AU2019210383B2 - High-value comprehensive utilization method for lithium slag - Google Patents
High-value comprehensive utilization method for lithium slag Download PDFInfo
- Publication number
- AU2019210383B2 AU2019210383B2 AU2019210383A AU2019210383A AU2019210383B2 AU 2019210383 B2 AU2019210383 B2 AU 2019210383B2 AU 2019210383 A AU2019210383 A AU 2019210383A AU 2019210383 A AU2019210383 A AU 2019210383A AU 2019210383 B2 AU2019210383 B2 AU 2019210383B2
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- AU
- Australia
- Prior art keywords
- lithium
- slag
- flotation
- magnetic separation
- lithium slag
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 177
- 239000002893 slag Substances 0.000 title claims abstract description 144
- 238000000034 method Methods 0.000 title claims abstract description 95
- 229910052903 pyrophyllite Inorganic materials 0.000 claims abstract description 68
- 239000003365 glass fiber Substances 0.000 claims abstract description 61
- 238000007885 magnetic separation Methods 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 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 claims abstract description 32
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 32
- 239000004568 cement Substances 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010440 gypsum Substances 0.000 claims abstract description 20
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000004566 building material Substances 0.000 claims abstract description 12
- 229910052600 sulfate mineral Inorganic materials 0.000 claims abstract description 12
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 8
- 230000023556 desulfurization Effects 0.000 claims abstract description 8
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005188 flotation Methods 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 39
- 230000002000 scavenging effect Effects 0.000 claims description 24
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 17
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 17
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 17
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000005642 Oleic acid Substances 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 17
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 230000005484 gravity Effects 0.000 claims description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 13
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- -1 amine salt Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000007380 fibre production Methods 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 13
- 239000011707 mineral Substances 0.000 abstract description 13
- 239000002002 slurry Substances 0.000 abstract 4
- 239000011449 brick Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 50
- 238000002360 preparation method Methods 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 11
- 229910052629 lepidolite Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000004567 concrete Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000006246 high-intensity magnetic separator Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940005740 hexametaphosphate Drugs 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [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 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical group [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/42—Glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0481—Other specific industrial waste materials not provided for elsewhere in C04B18/00
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0006—Alkali metal or inorganic ammonium compounds
- C04B2103/0008—Li
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
A comprehensive utilization method for lithium slag, which is used on slag obtained after extracting lithium from spodumene by means of a sulfuric acid method and which comprises the following steps: (1) slurrying and stirring lithium slag such that a sulfate mineral in the lithium slag is in a dispersed suspension state; (2) desulfurizing the product obtained in step (1) by using a manner of physical mineral separation to obtain a desulfurization slurry and a tailing output slag; (3) magnetically separating the desulfurized slurry obtained in step (2) under the condition of a magnetic field strength of 0.5-2.0 T to obtain a magnetic separation slurry and a magnetic separation tailing slag; then, concentrating, filtering and drying the obtained magnetic separation slurry to obtain a pyrophyllite raw material for use with glass fiber. The tailing output slag obtained in step (2) is dried and dehydrated, and then used as a gypsum-based putty or a mortar filler raw material; the magnetic separation slag obtained in step (3) is used as a building material, and the building material comprises a cement admixture or a brick making raw material.
Description
High-value Comprehensive Utilization Method for Lithium Slag
Field of the Invention
The present invention relates to the green and environmental protection disposal field of industrial solid waste, and involves the comprehensive utilization field of lithium slag, especially to a high-value green and comprehensive utilization treatment method for lithium slag.
Background of the Invention
The content of lithium in the earth's crust is about 0.0065%. It mainly exists in salt lake brine, spodumene, lepidolite, petalite and lasionite, and is mainly distributed in Bolivia, Chile, China, Argentina, the United States, Australia, Russia, Canada and Serbia, etc.
Spodumene ores are mainly distributed in Australia, Canada, Zimbabwe, Congo, Brazil and China; lepidolite ores are mainly distributed in Zimbabwe, Canada, the United States, Mexico and China. In China, spodumene is mainly concentrated in Sichuan Province, Xinjiang, Henan Province, and lepidolite is mainly concentrated in Jiangxi Province and Hunan Province.
Lithium slag is a general term for the waste slag produced after extracting lithium from lithium-rich resources. At present, lithium is mainly extracted from lithium ores in China. Lithium is mainly extracted from lepidolite by sodium chloride pressure cooking and from spodumene by sulfuric acid. Therefore, the lithium slag in China is mainly the slag of lithium-extracted by-products produced by the above two methods.
In recent years, China's lithium battery industry has developed rapidly, and the localization process of key materials is also accelerating, resulting in increasing demand for related lithium products. Meanwhile, the production of lithium slag is increasing, and the environmental pollution caused by lithium slag is becoming more and more serious. The best way to solve this problem is to recycle the lithium slag and make it into other industrial products. In this regard, some attempts have been made with existing technology.
The Chinese patent CN102126838A discloses a method for preparing lightweight building material ceramicite with lithium slag from lepidolite. The lightweight building material ceramsite can be obtained by high temperature sintering after adding clay powder and pore-forming agent, and its quality satisfies the quality requirements of excellent lightweight aggregate as specified in GB/T17431.2-1998. With this method, the extracted lithium slag from lepidolite can be recycled, but its processing added value is very limited. Compared with other raw materials used for the preparation of lightweight building material ceramsite, it does not produce significant cost reduction and value-added improvement effect. Similarly, the Chinese patent CN103979809A also has similar problems.
