CN117222767A - Recovery method of waste lithium aluminum silicon microcrystalline glass - Google Patents
Recovery method of waste lithium aluminum silicon microcrystalline glass Download PDFInfo
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- CN117222767A CN117222767A CN202380010133.4A CN202380010133A CN117222767A CN 117222767 A CN117222767 A CN 117222767A CN 202380010133 A CN202380010133 A CN 202380010133A CN 117222767 A CN117222767 A CN 117222767A
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- lithium aluminum
- aluminum silicon
- glass
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- 239000002699 waste material Substances 0.000 title claims abstract description 109
- 239000011521 glass Substances 0.000 title claims abstract description 107
- -1 lithium aluminum silicon Chemical compound 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000011084 recovery Methods 0.000 title claims abstract description 41
- 238000002386 leaching Methods 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000605 extraction Methods 0.000 claims abstract description 62
- 238000000498 ball milling Methods 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 24
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 52
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 52
- 239000002241 glass-ceramic Substances 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 41
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 229910001610 cryolite Inorganic materials 0.000 claims description 32
- 229910001220 stainless steel Inorganic materials 0.000 claims description 30
- 239000010935 stainless steel Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 28
- 238000004064 recycling Methods 0.000 claims description 28
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 239000000243 solution Substances 0.000 description 57
- 238000004519 manufacturing process Methods 0.000 description 23
- 235000017550 sodium carbonate Nutrition 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 17
- 239000000919 ceramic Substances 0.000 description 15
- 238000001514 detection method Methods 0.000 description 14
- 238000001994 activation Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 230000007613 environmental effect Effects 0.000 description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910007926 ZrCl Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910018516 Al—O Inorganic materials 0.000 description 6
- 229910018512 Al—OH Inorganic materials 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003605 opacifier Substances 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 3
- 229910006501 ZrSiO Inorganic materials 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- VRSRNLHMYUACMN-UHFFFAOYSA-H trilithium;hexafluoroaluminum(3-) Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[F-].[F-].[Al+3] VRSRNLHMYUACMN-UHFFFAOYSA-H 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010922 glass waste Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 229910052642 spodumene Inorganic materials 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
- C22B21/00—Obtaining aluminium
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Silicon Compounds (AREA)
Abstract
The application relates to a recovery method of waste lithium aluminum silicon microcrystalline glass, which comprises the following steps: ball milling is carried out on the waste lithium aluminum silicon microcrystalline glass to obtain glass powder; preparing hydrofluoric acid solution with preset concentration as a leaching agent, adding glass powder into the leaching agent according to a preset liquid-solid ratio, leaching according to a preset leaching temperature and a preset leaching time, and filtering to obtain an extract; adding a calcium chloride solution into the extract to dissolve the extract, and filtering to obtain a conversion solution; extracting the conversion liquid, mixing water phases obtained by two-stage extraction to obtain an extracted conversion liquid, mixing oil phases obtained by two-stage extraction to obtain an extraction liquid, back-extracting the extraction liquid in sulfuric acid solution, and filtering to obtain zirconium sulfate; and regulating the pH value of the obtained extracted conversion solution, and filtering to obtain aluminum hydroxide precipitate and lithium-containing solution.
Description
Technical Field
The disclosure relates to the field of waste resource recovery, in particular to a recovery method of waste lithium aluminum silicon glass ceramics.
Background
Glass is a material which has been used for thousands of years, and is closely related to industrial development and people's life. The traditional glass mainly comprises flat glass and daily glass, and basically covers various glass products for life and production. With the increasing consumption demands of glass products, especially glass packaging and decoration glass, the production amount of waste glass is increasing year by year, the waste glass mainly comes from the leftover materials and the normal waste of products in the production process, and the proportion of the waste glass in solid waste reaches 7 percent according to the related statistics of united nations. In the urban household garbage, the waste glass in developed European and American countries accounts for 4-8 percent. The situation in China is also optimistic, the waste glass produced each year is about 1040 ten thousand t, and the waste glass accounts for about 5% of the total amount of solid waste and rises year by year.
However, the waste of the traditional glass is a low-value waste, the quantity of the waste is huge and the waste is difficult to treat, if the waste is recycled, the benefit is not high, and if the waste is discarded for recycling and is directly treated as primary garbage, the environment is not only endangered, but also the resource is wasted; although some conventional glasses are added with metal oxides (such as Li 2 O、Al 2 O 3 、ZrO 2 Etc.), the value of the traditional glass waste is improved to a certain extent, but the recycling benefit is limited.
With the progress of scientific technology, the glass production process has been developed gradually, and new glass produced by new process has appeared on the market, including optical glass, energy glass, etc., wherein lithium aluminum silicon glass (also called lithium aluminum silicon glass-ceramic) is a new high-performance glass, which is prepared from Li 2 O-Al 2 O 3 -SiO 2 The microcrystalline glass is a basic component, is classified from the angle of main crystals, and also comprises quartz solid solution microcrystalline glass with high light permeability and zero expansion performance, spodumene solid solution microcrystalline glass and transparent aluminum lithium silicon microcrystalline glass; compared with common glass, the lithium aluminum silicon glass has the advantages of good chemical stability, high temperature resistance, high hardness, high mechanical strength and the like, and is widely applied in the field of electronic products; compared with the traditional glass waste, the lithium aluminum silicon microcrystalline glass has higher recovery value because the lithium aluminum silicon microcrystalline glass contains relatively more Li, al and Zr. However, there is no report on recovery of waste lithium aluminum silicon glass ceramics.
Disclosure of Invention
Based on the above, the present disclosure aims to provide a recovery method of waste lithium aluminum silicon glass ceramics, which realizes recovery and recycling of Li, al, zr, si in waste lithium aluminum silicon glass ceramics, and prepares Li, al, zr, si obtained by recovery into lithium carbonate, cryolite and zirconium silicate, and has the advantages of high recovery rate, environmental protection, high economic value and the like.
The recovery method of the waste lithium aluminum silicon microcrystalline glass comprises the following steps:
ball milling is carried out on the waste lithium aluminum silicon microcrystalline glass to obtain glass powder;
preparing hydrofluoric acid solution with preset concentration as a leaching agent, adding the glass powder into the leaching agent according to a preset liquid-solid ratio, leaching according to a preset leaching temperature and a preset leaching time, and filtering to obtain a leaching product;
adding a calcium chloride solution into the extract to dissolve the extract, and filtering to obtain a conversion solution;
extracting the conversion liquid, mixing water phases obtained by extraction to obtain an extracted conversion liquid, mixing oil phases obtained by extraction to obtain an extraction liquid, back-extracting the extraction liquid in sulfuric acid solution, and filtering to obtain zirconium sulfate;
and regulating the pH value of the obtained extracted conversion solution, and filtering to obtain aluminum hydroxide precipitate and lithium-containing solution.
