovered carbon material can be improved, the secondary process is not carried out, and the silicon dioxide with the fine particle size required by the composite white carbon black with fine particles, high specific surface and high purity can be obtained in a co-production mode.
Preferably, the modified carbon material is used as a negative electrode active material of a lithium secondary battery.
Advantageous effects
According to the invention, the lithium silicon aluminum glass powder and the carbonaceous material are subjected to calcination modification under negative pressure innovatively, so that the solid solution structure can be subjected to transformation modification, and the water leaching pre-extraction of lithium is realized, and other elements are extracted by acid leaching. The process can effectively improve the recovery of lithium, silicon, al and other components in the glass.
In the invention, the combination of a two-stage roasting mechanism, air cooling and water quenching is adopted, which is favorable for further solving the problem of non-ideal metal leaching rate caused by glass solid solution, and is favorable for recycling carbon residues with high electrochemical performance, fine particles and silicon dioxide with high specific surface area.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
The glass powder is powder containing waste lithium silicon aluminum glass, and the particle size of the powder is below 100 microns. The contents of the components such as Li, si, and Al are not particularly limited, and for example, in the following cases, unless specifically stated otherwise, the glass frit to be used has a content of Li of 1 to 1.5% by weight, A1 of 7 to 10% by weight, a Ca of 0.5 to 1% by weight, and a Mg of 1 to 2% by weight, and a trace amount of components (such as Mn and Ni, which are contained in the pickle liquor and are not additionally indicated) of not more than 0.2% by weight in total, and the balance Si.
In the present invention, the production scale of the glass frit is not particularly limited, and may be, for example, a small scale, a pilot scale, or an actual production scale. In the following cases, unless otherwise specified, the preparation scale is a pilot scale, and the preparation amount is, for example, 100 to 150g.
In the present invention, the carbon raw material is a raw material containing a carbon element, and in the following cases, the carbon raw material used is graphite unless specifically stated.
The acid leaching residue obtained can be subjected to the recovery of carbon and SiO therein based on the known method 2 The separation is carried out, as a typical example, by the following cases, unless specifically stated otherwise, using a method of flotation, in which the steps and conditions of flotation are: adding a flotation agent (the collecting agent is kerosene, the dosage is 950-1000 g/t, the inhibitor is sodium hexametaphosphate 2950-3000 g/t), and obtaining the carbon material and silicon dioxide through flotation.
In the invention, the regenerated carbon material can be subjected to physical and chemical modification by utilizing the operation of the recovery stage and the characteristics of substances, and compared with the raw materials, the performance of the regenerated carbon material is improved, and the invention discloses the improvement of the electrochemical performance by taking the regenerated carbon material as a typical example. In the present invention, as a typical example, the test steps and conditions for the electrochemical performance of the carbon material are:
the performance of the regenerated carbon material is detected by a blue electric test system in the test process, particularly in the test condition. According to the active substances: and (2) a binder: conductive agent = 90:5: 5. The battery cycle rate was set to 1C, the number of cycles was 200, and the test was performed at room temperature (25 ℃).
Example 1:
(1) pretreatment: glass powder and graphite are mixed according to the mass ratio of 1:2, is placed in a tube furnace, is kept at 0.1atm (0.1 atm), 650 ℃ for 2 hours, and is cooled to room temperature along with the furnace.
(2) Leaching lithium: the beaker is placed in a water bath kettle with the constant temperature of 30 ℃ for leaching for 2 hours according to the liquid-solid ratio of 30 ml/g. Then carrying out liquid-solid separation to obtain water immersion liquid and water immersion slag (lithium extraction slag);
(3) acid leaching: leaching lithium extraction slag by using 1M sulfuric acid according to the liquid-solid ratio of 20ml/g, wherein the leaching temperature is 45 ℃ and the time is 1h, so as to obtain acid leaching liquid and acid leaching slag, and washing the acid leaching slag to be neutral and drying to obtain mixed slag containing silicon dioxide and carbon materials;
(4) and (3) flotation: and (3) floating the mixed slag in the step (3) to obtain an upper carbon material and a bottom silicon dioxide. And washing the upper layer solid to be neutral, and drying to obtain the regenerated carbon material.
In the obtained water immersion liquid, the leaching rate of lithium ions is 97.5%; in the pickle liquor, the main ion leaching rates are respectively as follows: ca97.1%, mg97.7% and Al97.8%.