Influence of Lithium Slag from Lepidolite on the Durability of Concrete (doi:10.1088/1755-1315/61/1/012151) also studies the lithium slag from lepidolite as cement additive, and finds that it can improve the quality of cement.
Nanoindentation Characteristics of Cementitious Materials Containing Lithium Slag (DOI: 10.1166/nnl.2017.2276), Utilization of Lithium Slag as An Admixture in Blended Cements: Physico-mechanical and Hydration Characteristics (DOI: 10.1007/11595-015-1113-x), Mechanical Properties of Concretes Containing Super-fine Mineral Admixtures (DOI: 10.4028/www.scientific.net/AMM.174-177.1406) and Study on PreparingAero-Concrete Using Leaching Residual Slag of Lepidolite ore (DOI: 10.4028/www.scientific.net/AMM.99-100.375) study on lithium slag as cement additive in different aspects.
The Chinese patent CN 103922626A provides a recycling method for lithium slag, a lithium by-product from salt lake, to prepare concrete alkali aggregate reaction inhibitor. The inhibitor for concrete alkali aggregate reaction is prepared by reducing the harmful component, namely sodium chloride, in lithium slag. Similarly, this method can recycle the waste lithium slag to a certain extent, but its added value is not greatly improved.
The problem with these and other similar existing technologies is that these technologies can only realize the low-value and single-application recovery processing of lithium slag. As the production industry of concrete materials, cement, building material ceramsite, etc. has already developed into a mature industry, lithium slag as the raw material for these products does not have advantages, so it can not solve the problem of lithium slag recycling.
There are two ways to solve the low recycling value of lithium slag. One is to study the comprehensive utilization method of lithium slag, so that all parts of the lithium slag can be effectively utilized after processing; the other is to enable lithium slag become a competitive high-value product after processing.
The Chinese patent CN 103789553A provides a method for comprehensive utilization of lithium slag by phase reconstruction of lepidolite. Calcium chloride, aluminum rich slag, aluminosilicate and fluorite concentrate can be obtained by adding acid and alkali solutions for processing and then countercurrent flotation. Although a variety of products can be obtained by this technology, it does not have obvious advantages compared with other ways. Moreover, the technology requires a large amount of acid-base solution, which is easy to cause pollution, making it impossible to recover lithium slag to avoid pollution.
The Chinese patent CN 103601230A provides a method for comprehensive utilization of lithium slag to produce chemical raw materials, which absorbs the exhaust gas with ammonia water to reduce the pollution of waste gas and reduce the pollution of waste water as the liquid is not directly discharged. In the said invention, the calcium chloride, ammonium fluoride, silica, aluminum salt and ammonium sulfate were obtained in multiple steps. Compared with CN 103789553A, the patent has made certain progress in reducing water, gas and slag emission, but the products obtained by it have no obvious advantages compared with other common preparation methods. In addition, the patent also requires a large amount of acid-base solutions, and its safety and pollution control problems make it difficult to popularize.
The lithium slag as mentioned in the patent is a by-product slag obtained by extracting lithium from lepidolite or salt lake.
At present, the research on how to deal with the lithium slag produced by extracting lithium from spodumene has been carried out in China. When extracting lithium carbonate from spodumene using the sulfuric acid method, about 8-10 tons of lithium slag will be discharged when producing 1 ton of lithium salt. As a result, how to deal with the lithium slag becomes an urgent problem. However, the research on this aspect is still in the preliminary stage, so the high-value, green and efficient comprehensive utilization of lithium slag have not been realized.
The Discussion on the Source of Lithium Slag and the Strengthening Impermeability Mechanism of Lithium Slag Concrete (Sichuan Nonferrous Metals, Issue 04, 2000) proposes the technology of using lithium slag as the concrete enhancer and cement additive. However, the supply-side structural reform in China has the requirements of "cutting overcapacity, reducing excess inventory, deleveraging, lowering costs, and strengthening areas of weakness" for the cement industry, so the application of lithium slag as cement additive will be limited. In addition, the method of using lithium slag as cement additive has limited value for lithium slag.
The Chinese patent CN 1112335C provides a technology for the preparation of gypsum enhancer with the waste slag produced from the production of lithium carbonate from spodumene by acid method. The Chinese patent CN 106082739A provides a technology that uses the products after mixing and drying the waste slag from the production of lithium carbonate from spodumene by acid and alkali methods as cement admixture. The Chinese patent CN 1090597C discloses a method for manufacturing ceramic glazed tiles from acidic lithium slag. However, the economic value of these technologies to lithium slag is limited.
The Chinese patent CN101624191B provides a method to prepare 13X molecular sieve from lithium slag. The market price of the product obtained by this method is higher, so the added value of the recovery and processing of lithium slag has been greatly improved. However, this method needs to add alkali reagent for high temperature alkali fusion, which requires high energy consumption and waste water treatment, so its industrial application is limited. Studies on Structure Characterization and Adsorption Characteristics of NaX Zeolite Synthesized by Lithium Slag, Synthesis and Characterization of Zeolite X from Lithium Slag (DOI: 10.1016/j.clay.2012.02.017) and Structural Characterization of NaX Zeolite Synthesised by Solution-HydrothermalMethordfrom Lithium Slag also made corresponding research in this respect.
