CN108273826A - A kind of complete mutually high-valued recoverying and utilizing method of lithium slag - Google Patents
A kind of complete mutually high-valued recoverying and utilizing method of lithium slag Download PDFInfo
- Publication number
- CN108273826A CN108273826A CN201810044953.6A CN201810044953A CN108273826A CN 108273826 A CN108273826 A CN 108273826A CN 201810044953 A CN201810044953 A CN 201810044953A CN 108273826 A CN108273826 A CN 108273826A
- Authority
- CN
- China
- Prior art keywords
- lithium
- slag
- lithium slag
- pyrophillite
- treatment process
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 206
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 239000002893 slag Substances 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 110
- 230000008569 process Effects 0.000 claims abstract description 65
- 239000011521 glass Substances 0.000 claims abstract description 60
- 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 39
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000007885 magnetic separation Methods 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052600 sulfate mineral Inorganic materials 0.000 claims abstract description 10
- 150000005323 carbonate salts Chemical class 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000004568 cement Substances 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 6
- 239000004035 construction material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000007701 flash-distillation Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 description 14
- 239000011707 mineral Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 239000003595 mist Substances 0.000 description 12
- 229910052629 lepidolite Inorganic materials 0.000 description 10
- 239000004567 concrete Substances 0.000 description 9
- 239000004566 building material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000009428 plumbing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- -1 compound calcium sulfate Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000008235 industrial water Substances 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- 239000012265 solid product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000010457 zeolite 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 group 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
- 241001131796 Botaurus stellaris Species 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
- 239000004117 Lignosulphonate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910000329 aluminium sulfate 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
- 239000000908 ammonium hydroxide Substances 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
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 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
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
- 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
- C04B18/0427—Dry materials
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Civil Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
Abstract
The present invention provides a kind of complete mutually high-valued recoverying and utilizing method of lithium slag, the lithium slag be to spodumene using sulfuric acid process through leaching lithium process carry lithium after gained slag comprising following steps：(1) it sizes mixing, stirs to the lithium slag so that sulfate mineral is in dispersion suspended state in lithium slag；(2) reaction treatment is carried out using soluble carbonate salt in any order to step (1) gains and carries out wet magnetic separation processing；(3) gained slurry after step (2) processing is concentrated, filtered and is dried, obtain glass pyrophillite raw material.The present invention is efficient when handling lithium slag and three wastes generate, and realizes the leap of the high-valued recycling of lithium slag, has significant economic benefit and environmental benefit.
Description
Technical field
The invention belongs to the environmentally protective recycling fields of Industrial Solid Waste, are related to lithium slag for comprehensive and utilize field, and in particular to one
Complete mutually recycling and the high-valued method of product of kind lithium slag.
Background technology
Content of the lithium in the earth's crust is about 0.0065%, mainly with salt lake bittern, spodumene, lepidolite, petalite and
Phosphorus aluminium ore exist, be mainly distributed on Bolivia, Chile, China, Argentina, the U.S., Australia, Russia, Canada and
The states such as Serbia.
Tellurian spodumene mine is distributed mainly on Australia, Canada, Zimbabwe, the Congo, Brazil and China；Lithium
Mica Mine is distributed mainly on Zimbabwe, Canada, the U.S., Mexico and China.In China, spodumene is concentrated mainly on four
The ground such as river, Xinjiang, Henan, lepidolite are concentrated mainly on Jiangxi Province and Hunan Province.
Lithium slag, be to rich lithium resource carry after lithium caused by waste residue general designation.Currently, China is mainly from lithium ore
In carry lithium.China carries lithium mainly using sodium chloride autoclaving method from lepidolite, and lithium is carried from spodumene and mainly uses sulfuric acid
Method.Therefore, the lithium slag in China caused by above two method predominantly by carrying lithium by-product slag.
In recent years, the lithium battery industry development in China is rapid, the nationalization process of wherein critical material is also constantly accelerated,
So that the demand of related lithium product is constantly promoted.Meanwhile the thing followed be corresponding lithium slag output it is increasing, lithium slag band
The problem of environmental pollution come constantly shows.The best way for solving the problems, such as this is to carry out recycling processing to lithium slag it is made
Its available industrial products.In this respect, the prior art has carried out some trials.