SiO obtained 2 Particle diameter of 20-40 nm and specific surface area of 331m 2 Per gram, the regenerated carbon material can exert 278.2mAhg at the multiplying power of 1C at normal temperature -1 Whereas the graphite starting in step (1) exhibited 207.3mAhg at 1C magnification at normal temperature -1 Is a reversible capacity of (a).
Example 2
The only difference compared to example 1 is that the firing regime is changed to staged heating, i.e. heat is maintained at 550 ℃ for one hour and at 650 ℃ for one hour. Other operations and parameters were the same as in example 1.
In the obtained water immersion liquid, the leaching rate of lithium ions is 98.7%; in the pickle liquor, the leaching rates of each ion are respectively as follows: ca98.3% and Mg982%, 98.5% of Al. SiO obtained 2 Particle diameter of 20-40 nm, specific surface area of 348m 2 Per gram, the derivative carbon material exerts 298.9mAhg at a magnification of 1C at normal temperature -1 Is a reversible capacity of (a).
Example 3
The difference from example 2 is that, after two hours of calcination, air is introduced into the calciner to perform air-cooling treatment, and other processes and parameters are the same as in example 2.
In the obtained water immersion liquid, the leaching rate of lithium ions is 99.1 percent; in the pickle liquor, the leaching rates of each ion are respectively as follows: 99.2% of Ca, 99.3% of Mg and 99.2% of Al. SiO obtained 2 Particle diameter of 20-40 nm and specific surface area of 355m 2 Per gram, the derivative carbon material exerts 302.7mAhg at the multiplying power of 1C at normal temperature -1 Is a reversible capacity of (a).
Example 4
The difference from example 3 is that in step (1), after the baked material was air-cooled to 180 to 200 ℃, distilled water at 10 ℃ was directly injected, water quenching treatment was performed, water was added to a liquid-solid ratio of 30ml/g, water leaching treatment was performed, and water leaching treatment was performed at 10 ℃, and other operations and parameters were the same as in example 3.
In the obtained water immersion liquid, the leaching rate of lithium ions is 99.4%; in the pickle liquor, the leaching rates of each ion are respectively as follows: 99.4% of Ca, 99.1% of Mg and 99.7% of Al. SiO obtained 2 Particle diameter of 20-40 nm and specific surface area of 367m 2 Per gram, the derivative carbon material exerts 312.8mAhg at a magnification of 1C at normal temperature -1 Is a reversible capacity of (a).
Example 5
The only difference compared to example 1 is that the mass ratio of glass frit to graphite is changed to 1:3.
in the obtained water immersion liquid, the leaching rate of lithium ions is 97.6%; in the pickle liquor, the leaching rates of each ion are respectively as follows: 98.7% of Ca, 98.8% of Mg and 98.2% of Al. SiO obtained 2 Particle diameter of 20-40 nm, specific surface area of 347m 2 Per gram, the derivative carbon material exerts 285.9mAhg at a magnification of 1C at normal temperature -1 Is a reversible capacity of (a).
Comparative example 1
The difference from example 1 is that the glass frit was directly subjected to the acid leaching treatment of step 3 without performing the treatment of step (1), and the result was:
in the obtained water immersion liquid, the leaching rate of lithium ions is 41.3%; in the pickle liquor, the leaching rates of each ion are respectively as follows: ca80.3%, mg82.5% and Al81.7%. SiO obtained 2 Particle size of 80-100 nm, specific surface area of 217m 2 /g。
Comparative example 2:
compared with example 1, the difference is only that: in step (1), the calcination stage was carried out not under negative pressure but under normal pressure, and other operations and parameters were the same as in example 1.
In the obtained water immersion liquid, the leaching rate of lithium ions is 78.3%; in the pickle liquor, the leaching rates of each ion are respectively as follows: 71.3% of Ca, 80.2% of Mg and 80.7% of Al. SiO obtained 2 Particle diameter of 80-100 nm and specific surface area of 207m 2 Per gram, the derivative carbon material exerts 223.1mAhg at a magnification of 1C at normal temperature -1 Is a reversible capacity of (a).
Comparative example 3:
compared with example 1, the difference is only that: in the step (1), the baking temperature was changed to 300 ℃. Other operations and parameters were the same as in example 1.