Hence, the disposal problem of lithium slag is still not well solved in China's lithium extraction industry. The key to solve this problem is how to minimize the pollution on the basis of improving the economic added value of lithium slag recovery and processing.
Pyrophyllite powder is an important raw material for the preparation of glass fiber, and is obtained by crushing the pyrophyllite ore. Currently, during the preparation of glass fiber, spodumene is required to reduce the melting temperature and viscosity of the glass, improve the glass density and finish, and improve the strength, ductility, corrosion resistance and thermal shock resistance of glass products. According to the study on the application of spodumene conducted by Johns Manvile, one of the largest glass fiber factories in the world, the advantages of adding spodumene in the production of glass fiber are as follows: cost reduction: after adding spodumene, the flow capacity of glass liquid in platinum alloy furnace is increased by 6.5%; glass quality improvement: the anti-hydrolysis capacity is increased by 20-30%, and the acid resistance capacity is increased by 30-35%; environmental protection: the fluorine consumption is reduced by 20-30%. However, the high price of spodumene increases the production cost of glass fiber, which limits the application and development of this industry and other related industries.
To sum up, if a method can be found to make use of the slag obtained by extracting lithium from spodumene by sulfuric acid method to produce pyrophyllite powder for the preparation of glass fiber, and solve the problem of adding spodumene, a valuable raw material, it will greatly promote the development of lithium slag resource conservation and efficient utilization industry. In addition, if no waste water and waste gas emission is achieved by the said technology, and all parts of lithium slag can be effectively utilized without solid waste after treatment, it will solve the major problems in the lithium slag treatment industry.
Summary of the Invention
In view of the deficiencies and technical requirements of the prior art, the purpose of this invention is to provide a method for comprehensive utilization of lithium slag which refers to the tailings obtained by extracting lithium from spodumene by sulfuric acid method, including the steps of:
(1) Mixing and stirring the said lithium slag so that the sulfate minerals in lithium slag are dispersed and suspended;
(2) Desulfurizing the products obtained from step (1) using the physical beneficiation method to acquire desulfurized pulp and thrown-out slag, so that the sulfur content (calculated by S03, the composition mainly refers to calcium sulfate mineral) of slag phase in desulfurized pulp is not higher than 0.5%;
(3) Performing magnetic separation on the desulfurized pulp obtained from step (2) at the magnetic field intensity of 0.5~2.0T to get magnetic separation pulp and tailings, so that the content of ferric oxide in magnetic separation pulp is reduced to less than 0.5%; then, the magnetic separation pulp is concentrated, filtered and dried to get pyrophyllite raw material for glass fiber;
The thrown-out slags obtained from step (2) are used as raw material of gypsum-based putty or mortar filler after drying and dehydration;
The magnetic separation tailings obtained from step (3) are used as building materials which include cement admixtures or brick-making raw materials;
The said pyrophyllite raw material for glass fiber contains all components of pyrophyllite used for preparing glass fiber and lithium oxide with a content of 0 . 1 -1%.
After long-term exploration, the invention finds that the said pyrophyllite raw material for glass fiber can be easily obtained after gravity separation, flotation and magnetic separation, and the tailings generated in these processes can be used as gypsum-based putty or mortar filler material, cement admixture or brick-making raw material.
The lithium slag obtained after the spodumene is soaked in lithium by sulfuric acid method is applicable to the present invention. In other words, the tailings obtained by the specific lithium leaching process against the specific spodumene are applicable to the present invention.
For the process of extracting lithium from spodumene (production of lithium carbonate and other lithium salts) by sulfuric acid method, please refer to the Comprehensive Recovery and
Utilization of Lithium Slag (Xinjiang Nonferrous Metals, Issue 4, 2014) and Discussion on the Source of Lithium Slag and the Strengthening Impermeability Mechanism of Lithium Slag Concrete (Sichuan Nonferrous Metals, Issue 04, 2000). It is worth noting that the two reports above are only used for understanding the lithium slag and leaching process as recited in the invention, and are not the limitation of the invention.
Compared with the prior art, the present invention solves the problem of waste water pollution from the source without adding a large amount of acid or alkali solution. In step (1) of the invention, any conventional pulp mixing method is available, so that the sulfate minerals in lithium slag are suspended. The water generated after desulfurization treatment in step (2) can be directly reused for pulp mixing in step (1). Wet high-intensity magnetic separation is carried out in step (3), and the water generated can also be reused in step (1) or high-intensity magnetic separation process.
Hence, the present invention not only solves the problem of waste water generation and treatment from the source, but also realizes the complete internal circulation of the generated water in the whole process, so as to achieve zero discharge. When the whole process stops running, the water generated in the process can be stored for the next lithium slag treatment, or can be discharged after relevant waste water treatment process. It is worth noting that the cost of the invention is lower even during the waste water treatment, as no exogenous acid or alkali is added in the whole process, and only an appropriate amount of dispersant is added.