The recovery method of the waste lithium aluminum silicon microcrystalline glass realizes the recovery of Li, al and Zr in the waste lithium aluminum silicon microcrystalline glass, and has the advantages of high recovery rate, high economic value and the like.
In an embodiment, the method further comprises the steps of: and adding citric acid and oxalic acid according to a preset molar ratio in the ball milling process. Citric acid and oxalic acid can reduce the energy required for destroying Si/Al-O bonds on the surface of waste glass, namely, the activation energy required by the reaction is reduced, and the decomposition rate of the transition state complex is improved; and the formed surface complex can change the geometric shape of Si/Al-OH bond, so that the waste glass is easier to dissolve.
In one embodiment, the ball milling method comprises the following steps: adding a preset stainless steel ball group into a ball mill, adding the waste lithium aluminum silicon microcrystalline glass into the ball mill according to a preset ball-material ratio, and performing ball milling according to a preset ball milling rotating speed and a preset ball milling time.
In an embodiment, in the leaching step, the preset concentration is 39-41%, the preset liquid-solid ratio is (6:1) - (10:1), the preset leaching temperature is 80-100 ℃, and the preset leaching time is 240-360 min. The preset concentration is more than 41%, the material consumption is excessive, the production cost is excessive, the preset concentration is less than 39%, and the leaching rate of Li is low; the preset liquid-solid ratio is smaller than 6:1, incomplete leaching is easy to occur, and the waste of leaching liquid is caused when the preset liquid-solid ratio is larger than 10:1; the preset leaching temperature is lower than 80 ℃, the leaching reaction is not thorough, the production efficiency is low, the preset temperature is higher than 100 ℃, the energy consumption is excessive, and the leaching effect is limited; if the preset leaching time is too short, the leaching is incomplete, if the preset leaching time is too long, the recovery rhythm is slowed down, and the recovery cost is increased.
In one embodiment, the conversion solution is extracted with a preset extractant compounded from trioctylamine, tributyl phosphate and sulfonated kerosene at a preset oil-water ratio, a preset extraction temperature and a preset extraction time
In one embodiment, the volume ratio of the trioctylamine, the tributyl phosphate, and the sulfonated kerosene is 1:1:4. The volume ratio has high cost performance, the ratio of trioctylamine or tributyl phosphate is improved on the basis, the extraction effect is improved to a certain extent, but the cost improvement range is larger, the ratio of trioctylamine or tributyl phosphate is reduced on the basis, the extraction effect is reduced, and the normal production is influenced.
In an embodiment, the preset oil-water ratio is (2:1) - (3:1), the preset extraction temperature is 25-30 ℃, and the preset extraction time is 5-8 min. If the preset oil-water ratio is less than 2:1, incomplete extraction can occur, and if the preset oil-water ratio is greater than 3:1, on one hand, the extraction capacity of the extractant is excessive, and on the other hand, the time spent in the extraction process is increased due to the increase of the extractant, so that the production efficiency is affected; the extraction temperature is lower than 25 ℃, the extraction efficiency is low, the extraction temperature is higher than 30 ℃, more energy consumption and time are spent for heating, and the production efficiency is influenced due to high energy consumption; the extraction time is too short, so that the extraction is ended after incomplete extraction, and the yield is affected; the extraction time is too long, and the extraction efficiency is affected.
In one embodiment, the predetermined molar ratio is (1:2) - (1:1). The molar ratio is less than 1:2, the activation effect is poor, the molar ratio is more than 1:1, the cost is increased, and the economic benefit is influenced.
In an embodiment, the preset stainless steel ball group comprises a stainless steel ball with the radius of 5mm and a stainless steel ball with the radius of 3mm, and the mass ratio of the stainless steel ball with the radius of 5mm to the stainless steel ball with the radius of 3mm is (1:2-1:1); the preset ball-to-material ratio is (2:1) - (4:1); the preset ball milling rotating speed is 400-600 r/min; the preset ball milling time is 180-240 min. The ball-material ratio is less than 2:1, and the amount of the added materials is excessive and exceeds the ball milling capability, so that the expected ball milling effect cannot be realized; ball material ratio is larger than 4:1, which easily causes waste of ball milling resources; the ball milling rotating speed is small and 400r/min, so that the ball milling speed is low, even the ball milling is uneven, and the device is easy to lose the crushing effect when the ball milling rotating speed is more than 600r/min; the ball milling time is shorter than 180min, and the materials are not completely ball-milled; if the ball milling time is longer than 240min, the ball milling time is too long, and the production efficiency is affected.
In one embodiment, the glass powder has a particle size of 0.2mm to 0.8mm. The granularity is smaller than 0.2mm, the grinding is too fine, the production efficiency is low, the granularity is larger than 0.8mm, and the reaction is insufficient.
In one embodiment, the aluminum hydroxide precipitate is combined with soda ash and hydrofluoric acid to synthesize cryolite. The recovered aluminum hydroxide is further prepared into a high-purity cryolite product, the cryolite has wide industrial application and can be used in electrolytic aluminum industry, glass enamel industry and pesticide manufacturing, so that the further preparation of the aluminum hydroxide into the cryolite can improve the value of the recovered product.
In one embodiment, the zirconium sulfate is reacted with silica to produce zirconium silicate. The zirconium sulfate which is easy to bring environmental risk is further prepared into zirconium silicate, so that on one hand, the possible environmental hazard of the recycled material can be avoided, on the other hand, the zirconium silicate is a high-quality opacifier, and can be used in the production of various building ceramics, artware ceramics and the like, and the value of the recycled material can be improved by preparing the zirconium sulfate into the zirconium silicate.
In one embodiment, the lithium-containing solution is reacted with sodium carbonate to obtain lithium carbonate. The lithium-containing solution is further prepared into lithium carbonate, the lithium carbonate is widely applied in new energy industry, crude lithium carbonate can be sold for customers to prepare battery-grade lithium carbonate, and likewise, battery-grade lithium carbonate can be prepared by self and then sold, and the lithium-grade lithium carbonate is prepared by only extracting and removing impurities from the lithium-containing solution and then preparing lithium carbonate, so that the value of a recovery product can be improved by preparing the lithium-containing solution into the lithium carbonate.