102126838 A of Chinese patent CN disclose a kind of side preparing light building material ceramic using lepidolite extracted lithium slag
Method carries out high temperature sintering by being added after clay powder and pore creating material, can obtain light building material ceramic, product quality reaches
To the quality requirement of common light-weight aggregate high-class product as defined in GB/T 17431.2-1998.Although this method realizes lepidolite and carries
The recycling of lithium slag, but processing added value caused by it is extremely limited, with other light building material ceramics that are used to prepare
Raw material is compared, and does not generate the effect that significant cost reduction and added value are promoted.Likewise, Chinese patent CN
There is also similar problems by 103979809 A.
《Influence of lithium slag from lepidolite on the durability of
concrete》(doi:10.1088/1755-1315/61/1/012151) for lepidolite extracted lithium slag as cement additive
It is studied, it is found that it can promote 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 Preparing Aero-Concrete Using
Leaching Residual Slag of Lepidolite ore》(DOI:10.4028/www.scientific.net/
AMM.99-100.375) also to having carried out different research using lithium slag as cement additive aspect.
103922626 A of Chinese patent CN provide a kind of recoverying and utilizing method carrying lithium by-product lithium slag to salt lake, are used for
Prepare concrete alkali aggregate reaction inhibitor.Concrete has been prepared by reducing the harmful components sodium chloride in lithium slag in it
The inhibitor of alkali.Likewise, this method only realizes the recycling of discarded lithium slag to a certain extent, but
Its added value does not bring larger promotion.
Above-mentioned technology and other similar problems of the existing technology are：These technologies are only capable of realizing the low value of lithium slag
Change, the recovery processing of single application.Since the production industries such as concrete material, cement, building material ceramic have been matures
Industry does not have advantage using lithium slag as the raw material for producing these products, is solved at lithium slag recycling to realize very well
The problem of reason.
It solves lithium slag and recycles to be worth there are mainly two types of low methods, one is the method for comprehensive utilization of research lithium slag,
So that lithium slag is after treatment, various pieces are effectively utilized；Another kind be so that lithium slag after treatment become have
Emulative high-value product.
103789553 A of Chinese patent CN provide a kind of lepidolite ore phase reconstruction and put forward the method that lithium slag for comprehensive utilizes, and lead to
Countercurrent flotation is carried out again after crossing acid adding plus base extraction, can obtain calcium chloride, rich aluminium slag, aluminosilicate and fluorite concentrate.It should
Although technology can obtain multiple product, for other acquisition modes of its product, do not have equally apparent excellent
Gesture.Meanwhile the technology needs to use a large amount of acid-base solution, and it is difficult to realize the recycling of acid-base solution, it be easy to cause dirt
Dye problem so that recycling lithium slag cannot be realized to avoid the original idea of pollution.
103601230 A of Chinese patent CN provide a kind of method that lithium slag for comprehensive utilizes production industrial chemicals, this method
Discharge gas is absorbed using ammonium hydroxide, reduces exhaust emission, while liquid reduces the pollution of waste water without direct emission.
The patent obtains calcium chloride, ammonium fluoride, white carbon, aluminium salt and ammonium sulfate by multiple steps.With 103789553 A phases of CN
Than, the patent in terms of reducing water, gas and slag discharge, certain progress is achieved, but its products obtained therefrom and other common systems
In comparison Preparation Method, does not have clear superiority equally.In addition, the patent is same unavoidable using a large amount of acid solution, together
Sample is also difficult to realize the recycling of acid solution, and the safety of operation and blowdown control aspect face problem, keeps it same difficult
To promote and apply.
The targeted lithium slag of above-mentioned patent is carry lithium to lepidolite or salt lake carries by-product slag obtained by lithium.
Currently, China for how to handle carried from spodumene lithium slag caused by lithium further investigation it is less.Due to
When refining lithium carbonate from spodumene using sulfuric acid process, about it is discharged therefore how 8~10 tons of lithium slags are handled when producing 1 ton of lithium salts
This kind of lithium slag becomes urgent problem to be solved.But, people fail to the research of this respect also still in the more preliminary stage
Realize that the high-valued and green high-efficient of lithium slag utilizes processing.
《The source of lithium slag and the impervious Exploration of Mechanism of the enhancing of lithium dreg concrete》(Sichuan non-ferrous metal 04 phase in 2000) carries
It has supplied using lithium slag as the technology of the reinforcing agent of concrete and the additive of cement.But, due to the supply side structure in China
Property reform have the requirement of " three go a drop one to mend " for cement industry so that the lithium slag will as the application of cement additive
It is limited.In addition, using lithium slag as the method for cement additive, it is also very limited for the value promotion of lithium slag.