In the present invention, the lithium slag can be used as the raw material for the preparation of glass fiber, a high-value industrial product, which greatly improves the added value of lithium slag recycling. Importantly, compared with the existing pyrophyllite powder for glass fiber production, the pyrophyllite raw material for glass fiber as cited in the invention also contains 0.1~1.0% lithium oxide, thus saving the usage amount of expensive spodumene in the production of glass fiber. It is not difficult to understand that the invention undoubtedly opens up an "energy-saving, green and efficient" production and application way for the recycling industry of lithium slag as the production process of the invention is green and environmentally-friendly, and the pyrophyllite raw material for glass fiber preparation is available.
In order to describe and distinguish the pyrophyllite raw material for glass fiber as cited in the invention from the existing pyrophyllite powder for glass fiber, the pyrophyllite raw material for glass fiber is called "lithium pyrophyllite" in the invention, so as to more clearly indicate that it contains 0.1~1.0% lithium oxide. It should be understood that the lithium oxide in the lithium pyrophyllite as cited in the present invention does not refer to pure lithium oxide powder, but refers to the lithium oxide component in the lithium pyrophyllite, specifically in the form of siliceous lithium oxide.
It should be emphasized that the core of the invention is that the pyrophyllite raw material for s glass fiber with excellent quality can be easily obtained using the process of the invention without any waste water and solid waste.
It is worth mentioning that the all-solid phase products can be utilized in the treatment process of lithium slag. The thrown-out slag produced in step (2) can be directly used as gypsum-based putty or mortar filler material after drying and dehydration; the magnetic separation tailings obtained from step (3) can be used as building materials. As a result, the invention does not produce solid waste.
Therefore, the invention can achieve the effect of no waste liquid, waste gas and solid waste discharge, which truly realizes the high-value utilization, full utilization and zero waste discharge of lithium slag.
According to the characteristics of lithium extraction process, it's required to press and filter the lithium slag in the process of extracting lithium and producing by-product lithium slag, which is easy to cause the adhesion and agglomeration of sulfate minerals in it. As a result, when the content of sulfur (calculated by SO 3 , the composition mainly refers to calcium sulfate mineral) in lithium slag is too high, dispersant can be added in step (1), so that sulfate minerals can be dispersed more easily. Generally speaking, when the content of sulfur in lithium slag (calculated by SO3 , the same below) is greater than or equal to 1%, it is easy to agglomerate. The caking adhesion agglomeration as cited in the invention refers to the agglomeration of sulfate minerals adhering to other minerals.
In the present invention, dispersant is added to make sure that sulfate minerals in lithium slag are uniformly dispersed, and to reduce the adhesion of sulfate minerals with other minerals and thus cause agglomeration. In other words, as long as it can play such a role, no matter what kind of dispersant is used, it is applicable to the present invention.
In particular, on the basis of adding reagents which can reduce the adhesion and agglomeration of sulfate minerals, persons skilled in the art can also add preparations for dispersing other minerals in lithium slag. Therefore, the "dispersant" as cited in the present invention does not exclude the addition of these preparations for dispersing other minerals.
In the present invention, the said "dispersed and suspended state" means that the sulfate minerals in lithium slag are dispersed and suspended, and does not mean that the lithium slag is dispersed and suspended as a whole, nor does it mean that sulfate minerals are not agglomerated under any micro scale, as long as it is conducive to the subsequent work.
Generally, the addition amount of the said dispersant is 0.-2Kg/t lithium slag.
The phosphate as cited in the invention can be sodium hexametaphosphate, lithium hexametaphosphate, etc., and organic acid binary low molecular copolymer can be tripolyphosphate, tannin, lignin sulfonate, etc., and organic acid ternary low molecular copolymer can be the product of ternary free radical copolymerization reaction of sodium allyl sulfonate, maleic anhydride and acrylic acid.
The purpose of step (2) of the present invention is to make sure the content of sulfur in slag phase (calculated by S03, the composition mainly refers to calcium sulfate mineral) is not higher than 0.5%. The invention can achieve this purpose by gravity separation or flotation. Under the premise of understanding that the purpose can be achieved by gravity separation and/or flotation, persons skilled in the art can also employ some instruments or auxiliary reagents to accelerate the process. It can be appreciated that the above schemes are within the spirit scope of the invention, and appropriate adjustments made in accordance with the spirit of the technology and based on specific environmental or production conditions are within the protection scope of the invention.
During the gravity separation, the equipment used is one of gravity separation equipment, e.g. spiral chute, hydrocyclone, table, centrifuge, swaging machine and so on. The equipment used for flotation is flotation column or flotation machine. An appropriate amount of collector is added during the flotation, and the non-foam products obtained after flotation are used as pulp and the foam products as thrown-out slag.
An appropriate amount of surfactant is added during flotation. The said collector is an anionic surfactant and/or a cationic surfactant, wherein the said anionic surfactant is composed of one or more of the carboxylate, sulfonate, sulfate and phosphate, and the said cationic surfactant is composed of one of the amine salt and quaternary ammonium salt; the dosage of the said collector is 10-200g/t lithium slag.
Preferably, the dosage of the said collector is 50-200g/t to ensure the desulfurization effect.
During the said flotation, oleic acid is used as the flotation collector, and the addition amount of oleic acid is 100~200g/t. The flotation process of primary roughing and primary scavenging is adopted, and the flotation process of primary roughing and secondary scavenging is preferred; more preferably, the addition amount of oleic acid is 200g/t.