In one embodiment, the silicon tetrafluoride produced in the leaching step is collected, reacted with a sodium carbonate solution to produce hydrofluoric acid, and the hydrofluoric acid derived from the silicon tetrafluoride is used to synthesize the cryolite. The colorless poisonous gas silicon tetrafluoride in the leaching process is collected and converted into hydrofluoric acid for preparing cryolite, so that pollution can be avoided and the cryolite can be recycled.
In one embodiment, the silicon tetrafluoride produced in the leaching step is collected, the silicon tetrafluoride is reacted with a sodium carbonate solution to produce orthosilicic acid, the orthosilicic acid is heated to obtain silica, and the silica derived from the silicon tetrafluoride is used to synthesize the zirconium silicate. The colorless poisonous gas silicon tetrafluoride in the leaching process is collected and converted into silicon dioxide for preparing zirconium silicate, so that pollution can be avoided and the zirconium silicate can be recycled.
In one embodiment, the calcium chloride solution is a hydrochloric acid solution of calcium chloride. The acidic environment can avoid the formation of aluminum hydroxide.
The beneficial effects of the present disclosure are:
1. the Li, al, zr, si in the waste lithium aluminum silicon microcrystalline glass is recycled;
2. realizes the recycling of Li, al, zr, si recovered from waste lithium aluminum silicon microcrystalline glass, and specifically, the Li, al, zr, si recovered is prepared into lithium carbonate, cryolite and zirconium silicate; wherein, the lithium carbonate is widely applied in new energy industry, the crude lithium carbonate can be sold, and the value of the refined lithium carbonate is higher; the cryolite has wide industrial application and can be used in electrolytic aluminum industry, glass enamel industry and pesticide manufacture; zirconium silicate is a high-quality opacifier and can be used in the production of various building ceramics, artware ceramics and the like;
3. the Si-O bond in the waste lithium aluminum silicon glass-ceramic is destroyed by physical actions such as collision among particles, so that the surface defect and the specific surface area of the waste lithium aluminum silicon glass-ceramic are increased, and the reaction capacity of the waste lithium aluminum silicon glass-ceramic is improved. Specifically, after the waste lithium aluminum silicon glass ceramics are ball-milled by a planetary ball mill, the waste lithium aluminum silicon glass ceramics can undergo microstructure collapse, lattice distortion, chemical bond fracture and other processes, so that the reactivity is increased. The structural integrity and the order of silicate in the mechanically activated waste lithium aluminum silicon microcrystalline glass are effectively reduced, so that the raw materials have higher reactivity;
4. by adding citric acid and oxalic acid in the ball milling process, the energy required for destroying Si/Al-O bonds on the surface of waste glass is reduced, namely the activation energy required by the reaction is reduced, and the decomposition rate of the transition state complex is improved; the formed surface complex can change the geometric shape of Si/Al-OH bond, so that the waste glass is easier to dissolve;
5. through the combined action of ball milling and organic acid, the microstructure collapse, lattice distortion and chemical bond fracture of the waste lithium aluminum silicon microcrystalline glass are realized, the reaction activity is increased, and the subsequent recovery is facilitated.
6. Collecting silicon tetrafluoride generated during hydrofluoric acid leaching, and enabling the silicon tetrafluoride and a sodium carbonate solution to undergo incomplete hydrolysis reaction to produce hydrofluoric acid and orthosilicic acid, wherein the hydrofluoric acid is used for participating in the preparation of cryolite, the orthosilicic acid is decomposed to prepare silicon dioxide, and the obtained silicon dioxide is used for participating in the preparation of zirconium silicate; the method realizes the harmlessness and recycling of the silicon tetrafluoride in the way, and the harmful substances are converted into valuable products in a green and efficient way;
7. extracting by adopting a preset extractant compounded by trioctylamine, tributyl phosphate and sulfonated kerosene to separate Zr in the conversion liquid, and obtaining zirconium sulfate by three times of extraction;
8. the recovery method of the waste lithium aluminum silicon glass ceramics has the advantages of high recovery rate, environment-friendly process and great economic value and environmental protection effect.
For a better understanding and implementation, the present disclosure is described in detail below with reference to the drawings.
Drawings
FIG. 1 is an XRD detection result of waste lithium aluminum silicon series microcrystalline glass of model 1 and model 2 selected for use in the present disclosure;
FIG. 2 is a flow chart of a method for recycling waste lithium aluminum silicon glass ceramics according to example 1;
FIG. 3 is an SEM image of the waste lithium aluminum silicon based glass ceramic of example 1 before activation;
FIG. 4 is an SEM image of the waste lithium aluminum silicon based glass ceramic of example 1 after activation;
FIG. 5 shows XRD measurements of high purity cryolite prepared in examples 1-3.
Detailed Description
The recovery method of the waste lithium aluminum silicon microcrystalline glass is suitable for common glass containing SiO 2 、Al 2 O 3 、Li 2 O and ZrO 2 The waste lithium aluminum silicon glass ceramics. In the following examples, the present disclosure exemplifies two common waste lithium aluminum silicon-based glass ceramics (model 1 and model 2), and the present application implements the recovery method of the waste lithium aluminum silicon-based glass ceramics of the present disclosure for model 1. The component contents (wt%) of model 1 and model 2 are shown in the following table 1, XRD detection results of model 1 and model 2 are shown in fig. 1, diffraction peaks of model 1 and model 2 are identical, and the object image composition is identical.