Chinese patent CN1112335C provides a kind of utilize to spodumene using caused by acid system production lithium carbonate
Waste residue prepares the technology of gypsum reinforcing agent.106082739 A of Chinese patent CN provide a kind of utilize and use acid system to spodumene
Technology of the drying products therefrom as cement admixture is carried out after being mixed with the waste residue caused by alkaline process production lithium carbonate.China
1090597 C of patent CN disclose the method for manufacturing glaze for glazed tile using acid lithium slag.But, these technologies are for lithium slag
Economic value promoted limitation.
101624191 B of Chinese patent CN provide the method for preparing 13X molecular sieves as raw material using lithium slag, this method institute
The product market price of acquisition is higher so that the added value of the recycling working process of lithium slag is increased dramatically.But, this method
It needs that base reagent progress high temperature alkali fuse is added, energy consumption is higher, while also needing to carry out wastewater treatment, and commercial Application is limited.《Lithium
Slag synthesizes NaX molecular sieve structures characterization and characterization of adsorption research》、《Synthesis and characterization of
zeolite X from lithium slag》(DOI:10.1016/j.clay.2012.02.017) and《Structural
characterization ofNaX zeolite synthesisedby solution-hydrothermal methord
from Lithium slag》It is also studied accordingly in this respect.
Therefore, lithium industry is put forward in China, the process problem of generated lithium slag is still not well solved.Such as
On the basis of the economic value added for where promoting the recycling processing of lithium slag, moreover it is possible to which the maximized generation for reducing pollution is that solve should
The key of problem.
Pyrophillite micro mist is the important source material for preparing glass, is by being obtained after being crushed to pyrophyllite deposit.Mesh
Before, when preparing glass, need to be added spodumene to reduce the temperature and melt viscosity when glass melting, improve glass density and
Finish improves intensity, ductility, corrosion resistance and the heat-resisting shock property of product.According to one of the world's largest glass fibre factory
Applicable cases research of the Johns Manvile companies of the U.S. for spodumene, be added when producing glass spodumene have it is as follows
Advantage：Reduce cost：After spodumene is added, the melt flow ability in platinum alloy smelting furnace improves 6.5%；Improve the nature of glass
Amount：20-30% can be improved in anti-hydrolysis ability, and 30-35% can be improved in acid-proof ability；Environmental-protection function：It reduces fluorine dosage and reaches 20-
30%.However, the price continuous rise of spodumene so that the production cost of glass is high, limits the sector and other
The application development of relevant industries.
In conclusion if a kind of method can be found, linking is existing to put forward lithium industrial system so that using using sulfuric acid process pair
Spodumene carries slag obtained by lithium and is used to prepare the pyrophillite micro mist of glass and solving to produce spodumene this valuable raw material need to be added
Problem, it will greatly facilitate the development of lithium Slag treatment industry.Meanwhile if the technology can realize no waste water and gas discharge, and
After processing, each section of lithium slag can be obtained efficiently using and be generated without solid waste with realizing, one action is solved lithium Slag treatment industry
In great main bugbear.
Invention content
In view of the deficiencies of the prior art and technical need, the purpose of the present invention is to provide a kind of the complete mutually high-valued of lithium slag
Recoverying and utilizing method, the lithium slag be to spodumene using sulfuric acid process through leaching lithium process carry lithium after gained slag, which is characterized in that
Described method includes following steps：
(1) it sizes mixing, stirs to the lithium slag so that sulfate mineral is in dispersion suspended state in lithium slag；
(2) B treatment process is carried out again using A treatment process is first carried out to step (1) gains, or first carries out B processing
The mode that process carries out A treatment process again is handled：
The A treatment process is：Soluble carbonate salt is added to be reacted, it is 7~14 to control the pH in slurry so that material
The sulfur content of slag phase in slurry is no more than 0.5%；
The B treatment process is：Under conditions of 0.5~2.0T of magnetic field intensity, handled using wet-type magnetic separation method,
So that the content of the di-iron trioxide in slurry obtained by magnetic separation is no more than 0.5%；
(3) gained slurry after step (2) processing is concentrated, filtered and is dried, obtain glass pyrophillite raw material；
The soluble carbonate salt includes Na2CO3、Li2CO3、(NH4)2CO3、NH4HCO3At least one of；
Tailings obtained by magnetic separation is used as construction material in step (2), and the construction material includes cement admixture or system
Brick raw material；
Wet magnetic separation of the filtrate recycle of filtering gained in the leaching lithium process or the B treatment process in step (3)；
The glass pyrophillite raw material contain the pyrophillite for being used to prepare glass whole components and content be 0.1~
1% lithia.