For lithium slag with sulfur content more than 1%, oleic acid is used as the flotation collector, and the addition amount of oleic acid is 100~200g/t. The sulfur content can be reduced to less than 0.5% during the flotation process of primary roughing and primary scavenging; on the basis of the above scheme, the sulfur content can be reduced to 0.4% using the flotation process of primary roughing and secondary scavenging; in particular, when the addition amount of oleic acid is 200g/t, the sulfur content can be reduced to below 0.3%.
At least primary magnetic separation shall be performed during the said magnetic separation, and the process of primary roughing and primary scavenging is preferred; during the magnetic separation, the magnetic field intensity is preferred to be 1.2-2.0T.
During the magnetic separation process of primary roughing and primary scavenging, the content of ferric oxide can be reduced to 0.4% and the content of titanium dioxide can not exceed 0.15%. When the magnetic field intensity is 1.2-2.OT, the effect is the best.
The sulfur content in lithium slag is generally less than 12%. The present invention only means that the invention is suitable for the treatment of lithium slag obtained under general conditions, but this does not mean that the invention is not suitable for the treatment of lithium slag with sulfur content higher than 12%.
Preferably, when the sulfur content in the said lithium slag is greater than 10%, gravity separation desulfurization and then flotation treatment can be performed to reduce the production cost. In this case, the sulfur content can be reduced partially by gravity separation, making subsequent flotation easier.
If no special instructions are given, the pulp mixing as cited in the invention is carried out by adding water to lithium slag. The invention has no limitation on the pH value and mineral content of the water used. Preferably, the pulp concentration is 10~65% by weight percent during the said pulp mixing, and the preferred pulp concentration is 30~60% considering the factors of water flow balance and water circulation.
Alternatively, the filtrate filtered in step (3) can be reused for the pulp mixing and the said wet magnetic separation through water balance flow regulation to realize the water supply and drainage balance circulation of the system.
Alternatively, the expansion drying method or fluidized bed drying method is adopted during the said drying process in step (3), and the drying temperature is 100~190°C.
For persons skilled in the art, it is not difficult to understand that the commonly used drying methods are suitable for the present invention, and the above drying methods are only two optional methods.
The benefits of the invention are as follows:
1. The invention realizes the high-value utilization, full utilization and zero waste discharge of lithium slag, and the whole process is green and environmentally-friendly, which solves the major bottleneck problem in the lithium slag treatment;
2. The invention can obtain the high-value pyrophyllite raw material for the preparation of glass fiber, and realizes the leap of preparing high-value industrial raw materials with lithium slag for the first time; compared with the preparation of glass fiber with the existing pyrophyllite powder and spodumene, the production cost is significantly reduced;
3. The invention realizes the utilization of all-solid phase products in the treatment process of lithium slag, and other solid phase products can be directly used for industrial use on the basis of producing pyrophyllite, which further enhances the economic value of lithium slag recovery treatment.
4. The invention can realize zero emission of polluting waste water and waste gas, realize green, high-value and comprehensive utilization of lithium slag, and has good social and environmental protection benefits.
Brief Description of the Drawings
Fig.1 is a schematic flowchart of a treatment method for lithium slag according to the present invention.
Detailed Description of the Embodiments
The present invention is described in detail in the following embodiments. It is necessary to point out that the following embodiments are only used to further explain the invention, and can not be understood as the limitation of the protection scope of the invention. Some nonessential improvements and adjustments made by persons skilled in the art according to the above invention contents are still within the protection scope of the invention.
In the following embodiments, "SO 3" refers to the sulfur content in SO 3 .
Embodiment 1
As for the lithium slag (Li2 0 0.3%, SO 3 6.58%, Fe 203 1.8%, SiO 2 62%, A1203 21%) produced from the preparation of lithium carbonate from spodumene by sulfuric acid method by a spodumene lithium extraction enterprise in Sichuan Province, water is added to mix the pulp with the concentration of 40%, and the dispersant (sodium silicate 1000 g/t lithium slag) is then added; the pulp experiences the desulfurization process. First, the pulp experiences the floatation desulphurization, and the flotation collector is oleic acid. The flotation process employs primary roughing and secondary scavenging, and the amount of oleic acid in roughing collector is 100g/t lithium slag, and the amount of oleic acid in primary scavenging collector is 50g/t lithium slag, and the amount of oleic acid in secondary scavenging collector is 50g/t lithium slag. The foam products generated in flotation are used as gypsum putty, and non-foam products generated in flotation operations enter the wet high-intensity magnetic separator. The high-intensity magnetic separation adopts the process of primary roughing and primary scavenging, and the magnetic field intensity for roughing and scavenging control is 1.2T and 1.5T, respectively, so as to acquire magnetic separation pulp and tailings; after magnetic separation, the magnetic separation pulp obtained is concentrated, filtered and dried to get lithium pyrophyllite for glass fiber. See Table 1 for specific product parameters.
Table 1
Productivity Product Composition Usage Quality Standard /00
Li20 0.5%, S03 0.28%, Fe 2 03 Lithium As raw material 75 0.34%, Al 2 0 3 25.2%0,SiO 2 of glass fiber a pyrophyllite 70.4,A2352%Si2 69.0%, moisture content 0.82%)
Magnetic 9.5 Fe203 15.5% As cement
separation tailings admixture
The composition As raw material conforms to GB/T of gypsum Foam product 15.5 CaSO 4 2H 20 89%o 9776-2008 national putty and standard for building mortar filler gypsum
Note: The market price of cement admixture obtained in this embodiment is about RMB 50 yuan/t, and the market price of gypsum putty is about RMB 300 yuan/t.