Table 1 component contents of model 1 and model 2
| The components | SiO 2 | Al 2 O 3 | B 2 O 3 | Li 2 O | Na 2 O | MgO | ZrO 2 |
| Model 1 | 60 | 24 | 0.5 | 4.4 | 6.9 | 0.7 | 3.5 |
| Model 2 | 60.1 | 23.8 | 0.5 | 4.2 | 7.1 | 0.9 | 3.4 |
Example 1
The embodiment provides a method for recycling waste lithium aluminum silicon glass ceramics, which is shown in fig. 2 and comprises the following steps:
adding a certain amount of waste lithium aluminum silicon microcrystalline glass into a planetary ball mill, and adding a stainless steel ball group according to a ball-material ratio of 2:1, wherein the stainless steel ball group consists of a stainless steel ball with a radius of 5mm and a stainless steel ball with a radius of 3mm, the mass ratio of the stainless steel ball with a radius of 5mm to the stainless steel ball with a radius of 3mm is 1:2, ball milling for 180min at a ball milling rotating speed of 400r/min, and adding a mixed solution with a mole ratio of 1:2 and a concentration of 1mol/L of citric acid and oxalic acid into the planetary ball mill during the ball milling; after ball milling, obtaining glass powder with the particle size of 0.2 mm-0.8 mm; the steps are the process of activating the waste lithium aluminum silicon microcrystalline glass, and SEM images before and after activation can be seen from fig. 3 and 4, so that the structure of the activated microcrystalline glass is looser; in the activation process, on one hand, si-O bonds in the waste lithium aluminum silicon microcrystalline glass are destroyed by physical actions such as collision among particles, so that the surface defects and the specific surface area of the waste lithium aluminum silicon microcrystalline glass are increased, and the reaction capacity of the waste lithium aluminum silicon microcrystalline glass is improved; on the other hand, the citric acid and oxalic acid can reduce the energy required for destroying Si/Al-O bonds on the surface of the waste glass, namely, the activation energy required for the reaction is reduced, and the decomposition rate of the transition state complex is improved; the formed surface complex can change the geometric shape of Si/Al-OH bond, so that the waste glass is easier to dissolve; through the combined action of ball milling and organic acid, the microstructure collapse, lattice distortion and chemical bond fracture of the waste lithium aluminum silicon microcrystalline glass are realized, the reaction activity is increased, and the subsequent recovery is facilitated.
Then preparing 40% hydrofluoric acid solution as a leaching agent, adding glass powder into the leaching agent according to a liquid-solid ratio of 6:1, leaching for 240min at 80 ℃, collecting gas (mainly silicon tetrafluoride gas) generated in the leaching process, and reacting the gas with sodium carbonate solution to obtain hydrofluoric acid and orthosilicic acid, wherein hydrofluoric acid is used for collecting and temporarily storing, orthosilicic acid is further prepared into silicon dioxide through modes of thermal decomposition and the like, and the silicon dioxide is collected and temporarily stored; and after leaching, filtering to obtain an extract. During leaching, reactions that occur include: liAlSi 2 O 6 +12HF＝＝AlF 3 (s)+LiF(s)+2SiF 4 (g)+6H 2 O; in addition, sodium oxide, zirconium oxide and the like in the waste lithium aluminum silicon glass ceramics react with hydrofluoric acid, so that Al, li and Zr in the lithium aluminum silicon glass ceramics are converted into AlF in the leaching process 3 Precipitation, liF precipitation and ZrF 4 Precipitation (i.e. the extract) is carried out, na in the lithium aluminum silicon glass ceramics is converted into NaF to be dissolved in hydrofluoric acid, si in the lithium aluminum silicon glass ceramics is converted into colorless and toxic SiF 4 The gas, therefore, is filtered through this leaching step, so that the three components of Al, li, zr mixture, na and Si can be separated preliminarily.
Adding hydrochloric acid solution of calcium chloride into the extract to dissolve the extract, and filtering to obtain conversion solution; in this step, the dissolution process involves reactions including: 2LiF+CaCl 2 ＝2LiCl+CaF 2 (s)；2AlF 3 +3CaCl 2 ＝2AlCl 3 +3CaF 2 (s)；ZrF 4 +2CaCl 2 ＝ZrCl 4 +2CaF 2 (s); the components of the conversion solution comprise LiCl and AlCl 3 And ZrCl 4 The contents of the main valuable metal components in the conversion solution are shown in the following table 2.
TABLE 2 content of the main valuable metals in the conversion solution of example 1
| The components | Al | Li | Zr |
| g/L | 14.6 | 3.4 | 4.3 |
Then a mixture of trioctylamine, tributyl phosphate and sulfonated kerosene was used at 1:1:4, mixing the volume ratio of the extracting agent obtained by compounding to 2:1, carrying out secondary extraction on the conversion liquid by oil-water ratio, wherein the extraction time is 5min, the extraction temperature is 25 ℃, mixing water obtained by the two-stage extraction to obtain an extracted conversion liquid, and the components of the extracted conversion liquid comprise LiCl and AlCl 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the oil phases obtained by the two-stage extraction to obtain an extract, wherein the components of the extract comprise ZrCl 4 Wherein the extraction rate of zirconium after the secondary extraction is 99.2%, then the extraction liquid is back extracted in sulfuric acid solution, wherein the back extraction rate of zirconium is 96.23%, and zirconium sulfate is obtained by filtration; zirconium sulfate will be an environmental risk because it is prone to environmental hazardsThe zirconium sulfate is further prepared into zirconium silicate, so that on one hand, the possible environmental hazard of the recycled material can be avoided, on the other hand, the zirconium silicate is a high-quality opacifier, and can be used in the production of various building ceramics, artware ceramics and the like, and the value of the recycled material can be improved by preparing the zirconium sulfate into the zirconium silicate; the method for preparing zirconium silicate comprises the steps of reacting zirconium sulfate with silicon dioxide, wherein in the process of preparing zirconium silicate, silicon dioxide prepared from silicon tetrafluoride gas in the leaching step can be adopted to realize recycling of the recovery product obtained in the leaching step; the zirconium silicate prepared in this example can meet the requirements of the standard of JC/T1094-2009 zirconium silicate for ceramics, and the dry basis detection results are shown in the following Table 3.
TABLE 3 Dry basis detection results of zirconium silicate prepared in example 1
| ZrSiO 4 | TiO 2 | Fe 2 O 3 |
| 99.83％ | 0.08％ | 0.09％ |
And regulating the pH value of the extracted conversion solution by using sodium carbonate until no precipitate is separated out, and filtering to obtain aluminum hydroxide precipitate and lithium-containing solution. The filtered aluminum hydroxide precipitate and sodium carbonate and HF react to synthesize high purity cryolite (Na 3 AlF 6 ) The XRD detection result of the high-purity cryolite prepared in the embodiment is shown in figure 5, the crystal form is good, no obvious impurity peak exists, and the preparation principle is as follows: 12HF+3Na 2 CO 3 +2Al(OH) 3 ＝2Na 3 AlF 6 +3CO 2 +9H 2 O and cryolite have wide industrial application and can be used in electrolytic aluminum industry, glass enamel industry and pesticide manufacturing, so that the further preparation of aluminum hydroxide into cryolite can improve the value of the recycle; in the process of preparing cryolite, HF prepared from silicon tetrafluoride gas in the leaching step can be adopted to realize recycling of the recovery material obtained in the leaching step.