Grope by long-term, the pleasantly surprised discovery of invention of the invention passes through the A treatment process and B by any order
After treatment process, so that it may which easily to obtain glass pyrophillite raw material of the present invention, and the tailings of magnetic separation can be made
For raw material of building materials such as the cement admixture or brick-making raw materials.
For the present invention, as long as after sulfuric acid process carries out spodumene leaching lithium process gained lithium slag, it is suitable
For the present invention.That is, whether for be which kind of spodumene using the tailings obtained by which kind of specific leaching lithium process, all
It is to be suitable for the invention.
The technique for carrying lithium (lithium salts such as production lithium carbonate) to spodumene for sulfuric acid process, can refer to《The synthesis of lithium slag is returned
It receives and utilizes》(《Xinjiang non-ferrous metal》, 2014, the 4th phase) and《The source of lithium slag and the impervious Discussion of Mechanism of the enhancing of lithium dreg concrete
It begs for》(《Sichuan non-ferrous metal, 2000, the 4th phase》) in record.It is worth noting that above-mentioned two reports are used only for pair
Lithium slag of the present invention and the understanding for leaching process, are not limitation of the present invention.
Compared with prior art, the present invention realizes the interior cycle of the waste liquid to being generated during lithium Slag treatment, in step
The filtrate of filtering gained can largely be back to during the wet magnetic separation in the B treatment process in step (3), small part
It can be back to the leaching lithium process, substantially carried out the zero-emission of waste water.When entire invention process flow is out of service,
Filtrate therein can store, and be arranged after can also carrying out relevant wastewater treatment process for next lithium Slag treatment
It puts.
The present invention can make what lithium slag became glass this high value industrial product to prepare raw material, be greatly improved
The added value that lithium slag recycles.Importantly, for existing glass production pyrophillite micro mist, institute of the present invention
The lithia for being also 0.1~1.0% containing content in the glass pyrophillite raw material obtained so that when producing glass, save
The usage amount of expensive spodumene.It is understandable to be, since production technology of the present invention is environmentally protective and can get and is used for
Prepare the pyrophillite raw material of glass, the present invention for the recycling industry of lithium slag, undoubtedly hewed out " it is energy saving, water-saving,
The production of environmental protection, high benefit " and application approach.
For ease of description and by obtained by the present invention glass pyrophillite raw material and the existing glass that is used to prepare
Pyrophillite micro mist distinguishes, and the glass of gained pyrophillite raw material is referred to as " lithium matter pyrophillite " by the present invention, with more than you know
Show wherein containing 0.1~1.0% lithia.It shall also be appreciated that the oxidation in lithium matter pyrophillite described in the present invention
Lithium does not imply that pure zirconia lithium powder, and refers to the lithia ingredient in lithium matter pyrophillite of the present invention, specifically with siliceous oxidation
The form of lithium exists.
It is important to note that core of the invention is, by the technique of the present invention, quality can be easily obtained
Excellent glass pyrophillite raw material, and not will produce any waste water and solid waste.
It is noted that the full solid formation utilization during lithium Slag treatment may be implemented in the present invention.Magnetic separation in step (2)
Tailings can be used as the construction materials such as the cement admixture or brick-making raw material.In addition, the present invention is during lithium Slag treatment
The liquid phase of generation can also realize recycling.
Therefore, no waste liquid may be implemented, without exhaust gas and without the effect that solid waste is discharged in the present invention, truly realizes
Lithium slag high price value utilization, complete utilization and non-waste-emission purpose.
The characteristics of according to lithium process is put forward, needs to press lithium slag during carrying out carrying lithium and generating by-product lithium slag
Filter be easy to cause sulfate mineral caking cohesive mass therein.Therefore, when the sulphur in lithium slag is (with S03Meter, ingredient are mainly
Refer to calcium sulfate mineral) too high levels when, in step (1), dispersant, which can be added, makes sulfate mineral be more easy to disperse.It is general and
Speech, when the sulfur content in lithium slag is (with S03Meter) be more than or equal to 1% when, be easy to caking reunite.Caking adherency of the present invention group
It is poly-, refer to that sulfate mineral is adhered to generation caking in other mineral.