"a" in the table refers to the quality standard of "glass fiber raw material" in "Table 5-11 Quality
Requirements of Various Industries for Pyrophyllite" as specified in Building MaterialMinerals (edited by Wang Suli, Chemical Industry Press, 2014. P253.). The lithium pyrophyllite obtained by this embodiment contains lithium oxide, and all the other components meet the quality standard requirements.
The production cost of lithium pyrophyllite obtained by the invention is RMB 220 yuan/t, while the market price of pyrophyllite powder for preparing glass fiber is RMB 620 yuan/t. When preparing glass fiber with lithium pyrophyllite, no spodumene is required in the pyrophyllite raw material for glass fiber, which can greatly reduce the preparation cost of glass fiber. Since the pyrophyllite raw material (lithium pyrophyllite) for glass fiber contains lithium, it is better than the pyrophyllite powder for glass fiber preparation on the market. The estimated market price is at least RMB 1000 yuan/t, which realizes the high-value utilization of lithium slag.
Embodiment 2
As for the lithium slag (Li2 0 0.5%, SO 3 11.05%, Fe 2 03 0.85%, SiO 2 55%, A1 2 0 3 21%) produced from the preparation of lithium carbonate from spodumene by sulfuric acid method by a spodumene lithium extraction enterprise in Sichuan Province, water is added to mix the pulp with the concentration of 50%, and the dispersant (sodium silicate 1500 g/t lithium slag) is then added; the pulp experiences the desulfurization process. First, the pulp enters the hydrocyclone for gravity separation, and the products with larger proportion obtained by gravity separation experience the flotation desulfurization, and the flotation collector is dodecyl amine. The flotation process employs primary roughing and secondary scavenging, and the amount of dodecyl amine in roughing collector is 50g/t lithium slag, and the amount of dodecyl amine in primary scavenging collector is 25g/t lithium slag, and the amount of dodecyl amine in secondary scavenging collector is lOg/t lithium slag. The foam products generated in flotation and the products with smaller proportion obtained by gravity separation are used as gypsum putty, and non-foam products generated in flotation operations enter the high-intensity magnetic separator. The high-intensity magnetic separation adopts the process of primary high-intensity magnetic separation, and the magnetic field intensity is controlled to be 1.5T to acquire magnetic separation pulp and tailings; then, the magnetic separation pulp obtained is concentrated, filtered and dried to get lithium pyrophyllite for glass fiber. See Table 2 for specific product parameters.
Table 2
Productivity Product Composition Usage Quality Standard /00
Lithium Li 200.62%, S030.24%, Fe 20 As raw material pyrophyllite 65 30.26%,Al 20 3 25.4%, SiO 2 a of glass fiber products 69.2%, moisture content 0.65%)
Magnetic separation 8 Fe2036.75% As cement tailings admixture
The composition As raw material conforms to GB/T Foam product 15.5 CaS0 4 2H 2087% of gypsum putty 9776-2008 national and mortar filler standard for building gypsum
Note: The market price of cement admixture obtained in this embodiment is about RMB 50 yuan/t, and the market price of gypsum putty is about RMB 300 yuan/t.
"a" in the table refers to the quality standard of "glass fiber raw material" in "Table 5-11 Quality Requirements of Various Industries for Pyrophyllite" as specified in Building Material Minerals (edited by Wang Suli, Chemical Industry Press, 2014. P253.). The lithium pyrophyllite obtained by this embodiment contains lithium oxide, and all the other components meet the quality standard requirements.
The production cost of lithium pyrophyllite obtained by the invention is RMB 260 yuan/t, while the market price of pyrophyllite powder for preparing glass fiber is RMB 620 yuan/t. When preparing glass fiber with lithium pyrophyllite, no spodumene is required in the pyrophyllite raw material for glass fiber, which can greatly reduce the preparation cost of glass fiber. Since the pyrophyllite raw material (lithium pyrophyllite) for glass fiber contains lithium, it is better than the pyrophyllite powder for glass fiber preparation on the market. The estimated market price is at least RMB 1000 yuan/t, which realizes the high-value utilization of lithium slag.
Embodiment 3
As for the lithium slag (Li200.27%, SO 3 1.92%, Fe 2 03 1.13%, SiO 2 67%, A1 20 3 23%) produced by a spodumene lithium extraction enterprise in Zhejiang Province, water is added by mortar pump for pulp mixing and then pumped into the agitating vessel, and the pulp concentration is controlled to be 30%. The pulp flows into the flotation column for flotation, and the flotation process employs primary roughing and primary scavenging, and the amount of roughing collector is 50g/t lithium slag, and the amount of oleic acid in primary scavenging collector is 20g/t lithium slag. The non-foam products generated in flotation enter the high-intensity magnetic separator. The high-intensity magnetic separation adopts the process of primary roughing and primary scavenging, and the magnetic field intensity for roughing and scavenging control is 1.5T and 1.8T, respectively. After magnetic separation, the magnetic separation pulp obtained is concentrated, filtered and dried to get lithium pyrophyllite for glass fiber. See Table 3 for specific product parameters.