The sodium carbonate is added into the lithium-containing solution to prepare crude lithium carbonate, the lithium carbonate is widely applied in new energy industry, the crude lithium carbonate can be sold for customers to prepare battery-grade lithium carbonate, and the battery-grade lithium carbonate can be sold after being prepared by themselves, and the lithium carbonate is prepared by only extracting and removing impurities from the lithium-containing solution, so that the value of the recovery product can be improved by preparing the lithium-containing solution into the lithium carbonate. The reaction principle is as follows: 2LiCl+Na 2 CO 3 ＝2NaCl+Li 2 CO 3 (s) after washing, the crude lithium carbonate prepared from the lithium-containing solution of the present disclosure can meet the GBT11075-2013 index requirements of lithium carbonate, and the dry basis detection result of the crude lithium carbonate of this example is shown in table 4 below.
TABLE 4 Dry basis test results for crude lithium carbonate prepared in example 1
| Li 2 CO 3 | Na | Fe | Ca | Mg | Cl - | SO 4 2- |
| 99.305％ | 0.08％ | 0.07％ | 0.2％ | 0.015％ | 0.02％ | 0.31％ |
Example 2
The embodiment provides a recovery method of waste lithium aluminum silicon glass ceramics, which comprises the following steps:
adding a certain amount of waste lithium aluminum silicon microcrystalline glass into a planetary ball mill, and adding a stainless steel ball group according to a ball-material ratio of 4:1, wherein the stainless steel ball group consists of a stainless steel ball with the radius of 5mm and a stainless steel ball with the radius of 3mm, the mass ratio of the stainless steel ball with the radius of 5mm to the stainless steel ball with the radius of 3mm is 1:1, ball milling is carried out for 240min at a ball milling rotating speed of 600r/min, and in the ball milling process, mixed liquid with the mole ratio of citric acid to oxalic acid of 1:1 and the concentration of 1mol/L is added into the planetary ball mill; after ball milling, obtaining glass powder with the particle size of 0.2 mm-0.8 mm; the method comprises the steps of activating the waste lithium aluminum silicon microcrystalline glass, so that the structure of the activated microcrystalline glass is looser; in the activation process, on one hand, si-O bonds in the waste lithium aluminum silicon microcrystalline glass are destroyed by physical actions such as collision among particles, so that the surface defects and the specific surface area of the waste lithium aluminum silicon microcrystalline glass are increased, and the reaction capacity of the waste lithium aluminum silicon microcrystalline glass is improved; on the other hand, the citric acid and oxalic acid can reduce the energy required for destroying Si/Al-O bonds on the surface of the waste glass, namely, the activation energy required for the reaction is reduced, and the decomposition rate of the transition state complex is improved; the formed surface complex can change the geometric shape of Si/Al-OH bond, so that the waste glass is easier to dissolve; through the combined action of ball milling and organic acid, the microstructure collapse, lattice distortion and chemical bond fracture of the waste lithium aluminum silicon microcrystalline glass are realized, the reaction activity is increased, and the subsequent recovery is facilitated.
Then preparing 40% hydrofluoric acid solution as a leaching agent, adding glass powder into the leaching agent according to a liquid-solid ratio of 6:1, leaching for 180min at 70 ℃, collecting gas (mainly silicon tetrafluoride gas) generated in the leaching process, and reacting the gas with sodium carbonate solution to obtain hydrofluoric acid and orthosilicic acid, wherein hydrofluoric acid is used for collecting and temporarily storing, orthosilicic acid is further prepared into silicon dioxide through modes of thermal decomposition and the like, and the silicon dioxide is collected and temporarily stored; and after leaching, filtering to obtain an extract. During leaching, reactions that occur include: liAlSi 2 O 6 +12HF＝＝AlF 3 (s)+LiF(s)+2SiF 4 (g)+6H 2 O; in addition, sodium oxide, zirconium oxide and the like in the waste lithium aluminum silicon glass ceramics react with hydrofluoric acid, so that Al, li and Zr in the lithium aluminum silicon glass ceramics are converted into AlF in the leaching process 3 Precipitation, liF precipitation and ZrF 4 Precipitation (i.e. the extract) is carried out, na in the lithium aluminum silicon glass ceramics is converted into NaF to be dissolved in hydrofluoric acid, si in the lithium aluminum silicon glass ceramics is converted into colorless and toxic SiF 4 The gas, therefore, is filtered through this leaching step, so that the three components of Al, li, zr mixture, na and Si can be separated preliminarily.
Adding hydrochloric acid solution of calcium chloride into the extract to dissolve the extract, and filtering to obtain conversion solution; in this step, the dissolution process involves reactions including: 2LiF+CaCl 2 ＝2LiCl+CaF 2 (s)；2AlF 3 +3CaCl 2 ＝2AlCl 3 +3CaF 2 (s)；ZrF 4 +2CaCl 2 ＝ZrCl 4 +2CaF 2 (s); the components of the conversion solution comprise LiCl and AlCl 3 And ZrCl 4 The contents of the main valuable metal components in the conversion solution are shown in Table 5 below.
TABLE 5 content of the Main valuable metals in the conversion solution of example 2
| The components | Al | Li | Zr |
| g/L | 14.52 | 3.35 | 4.25 |
Then a mixture of trioctylamine, tributyl phosphate and sulfonated kerosene was used at 1:1:4, mixing the volume ratio of the extracting agent obtained by compounding to 2:1, carrying out secondary extraction on the conversion liquid by oil-water ratio, wherein the extraction time is 8min, the extraction temperature is 30 ℃, mixing water obtained by the two-stage extraction to obtain an extracted conversion liquid, and the components of the extracted conversion liquid comprise LiCl and AlCl 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the oil phases obtained by the two-stage extraction to obtain an extract, wherein the components of the extract comprise ZrCl 4 Wherein the extraction rate of zirconium after the secondary extraction is 99.8%, then the extraction liquid is back extracted in sulfuric acid solution, wherein the back extraction rate of zirconium is 99.23%, and zirconium sulfate is obtained by filtration; because the zirconium sulfate is easy to bring environmental risk, the zirconium sulfate is further prepared into zirconium silicate, so that on one hand, the possible environmental hazard of the recycled material can be avoided, and on the other hand, the zirconium silicate is a high-quality opacifier, can be used in the production of various building ceramics, artware ceramics and the like, and the value of the recycled material can be improved by preparing the zirconium sulfate into the zirconium silicate; the method for preparing zirconium silicate comprises the steps of reacting zirconium sulfate with silicon dioxide, wherein in the process of preparing zirconium silicate, the zirconium silicate can be prepared from silicon tetrafluoride gas in a leaching stepThe recycling of the recovery obtained in the leaching step is realized; the zirconium silicate prepared in this example can meet the requirements of the standard of JC/T1094-2009 zirconium silicate for ceramics, and the dry basis detection results are shown in the following Table 6.