In the present invention, the purpose that dispersant is added is that the sulfate mineral of lithium slag is made to be in homogeneously dispersed state, drops
Being adhered to other mineral for protosulfate mineral, causes to reunite.As long as that is, can play the role of it is this, no matter use what
Kind dispersant, is suitable for the invention.
Especially it should be pointed out that the examination of the purpose in the cohesive mass added with achievable above-mentioned reduction sulfate mineral
On the basis of agent, the preparation for disperseing other mineral in lithium slag can also be added in those skilled in the art.Therefore, institute of the present invention
" dispersant " stated, which is not precluded, adds these preparations for being used to disperse other mineral.
In the present invention, " the dispersion suspended state " refers to that the sulfate mineral in lithium slag is in dispersion suspension
State does not imply that lithium slag generally in dispersion suspended state, is also not specific under any micro-scale sulfate mineral without group
Poly- phenomenon, as long as carrying out conducive to subsequent handling.
Under normal circumstances, the additive amount of the dispersant is 0.1~2Kg/t lithium slags.
Phosphate of the present invention can be calgon, hexa metaphosphoric acid lithium etc., the copolymerization of organic acid binary low molecule
Object can be tripolyphosphate, tannin, lignosulphonates etc., organic acid ternary low molecule copolymer can be sodium allylsulfonate,
The product of maleic anhydride, acrylic acid ternary free radicals copolymerization reaction.
The purpose of the step (2) of the present invention is so that the sulfur content of slag phase is not higher than 0.5%, Fe2O3Content, which is down to, not to be surpassed
Cross 0.5%.Realize that principle based on this effect is：In A treatment process, following reaction will be mainly generated：CaSO4+
CO3 2-=CaCO3+SO4 2-, which can convert the slightly soluble compound calcium sulfate of lithium slag to the very low indissoluble of solubility coefficient
Compound calcium carbonate, to realize the purpose of lithium slag desulfurization.The present invention is by largely testing the spy to lithium slag of the present invention
Point finds that it is relatively good so that this is obtained by the reaction to lithium slag of the present invention addition soluble carbonate salt after being groped
It carries out, in conventional reaction condition and can reach good effect in the reaction time so that the sulphur of the slag phase in slurry contains
Amount is no more than 0.5%.In B treatment process, wet magnetic separation processing realizes ferrotitanium mineral etc magnetic material by the magnetic field mode of magnetization
The poly- flocculation of matter group, is detached high-melting-point mineral with target minreal using the difference of magnetic mineral, realizes the dyeing mine such as removal ferrotitanium
It is miscellaneous that object achievees the purpose that upgrading is dropped.
Preferably, the soluble carbonate salt is Na2CO3、Li2CO3At least one of.
Preferably, in the A treatment process of step (2), the molar ratio of carbonate and the sulphur in lithium slag is 1.00~1.50.
Preferably, in the A treatment process of step (2), when carrying out the reaction, the reaction time is 5~120min, reaction temperature
Degree is 5~95 DEG C；And/or the liquid-solid ratio of slurry is 1.5~5.0.
When carrying out the magnetic separation, a magnetic separation is at least carried out, it is preferred to use one slightly sweeps technique；When magnetic separation, magnetic field intensity
Preferably 1.2-2.0T.
When the magnetic separation process slightly swept using one, ferric oxide content can be made to be down to 0.4%, titanium dioxide is not
More than 0.15%.When magnetic field intensity is 1.2~2.0T, effect is best.
Under normal circumstances, the sulfur content in lithium slag is (with SO3Meter) it is not higher than 12%.The present invention refers to only that the present invention is suitable
In the processing of the lithium slag of gained under normal circumstances, but this does not imply that the present invention is unsuitable for sulfur content (with SO3Meter) it is higher than
12% lithium slag is handled.When the sulfur content in lithium slag is (with SO3Meter) be not higher than 3% when, the present invention is easier to make for.