In the obtained water immersion liquid, the leaching rate of lithium ions is 70.5%; in the pickle liquor, the leaching rates of each ion are respectively as follows: ca71.5%, mg72.8% and Al73.8%. SiO obtained 2 Particle diameter of 80-100 nm and specific surface area of 210.2m 2 Per gram, the derivative carbon material exerts 228.5mAhg at the multiplying power of 1C at normal temperature -1 Is a reversible capacity of (a).
Comparative example 4:
compared with example 1, the difference is only that: in step (1), no carbon material was added, and other operations and parameters were the same as in example 1.
In the obtained water immersion liquid, the leaching rate of lithium ions is 55.6%; in the pickle liquor, the leaching rates of each ion are respectively as follows: 65.2% of Ca, 52.7% of Mg and 61.7% of Al. Excessive impurities remain in the slag.
Claims (10)
1. A recovery method of lithium silicon aluminum glass powder is characterized in that the lithium silicon aluminum glass powder and carbonaceous materials are roasted at a temperature of more than 500 ℃ under negative pressure to obtain roasting materials;
carrying out water leaching treatment on the roasting material to obtain lithium liquid and water leaching slag;
and carrying out acid leaching treatment on the water leaching slag to obtain acid leaching liquid enriched with other metal elements in the glass and acid leaching slag.
2. The method for recycling lithium silicon aluminum glass powder according to claim 1, wherein the lithium silicon aluminum glass powder comprises waste Li 2 O-A1 2 O 3 -SiO 2 Powder of solid solution glass;
preferably, the lithium silicon aluminum glass powder further comprises at least one of solid-solution magnesium oxide, calcium oxide and potassium oxide;
preferably, the lithium silicon aluminum glass powder also comprises at least one of Mn, sr and Ni;
preferably, the particle size of the lithium silicon aluminum glass powder is less than or equal to 100 microns; preferably 5 to 100 microns.
3. The method for recovering lithium silica alumina glass powder according to claim 1, wherein the carbonaceous material is at least one of graphite, lignite and pitch.
4. The method for recycling lithium silica alumina glass powder according to claim 1, wherein the weight ratio of the lithium silica alumina glass powder to the carbonaceous material is 1:2 to 5.
5. The method for recovering lithium silica alumina glass powder according to claim 1, wherein the negative pressure is less than or equal to 0.5atm, preferably 0.05 to 0.5atm.
6. The method for recovering lithium aluminosilicate glass powder according to claim 1, wherein the baking temperature is 500-1000 ℃, preferably 500-800 ℃;
preferably, the roasting time is more than 1h, preferably 1-6 h, and further 2-4 h;
preferably, the roasting process comprises a first heat preservation section and a second heat preservation section;
preferably, the temperature of the first heat preservation section is 530-560 ℃, and the temperature of the second heat preservation section is 600-700 ℃;
preferably, the time of the first heat preservation period and the second heat preservation period is respectively 0.5-1.5 h.
7. The method for recovering lithium silica alumina glass powder according to claim 1, wherein the baked material is subjected to air-cooling treatment;
preferably, the air-cooled atmosphere is air.
8. The method for recovering lithium silica alumina glass powder according to claim 7, wherein the baked material is air-cooled to 150-250 ℃, then directly contacted with water at a temperature of less than or equal to 40 ℃ for water quenching treatment, and then water leaching treatment is carried out;
preferably, the liquid-solid ratio in the water leaching stage is 10-50 mL/g;
preferably, the temperature of the water immersion stage is below 40 ℃; further preferably 4 to 30 ℃.
9. The method for recovering lithium silica alumina glass powder according to claim 1, wherein the acid solution in the acid leaching treatment stage is an inorganic strong acid solution with a concentration of 0.5-2M; the inorganic strong acid is preferably at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
the temperature of the acid leaching stage is less than or equal to 60 ℃, preferably 20-45 ℃, and the time of the acid leaching process is 1-4 h.
10. Recovery of lithium silicon aluminum glass powder and co-production of carbon material and SiO 2 The method of (2) is characterized in that the method of any one of claims 1 to 9 is used to obtain acid leaching slag, and the acid leaching slag is subjected to flotation treatment to obtain a modified carbon material and SiO 2 ；
Preferably, the modified carbon material is used as a negative electrode active material of a lithium secondary battery.
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