TABLE 6 Dry basis detection results of zirconium silicate prepared in example 2
| ZrSiO 4 | TiO 2 | Fe 2 O 3 |
| 99.85％ | 0.07％ | 0.08％ |
And regulating the pH value of the extracted conversion solution by using sodium carbonate until no precipitate is separated out, and filtering to obtain aluminum hydroxide precipitate and lithium-containing solution. The filtered aluminum hydroxide precipitate and sodium carbonate and HF react to synthesize high purity cryolite (Na 3 AlF 6 ) The XRD detection result of the high-purity cryolite prepared in the embodiment is shown in figure 5, the crystal form is good, no obvious impurity peak exists, and the preparation principle is as follows: 12HF+3Na 2 CO 3 +2Al(OH) 3 ＝2Na 3 AlF 6 +3CO 2 +9H 2 O and cryolite have wide industrial application and can be used in electrolytic aluminum industry, glass enamel industry and pesticide manufacturing, so that the further preparation of aluminum hydroxide into cryolite can improve the value of the recycle; in the process of preparing cryolite, HF prepared from silicon tetrafluoride gas in the leaching step can be adopted to realize recycling of the recovery material obtained in the leaching step.
The sodium carbonate is added into the lithium-containing solution to prepare crude lithium carbonate, the lithium carbonate is widely applied in new energy industry, the crude lithium carbonate can be sold for customers to prepare battery-grade lithium carbonate, and the battery-grade lithium carbonate can be sold after being prepared by themselves, and the lithium carbonate is prepared by only extracting and removing impurities from the lithium-containing solution, so that the value of the recovery product can be improved by preparing the lithium-containing solution into the lithium carbonate. The reaction principle is as follows: 2LiCl+Na 2 CO 3 ＝2NaCl+Li 2 CO 3 (s) after washing, the crude lithium carbonate prepared from the lithium-containing solution of the present disclosure can meet the GBT11075-2013 index requirements of lithium carbonate, and the dry basis detection result of the crude lithium carbonate of this example is shown in table 7 below.
TABLE 7 Dry basis test results for crude lithium carbonate prepared in example 2
| Li 2 CO 3 | Na | Fe | Ca | Mg | Cl - | SO 4 2- |
| 99.205％ | 0.08％ | 0.07％ | 0.25％ | 0.015％ | 0.03％ | 0.35％ |
Example 3
The embodiment provides a recovery method of waste lithium aluminum silicon glass ceramics, which comprises the following steps:
adding a certain amount of waste lithium aluminum silicon microcrystalline glass into a planetary ball mill, and adding a stainless steel ball group according to a ball-material ratio of 4:1, wherein the stainless steel ball group consists of a stainless steel ball with the radius of 5mm and a stainless steel ball with the radius of 3mm, the mass ratio of the stainless steel ball with the radius of 5mm to the stainless steel ball with the radius of 3mm is 1:1, ball milling is carried out for 240min at a ball milling rotating speed of 600r/min, and in the ball milling process, mixed liquid with the mole ratio of citric acid to oxalic acid of 1:1 and the concentration of 1mol/L is added into the planetary ball mill; after ball milling, obtaining glass powder with the particle size of 0.2 mm-0.8 mm; the method comprises the steps of activating the waste lithium aluminum silicon microcrystalline glass, so that the structure of the activated microcrystalline glass is looser; in the activation process, on one hand, si-O bonds in the waste lithium aluminum silicon microcrystalline glass are destroyed by physical actions such as collision among particles, so that the surface defects and the specific surface area of the waste lithium aluminum silicon microcrystalline glass are increased, and the reaction capacity of the waste lithium aluminum silicon microcrystalline glass is improved; on the other hand, the citric acid and oxalic acid can reduce the energy required for destroying Si/Al-O bonds on the surface of the waste glass, namely, the activation energy required for the reaction is reduced, and the decomposition rate of the transition state complex is improved; the formed surface complex can change the geometric shape of Si/Al-OH bond, so that the waste glass is easier to dissolve; through the combined action of ball milling and organic acid, the microstructure collapse, lattice distortion and chemical bond fracture of the waste lithium aluminum silicon microcrystalline glass are realized, the reaction activity is increased, and the subsequent recovery is facilitated.
Then preparing 40% hydrofluoric acid solution as a leaching agent, adding glass powder into the leaching agent according to a liquid-solid ratio of 6:1, leaching for 180min at 70 ℃, and collecting gas (mainSilicon tetrafluoride gas), and reacting the gas with sodium carbonate solution to obtain hydrofluoric acid and orthosilicic acid, wherein the hydrofluoric acid is collected and temporarily stored, the orthosilicic acid is further prepared into silicon dioxide through modes of heating decomposition and the like, and the silicon dioxide is collected and temporarily stored; and after leaching, filtering to obtain an extract. During leaching, reactions that occur include: liAlSi 2 O 6 +12HF＝＝AlF 3 (s)+LiF(s)+2SiF 4 (g)+6H 2 O; in addition, sodium oxide, zirconium oxide and the like in the waste lithium aluminum silicon glass ceramics react with hydrofluoric acid, so that Al, li and Zr in the lithium aluminum silicon glass ceramics are converted into AlF in the leaching process 3 Precipitation, liF precipitation and ZrF 4 Precipitation (i.e. the extract) is carried out, na in the lithium aluminum silicon glass ceramics is converted into NaF to be dissolved in hydrofluoric acid, si in the lithium aluminum silicon glass ceramics is converted into colorless and toxic SiF 4 The gas, therefore, is filtered through this leaching step, so that the three components of Al, li, zr mixture, na and Si can be separated preliminarily.
Adding hydrochloric acid solution of calcium chloride into the extract to dissolve the extract, and filtering to obtain conversion solution; in this step, the dissolution process involves reactions including: 2LiF+CaCl 2 ＝2LiCl+CaF 2 (s)；2AlF 3 +3CaCl 2 ＝2AlCl 3 +3CaF 2 (s)；ZrF 4 +2CaCl 2 ＝ZrCl 4 +2CaF 2 (s); the components of the conversion solution comprise LiCl and AlCl 3 And ZrCl 4 The contents of the main valuable metal components in the conversion solution are shown in the following table 8.