Such as not special explanation is that water is added to lithium slag to size mixing when carrying out of the present invention size mixing.The present invention
There is no limit for pH value and mineral content for water used.Preferably, when sizing mixing described in progress, percentage meter by weight, mine
Starch a concentration of 10~65%, it is contemplated that the factor of flow dynamic balancing and water cycle, preferred pulp density are 30~60%.In profit
When with Production By Sulfuric Acid Process lithium carbonate, technique liquid amount balance is the critical issue for solving the lithium rate of recovery, can be by mine in actual work
Slurry concentration be adjusted to soak lithium process in liquid-solid ratio it is consistent, to ensure the closed circulation of water balance and ADSORPTION STATE lithium so that this hair
The bright treatment process for lithium slag can propose lithium operation with spodumene and realize optimal be connected.
Optionally, in step (3), when carrying out the drying, using expansion drying method or fluidized bed drying, drying temperature
It is 100~190 DEG C.
To those skilled in the art, above-mentioned dry it can be appreciated that common drying mode may be adapted to the present invention
Dry mode is only optional two ways.
Under normal circumstances, the sulfate concentration in rate-determining steps (3) in the filtrate of filtering gained is no more than 50g/L.Work as filter
When sulfate concentration in liquid is more than 50g/L, water can be added thereto, it, can also be right in order to be back to the leaching lithium process
It carries out crystallization treatment, obtains crystalline sulfuric acid salt.
Beneficial effects of the present invention：
1, the present invention realizes the processing of the higher value application to lithium slag, solids product complete utilization, solves lithium Slag treatment
Present in great difficult problem；
2, the present invention can obtain the pyrophillite raw material for being used to prepare glass-lithium matter pyrophillite with high value, first
Degree realizes the leap to the preparation high value raw material of industry by lithium slag；Glass is prepared compared to using existing pyrophillite micro mist and spodumene
For fibre, lithium matter pyrophillite of the present invention has the speciality of pyrophillite micro mist and spodumene concurrently, significantly reduces being produced into for glass
This；
3, the present invention realizes the full solid product utilization during lithium Slag treatment, on the basis for producing lithium matter pyrophillite
On, other solid products can directly carry out industrial utilization, further improve the economic value of lithium slag recovery processing；
4, the zero-emission of pollution exhaust gas and solid waste, the basic zero-emission for realizing waste liquid may be implemented in the present invention, has good
Good social benefit and environmental benefit；
5, the present invention can also propose the realization of lithium technique with sulfuric acid process and be connected, while promoting glass-fiber industry development, greatly
Alleviate the problem that spodumene proposes lithium industry environmental protection production.Substantially, the present invention is to be realized for the first time to glass production industry, carried
The organic combination of lithium industry and lithium slag fixed-end forces industry has high application prospect.
Description of the drawings
Fig. 1 is process chart of the present invention to lithium slag；In figure, described is not limited to pure water or industry life " with water "
Fisheries water, according to the understanding of the present invention comprising the feed liquid and additional water that the present invention generates.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
It is further detailed in the present invention, should not be understood as limiting the scope of the invention, which is skilled in technique
Personnel still fall within protection scope of the present invention according to some nonessential modifications and adaptations that foregoing invention content is made.
The present invention is using the tailings product that lithium slag is that certain domestic Ti Li enterprises spodumene sulfuric acid process soaks lithium process.
In following embodiments, " SO3" refer to SO3The sulfur content of meter.
Embodiment 1
For Sichuan spodumene Ti Li enterprises lithium slag caused by lithium carbonate is prepared using sulfuric acid process for spodumene
(Li2O 0.3%, SO36.58%, Fe2O31.8%, SiO262%, Al2O321%), water is added to size mixing, pulp density 40%, and add
Enter 1000 g ton lithium slag of dispersant sodium metasilicate；Sodium carbonate (87.5kg/t lithiums slag) is added to ore pulp and carries out desulphurization reaction, controls pH
9.2, room temperature of sizing mixing leaches 100min；Desulfurization slurry enters Wet-type strong magnetic separator, and high intensity magnetic separation slightly sweeps technique using one, slightly
Selected control magnetic field intensity is 1.2T, and it is 1.5T to scan control magnetic field intensity, obtains magnetic separation slurry and magnetic separation tailings；Magnetic separation is then right
Gained magnetic separation slurry is concentrated, filtered and is dried, and glass lithium matter pyrophillite product is obtained.The filtrate of filtering gained passes through water
Balanced flow regulates and controls the filtrate recycle of 15% (v/v) in desulphurization reaction；Regulate and control the filtrate of 15% (v/v) and is returned with substituting industrial water
For put forward the leaching lithium process in lithium to spodumene using sulfuric acid process, the leaching rate 99.3% of acquisition reaches spodumene sulfuric acid
Method soaks the production target of lithium.Regulate and control the filtrate recycle of 70% (v/v) in wet magnetic separation；The filtrate equivalent of regulation and control and 15% (v/v)
New water for product wash, realize system plumbing balanced recycle.Specific product parameter is shown in Table 1.