Table 3
Product Productivity Composition Usage Quality Standard /00
Lithium Li2 0 0.42%, S03 0.16%, Fe 20 As raw material pyrophyllite 86.4 0.25%, A1 20 3 25.5%, SiO 2 a of glass fiber products 79.1%, moisture content 0.85%)
Magnetic 9 Fe203 7.68% As cement
separation tailings admixture
The composition
As raw material conforms to GB/T
Foam product 4.6 CaS04-2H 20 88% of gypsum putty 9776-2008 national and mortar filler standard for building
gypsum
Note: The market price of cement admixture obtained in this embodiment is about RMB 50 yuan/t, and the market price of gypsum putty is about RMB 300 yuan/t.
"a" in the table refers to the quality standard of "glass fiber raw material" in "Table 5-11 Quality
Requirements of Various Industries for Pyrophyllite" as specified in Building Material Minerals (edited by Wang Suli, Chemical Industry Press, 2014. P253.). The lithium pyrophyllite obtained by this embodiment contains lithium oxide, and all the other components meet the quality standard requirements.
The production cost of lithium pyrophyllite obtained by the invention is RMB 190 yuan/t, while the market price of pyrophyllite powder for preparing glass fiber is RMB 620 yuan/t. When preparing glass fiber with lithium pyrophyllite, no spodumene is required in the pyrophyllite raw material for glass fiber, which can greatly reduce the preparation cost of glass fiber. Since the pyrophyllite raw material (lithium pyrophyllite) for glass fiber contains lithium, it is better than the pyrophyllite powder for glass fiber preparation on the market. The estimated market price is at least RMB 1000 yuan/t, which realizes the high-value utilization of lithium slag.
Embodiment 4
As for the lithium slag in embodiment 3, water is added by mortar pump for pulp mixing and then pumped into the agitating vessel, and the pulp concentration is controlled to be 20%. The pulp flows into the hydrocyclone for gravity separation and grading, and the technical parameters of hydrocyclone are as follows: the feed concentration is controlled to be 20%, the feed pressure is 1.Ox10-3MPa, and the separation size is 0.019mm. Products greater than 0.019mm enter the high-intensity magnetic separator, and the high-intensity magnetic separation adopts the process of primary roughing and primary scavenging, and the magnetic field intensity for roughing and scavenging control is 1.5T and 1.8T, respectively. After magnetic separation, the magnetic separation pulp obtained is concentrated, filtered and dried to get lithium pyrophyllite for glass fiber. See Table 4 for specific product parameters.
Table 4
Productivity Product Composition Usage Quality Standard /00
Lithium Li20 0.48%, S03 0.1%, Fe 20 As raw material pyrophyllite 78 0.25%, Al 20 3 25.2%, SiO 2 a of glass fiber products 69.2%, moisture content 0.86%)
Magnetic separation 9 Fe203 7.68% As cement
tailings admixture
The composition
As raw material conforms to GB/T
Foam product 4.6 CaSO42H 20 45% of gypsum putty 9776-2008 national and mortar filler standard for building
gypsum
Note: The market price of cement admixture obtained in this embodiment is about RMB 50 yuan/t, and the market price of gypsum putty is about RMB 300 yuan/t.
"a" in the table refers to the quality standard of "glass fiber raw material" in "Table 5-11 Quality Requirements of Various Industries for Pyrophyllite" as specified in Building Material Minerals (edited by Wang Suli, Chemical Industry Press, 2014. P253.). The lithium pyrophyllite obtained by this embodiment contains lithium oxide, and all the other components meet the quality standard requirements.
The production cost of lithium pyrophyllite obtained by the invention is RMB 180 yuan/t, while the market price of pyrophyllite powder for preparing glass fiber is RMB 620 yuan/t. When preparing glass fiber with lithium pyrophyllite, no spodumene is required in the pyrophyllite raw material for glass fiber, which can greatly reduce the preparation cost of glass fiber. Since the pyrophyllite raw material (lithium pyrophyllite) for glass fiber contains lithium, it is better than the pyrophyllite powder for glass fiber preparation on the market. The estimated market price is at least RMB 1000 yuan/t, which realizes the high-value utilization of lithium slag.
Embodiment 5
Except that the process of primary roughing and primary scavenging is employed during the flotation, others are consistent with the embodiment 1. All products can satisfy the quality standards of the corresponding products obtained in embodiment 1.
Embodiment 6
Except that the dispersant is sodium hexametaphosphate, others are consistent with embodiment 1. All products can satisfy the quality standards of the corresponding products obtained in embodiment 1.
Embodiment 7
Except that the dispersant is lithium hexametaphosphate, others are consistent with embodiment 1. All products can satisfy the quality standards of the corresponding products obtained in embodiment 1.
Embodiment 8
Except that the magnetic field intensity for magnetic separation roughing is 0.5T, others are consistent with embodiment 2. All products can satisfy the quality standards of the corresponding products obtained in embodiment 2.
Embodiment 9
Except that the primary high-intensity magnetic separation is only performed in the magnetic separation and the magnetic field intensity is 2.OT, others are consistent with embodiment 2. All products can satisfy the quality standards of the corresponding products obtained in embodiment 2.