TABLE 8 content of the Main valuable metals in the conversion solution of example 3
| The components | Al | Li | Zr |
| g/L | 14.51 | 3.37 | 4.2 |
Then a mixture of trioctylamine, tributyl phosphate and sulfonated kerosene was used at 1:1:4, mixing the volume ratio of the extracting agent obtained by compounding to 2:1, carrying out secondary extraction on the conversion liquid by oil-water ratio, wherein the extraction time is 8min, the extraction temperature is 30 ℃, mixing water obtained by the two-stage extraction to obtain an extracted conversion liquid, and the components of the extracted conversion liquid comprise LiCl and AlCl 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the oil phases obtained by the two-stage extraction to obtain an extract, wherein the components of the extract comprise ZrCl 4 Wherein the extraction rate of zirconium after the secondary extraction is 99.8%, then the extraction liquid is back extracted in sulfuric acid solution, wherein the back extraction rate of zirconium is 99.23%, and zirconium sulfate is obtained by filtration; because the zirconium sulfate is easy to bring environmental risk, the zirconium sulfate is further prepared into zirconium silicate, so that on one hand, the possible environmental hazard of the recycled material can be avoided, and on the other hand, the zirconium silicate is a high-quality opacifier, can be used in the production of various building ceramics, artware ceramics and the like, and the value of the recycled material can be improved by preparing the zirconium sulfate into the zirconium silicate; the method for preparing zirconium silicate comprises the steps of reacting zirconium sulfate with silicon dioxide, wherein in the process of preparing zirconium silicate, silicon dioxide prepared from silicon tetrafluoride gas in the leaching step can be adopted to realize recycling of the recovery product obtained in the leaching step; the zirconium silicate prepared in this example can meet the requirements of the standard of JC/T1094-2009 zirconium silicate for ceramics, and the dry basis detection results are shown in the following Table 9.
TABLE 9 Dry basis detection results of zirconium silicate prepared in example 3
| ZrSiO 4 | TiO 2 | Fe 2 O 3 |
| 99.83％ | 0.07％ | 0.1％ |
And regulating the pH value of the extracted conversion solution by using sodium carbonate until no precipitate is separated out, and filtering to obtain aluminum hydroxide precipitate and lithium-containing solution. The filtered aluminum hydroxide precipitate and sodium carbonate and HF react to synthesize high purity cryolite (Na 3 AlF 6 ) The XRD detection result of the high-purity cryolite prepared in the embodiment is shown in figure 5, the crystal form is good, no obvious impurity peak exists, and the preparation principle is as follows: 12HF+3Na 2 CO 3 +2Al(OH) 3 ＝2Na 3 AlF 6 +3CO 2 +9H 2 O and cryolite have wide industrial application and can be used in electrolytic aluminum industry, glass enamel industry and pesticide manufacturing, so that the further preparation of aluminum hydroxide into cryolite can improve the value of the recycle; in the process of preparing cryolite, HF prepared from silicon tetrafluoride gas in the leaching step can be adopted to realize recycling of the recovery material obtained in the leaching step.
The sodium carbonate is added into the lithium-containing solution to prepare crude lithium carbonate, the lithium carbonate is widely applied in new energy industry, the crude lithium carbonate can be sold for customers to prepare battery-grade lithium carbonate, and the battery-grade lithium carbonate can be sold after being prepared by themselves, and the lithium carbonate is prepared by only extracting and removing impurities from the lithium-containing solution, so that the value of the recovery product can be improved by preparing the lithium-containing solution into the lithium carbonate. The reaction principle is that：2LiCl+Na 2 CO 3 ＝2NaCl+Li 2 CO 3 (s) after washing, the crude lithium carbonate prepared from the lithium-containing solution of the present disclosure can meet the GBT11075-2013 index requirements of lithium carbonate, and the dry basis detection results of the crude lithium carbonate of this example are shown in table 10 below.
TABLE 10 Dry basis test results for crude lithium carbonate prepared in example 3
| Li 2 CO 3 | Na | Fe | Ca | Mg | Cl - | SO 4 2- |
| 99.325％ | 0.08％ | 0.07％ | 0.13％ | 0.015％ | 0.03％ | 0.35％ |
The beneficial effects of the present disclosure are:
1. the Li, al, zr, si in the waste lithium aluminum silicon microcrystalline glass is recycled;
2. realizes the recycling of Li, al, zr, si recovered from waste lithium aluminum silicon microcrystalline glass, and specifically, the Li, al, zr, si recovered is prepared into lithium carbonate, cryolite and zirconium silicate; wherein, the lithium carbonate is widely applied in new energy industry, the crude lithium carbonate can be sold, and the value of the refined lithium carbonate is higher; the cryolite has wide industrial application and can be used in electrolytic aluminum industry, glass enamel industry and pesticide manufacture; zirconium silicate is a high-quality opacifier and can be used in the production of various building ceramics, artware ceramics and the like;
3. the Si-O bond in the waste lithium aluminum silicon glass-ceramic is destroyed by physical actions such as collision among particles, so that the surface defect and the specific surface area of the waste lithium aluminum silicon glass-ceramic are increased, and the reaction capacity of the waste lithium aluminum silicon glass-ceramic is improved. Specifically, after the waste lithium aluminum silicon glass ceramics are ball-milled by a planetary ball mill, the waste lithium aluminum silicon glass ceramics can undergo microstructure collapse, lattice distortion, chemical bond fracture and other processes, so that the reactivity is increased. The structural integrity and the order of silicate in the mechanically activated waste lithium aluminum silicon microcrystalline glass are effectively reduced, so that the raw materials have higher reactivity;
4. by adding citric acid and oxalic acid in the ball milling process, the energy required for destroying Si/Al-O bonds on the surface of waste glass is reduced, namely the activation energy required by the reaction is reduced, and the decomposition rate of the transition state complex is improved; the formed surface complex can change the geometric shape of Si/Al-OH bond, so that the waste glass is easier to dissolve;
5. through the combined action of ball milling and organic acid, the microstructure collapse, lattice distortion and chemical bond fracture of the waste lithium aluminum silicon microcrystalline glass are realized, the reaction activity is increased, and the subsequent recovery is facilitated.
6. Collecting silicon tetrafluoride generated during hydrofluoric acid leaching, and enabling the silicon tetrafluoride and a sodium carbonate solution to undergo incomplete hydrolysis reaction to produce hydrofluoric acid and orthosilicic acid, wherein the hydrofluoric acid is used for participating in the preparation of cryolite, the orthosilicic acid is decomposed to prepare silicon dioxide, and the obtained silicon dioxide is used for participating in the preparation of zirconium silicate; the method realizes the harmlessness and recycling of the silicon tetrafluoride in the way, and the harmful substances are converted into valuable products in a green and efficient way;
7. extracting by adopting a preset extractant compounded by trioctylamine, tributyl phosphate and sulfonated kerosene to separate Zr in the conversion liquid, and obtaining zirconium sulfate by three times of extraction;
8. the recovery method of the waste lithium aluminum silicon glass ceramics has the advantages of high recovery rate, environment-friendly process and great economic value and environmental protection effect.
Claims (16)
1. The recovery method of the waste lithium aluminum silicon microcrystalline glass is characterized by comprising the following steps of:
ball milling is carried out on the waste lithium aluminum silicon microcrystalline glass to obtain glass powder;
preparing hydrofluoric acid solution with preset concentration as a leaching agent, adding the glass powder into the leaching agent according to a preset liquid-solid ratio, leaching according to a preset leaching temperature and a preset leaching time, and filtering to obtain a leaching product;
adding a calcium chloride solution into the extract to dissolve the extract, and filtering to obtain a conversion solution;
extracting the conversion liquid, mixing water phases obtained by extraction to obtain an extracted conversion liquid, mixing oil phases obtained by extraction to obtain an extraction liquid, back-extracting the extraction liquid in sulfuric acid solution, and filtering to obtain zirconium sulfate;
and regulating the pH value of the obtained extracted conversion solution, and filtering to obtain aluminum hydroxide precipitate and lithium-containing solution.
2. The method for recycling waste lithium aluminum silicon series glass ceramics according to claim 1, further comprising the steps of: and adding citric acid and oxalic acid according to a preset molar ratio in the ball milling process.
3. The method for recycling waste lithium aluminum silicon series microcrystalline glass according to claim 1, wherein the ball milling method is as follows: adding a preset stainless steel ball group into a ball mill, adding the waste lithium aluminum silicon microcrystalline glass into the ball mill according to a preset ball-material ratio, and performing ball milling according to a preset ball milling rotating speed and a preset ball milling time.
4. The method for recycling waste lithium aluminum silicon series glass ceramics according to claim 1, wherein in the leaching step, the preset concentration is 39-41 wt%, the preset liquid-solid ratio is (6:1) - (10:1), the preset leaching temperature is 80-100 ℃, and the preset leaching time is 240-360 min.
5. The method for recycling waste lithium aluminum silicon series glass ceramics according to claim 1, wherein the conversion solution is extracted by adopting a preset extractant compounded by trioctylamine, tributyl phosphate and sulfonated kerosene according to a preset oil-water ratio, a preset extraction temperature and a preset extraction time.
6. The method for recycling waste lithium aluminum silicon series microcrystalline glass according to claim 5, wherein the volume ratio of trioctylamine to tributyl phosphate to sulfonated kerosene is 1:1:4.
7. The method for recycling waste lithium aluminum silicon series glass ceramics according to claim 5, wherein the preset oil-water ratio is (2:1) - (3:1), the preset extraction temperature is 25-30 ℃, and the preset extraction time is 5-8 min.
8. The method for recycling waste lithium aluminum silicon series microcrystalline glass according to claim 2, wherein the preset molar ratio is (1:2) - (1:1).
9. The method for recycling waste lithium aluminum silicon glass ceramics according to claim 3, wherein the preset stainless steel ball group comprises stainless steel balls with the radius of 5mm and stainless steel balls with the radius of 3mm, and the mass ratio of the stainless steel balls with the radius of 5mm to the stainless steel balls with the radius of 3mm is (1:2) - (1:1); the preset ball-to-material ratio is (2:1) - (4:1); the preset ball milling rotating speed is 400-600 r/min; the preset ball milling time is 180-240 min.
10. The method for recycling waste lithium aluminum silicon glass ceramics according to claim 1, wherein the granularity of the glass powder is 0.2 mm-0.8 mm.
11. The method for recycling waste lithium aluminum silicon series glass ceramics according to claim 1, wherein the aluminum hydroxide precipitate, sodium carbonate and hydrofluoric acid are synthesized into cryolite.
12. The method for recycling waste lithium aluminum silicon glass ceramics according to claim 1, wherein zirconium sulfate is reacted with silica to produce zirconium silicate.
13. The method for recycling waste lithium aluminum silicon glass ceramics according to claim 1, wherein lithium carbonate is obtained by reacting the lithium-containing solution with sodium carbonate.
14. The method according to claim 11, wherein silicon tetrafluoride produced in the leaching step is collected, the silicon tetrafluoride is reacted with a sodium carbonate solution to produce hydrofluoric acid, and the hydrofluoric acid derived from the silicon tetrafluoride is used for synthesizing the cryolite.
15. The method according to claim 12, wherein silicon tetrafluoride produced in the leaching step is collected, the silicon tetrafluoride is reacted with a sodium carbonate solution to produce orthosilicic acid, the orthosilicic acid is heated to obtain silica, and the silica derived from the silicon tetrafluoride is used for synthesizing the zirconium silicate.
16. The method for recycling waste lithium aluminum silicon glass ceramics according to claim 1, wherein the calcium chloride solution is a hydrochloric acid solution of calcium chloride.
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| PCT/CN2023/109572 WO2024037305A1 (en) | 2023-07-27 | 2023-07-27 | Method for recovering waste lithium-aluminum-silicon glass ceramic |
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| CN102344251B (en) * | 2011-07-20 | 2013-07-10 | 大连交通大学 | Preparation method for lepidolite glass ceramic |
| CN102745837A (en) * | 2012-07-18 | 2012-10-24 | 上海交通大学 | Method for treating and recycling glass thinning and etching waste liquor |
| CN106145685A (en) * | 2016-06-24 | 2016-11-23 | 湖南省小尹无忌环境能源科技开发有限公司 | A kind of resource utilization method of useless laminated glass |
| CN109437255B (en) * | 2018-11-25 | 2021-04-16 | 长沙市原鹏化工科技有限公司 | Method for extracting lithium carbonate from lithium ore |
| JP7121676B2 (en) * | 2019-03-07 | 2022-08-18 | Ｕｂｅ三菱セメント株式会社 | WASTE GLASS PROCESSING METHOD AND PROCESSING DEVICE |
| CN113233789B (en) * | 2021-06-30 | 2023-05-30 | 重庆鑫景特种玻璃有限公司 | Recycling method of reinforced microcrystalline glass |
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