Claims (18)
1. A comprehensive utilization method for lithium slag which refers to the tailings obtained after extracting lithium from spodumene by sulfuric acid method, including the steps of:
(1) Mixing and stirring the said lithium slag so that the sulfate minerals in lithium slag are dispersed and suspended;
(2) Desulfurizing the products obtained from step (1) using the physical beneficiation method to acquire desulfurized pulp and thrown-out slag, the sulfur content of slag phase in the said desulfurized pulp is not higher than 0.5%;
(3) Performing magnetic separation on the desulfurized pulp obtained from step (2) at the magnetic field intensity of 0.5~2.T to get magnetic separation pulp and tailings, so that the content of ferric oxide in magnetic separation pulp is reduced to less than 0.5%; then, the magnetic separation pulp is concentrated, filtered and dried to get pyrophyllite raw material for glass fiber production;
In step (2), the said physical beneficiation method refers to gravity separation and/or flotation;
The thrown-out slags obtained from step (2) are used as raw material of gypsum-based putty or mortar filler after drying and dehydration;
The magnetic separation tailings obtained from step (3) are used as building materials which include cement admixtures or brick-making raw materials;
The said pyrophyllite raw material for glass fiber contains all components of pyrophyllite used for preparing glass fiber and lithium oxide with a content of 0 . 1 -1%.
2. The method of claim 1 wherein the sulfur content in the said lithium slag is not higher than 12%.
3. The method of claim 1 wherein the sulfur content in the said lithium slag is greater than or equal to 1%, and an appropriate amount of dispersant is added during the mixing process described in step (1); the said dispersant is composed of at least one of the binary or ternary low molecular copolymers of silicate, phosphate and organic acid.
4. The method of claim 3 wherein the addition amount of the said dispersant is 0.~2Kg/t lithium slag.
5. The method of claims 1, 3 or 4 wherein the pulp concentration is 10~65% by weight percentage during the said mixing process in step (1).
6. The method of claim 5 wherein the said pulp concentration is 30~60%.
7. The method of claim 1 wherein the equipment used is one of spiral chute, hydrocyclone, table, centrifuge and swaging machine when the said physical beneficiation method refers to gravity separation; the equipment used is flotation column or flotation machine when the said physical beneficiation method refers to flotation; an appropriate amount of collector is added during the flotation, and the non-foam products obtained after flotation are used as pulp and the foam products as thrown-out slag.
8. The method of claim 1 wherein the sulfur content in the said lithium slag is greater than 10%. In step (2), the desulfurization process is carried out by gravity separation and then flotation.
9. The method of claim 7 wherein the said collector is an anionic surfactant and/or a cationic surfactant, wherein the said anionic surfactant is composed of one or more of the carboxylate, sulfonate, sulfate and phosphate, and the said cationic surfactant is composed of one of the amine salt and quaternary ammonium salt; the dosage of the said collector is 10-200g/t lithium slag.
10. The method of claim 9 wherein the dosage of the said collector is 50-200g/t lithium slag.
11. The method of claims 1, 8, 9 or 10 wherein oleic acid is used as the flotation collector during the said flotation, and the addition amount of oleic acid is 100~200g/t. The flotation process of primary roughing and primary scavenging is adopted.
12. The method of claim 11 wherein the addition amount of oleic acid is 200g/t.
13. The method of claims 1, 8, 9 or 10 wherein oleic acid is used as the flotation collector during the said flotation, and the addition amount of oleic acid is 100~200g/t. The flotation process of primary roughing and secondary scavenging is adopted.
14. The method of claim 13 wherein the addition amount of oleic acid is 200g/t.
15. The method of claim 1 wherein at least primary magnetic separation shall be performed during the said magnetic separation.
16. The method of claim 15 wherein the process of primary roughing and primary scavenging is adopted during the said magnetic separation.
17. The method of claims 15 or 16 wherein the magnetic field intensity is 1.2-2.OT during the said magnetic separation.
18. The method of claim 1 wherein the expansion drying method or fluidized bed drying method is adopted during the said drying process in step (3), and the drying temperature is 100~190°C.
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| PCT/CN2019/070556 WO2019141098A1 (en) | 2018-01-17 | 2019-01-07 | High-value comprehensive utilization method for lithium slag |
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| CN108147658B (en) * | 2018-01-17 | 2018-12-11 | 成都绿锂环保科技有限公司 | A kind of high-valued method of comprehensive utilization of lithium slag |
| CN108745639B (en) * | 2018-05-15 | 2019-09-17 | 赣州金环磁选设备有限公司 | A kind of method of floating spodumene tailing resource recycling |
| AU2020223864B2 (en) * | 2019-02-22 | 2022-08-18 | Gebrüder Dorfner GmbH & Co. Kaolin- und Kristallquarzsand-Werke KG | Method for producing solid particles, solid particles, and the use thereof |
| CN110270308A (en) * | 2019-06-27 | 2019-09-24 | 四川大学 | A kind of adsorbent and preparation method thereof for sewage treatment |
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| CN116462522B (en) * | 2023-06-19 | 2023-08-22 | 湖南永杉锂业有限公司 | Method for preparing sagger |
| CN116874252A (en) * | 2023-07-05 | 2023-10-13 | 江西省建材科研设计院有限公司 | Cement, mineral powder, lithium slag-based curing agent and application thereof in soil |
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| CN108147658B (en) * | 2018-01-17 | 2018-12-11 | 成都绿锂环保科技有限公司 | A kind of high-valued method of comprehensive utilization of lithium slag |
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