Table 1
Note：The market price of cement blending agent is about 50 yuan/ton obtained by the present embodiment.
" a " in table is referred to《Building material mineral products》In (Wang Suli writes, Chemical Industry Press, 2014.P253.)
The quality standard of " glass raw material " project in " quality requirement of the table 5-11 every profession and trades to pyrophillite ".Lithium matter obtained by the present embodiment
Pyrophillite, other than containing lithia, remaining ingredient reaches quality standard requirement.
The production cost of the lithium matter pyrophillite of gained of the invention is 310 yuan/ton, and prepare the pyrophillite micro mist of glass
Market price is 620 yuan/ton.When preparing glass using lithium matter pyrophillite, using glass of the present invention with pyrophillite raw material without adding
Enter spodumene, can significantly reduce the manufacturing cost of glass.Since gained glass pyrophillite raw material (lithium matter pyrophillite) contains
Lithium prepares glass pyrophillite micro mist better than commercially available, and the potential market estimated is worth at least at 1000 yuan/ton, realizes lithium
The higher value application that slag recycles.
Embodiment 2
For Sichuan spodumene Ti Li enterprises lithium slag caused by lithium carbonate is prepared using sulfuric acid process for spodumene
(Li2O 0.5%, SO311.05%, Fe2O30.85%, SiO255%, Al2O321%), water is added to size mixing, pulp density 50%, and
1500 g ton lithium slag of dispersant sodium metasilicate is added；Ore pulp enters Wet-type strong magnetic separator, and high intensity magnetic separation slightly sweeps work using one
Skill, it is 1.3T that roughing, which controls magnetic field intensity, and it is 1.5T to scan control magnetic field intensity, obtains magnetic separation slurry and magnetic separation tailings；Xiang Ci
Ore dressing slurry is added sodium carbonate (148kg/t lithiums slag) and is reacted, and controls pH 10.5, and room temperature of sizing mixing leaches 90min；Then to institute
It obtains desulfurization slurry to be concentrated, filtered and dried, obtains glass lithium matter pyrophillite product.The filtrate of filtering gained passes through level
The filtrate recycle of weighing apparatus flow control 68% (v/v) is in wet magnetic separation；The filtrate recycle for regulating and controlling 12% (v/v) is converted in hybrid reaction
Desulfurization process；The filtrate recycle of 20% (v/v) of regulation and control recycles after crystalline sulfuric acid salt；The filtrate of regulation and control and 20% (v/v)
The new water of equivalent is washed for product, realizes system plumbing balanced recycle.Specific product parameter is shown in Table 2.
Table 2
Note：The market price of cement blending agent is about 50 yuan/ton obtained by the present embodiment.
" a " in table is referred to《Building material mineral products》In (Wang Suli writes, Chemical Industry Press, 2014.P253.)
The quality standard of " glass raw material " project in " quality requirement of the table 5-11 every profession and trades to pyrophillite ".Lithium matter obtained by the present embodiment
Pyrophillite, other than containing lithia, remaining ingredient reaches quality standard requirement.
The production cost of the lithium matter pyrophillite of gained of the invention is 425 yuan/ton, and prepare the pyrophillite micro mist of glass
Market price is 620 yuan/ton.When preparing glass using lithium matter pyrophillite, using glass of the present invention with pyrophillite raw material without adding
Enter spodumene, can significantly reduce the manufacturing cost of glass.Since gained glass pyrophillite raw material (lithium matter pyrophillite) contains
Lithium prepares glass pyrophillite micro mist better than commercially available, and the market price estimated realizes the recycling of lithium slag at least at 1000 yuan/ton
The higher value application utilized.
Embodiment 3
For lithium slag (Li caused by the spodumene Ti Li enterprises of Jiangsu2O 0.27%, SO31.92%,
Fe2O31.13%, SiO267%, Al2O323%) it, is sized mixing by mortar pump water adding and squeezes into agitator, control pulp density 30%,
And 1000 g ton lithium slag of dispersant sodium metasilicate is added；Sodium carbonate (27kg/t lithiums slag) is added to ore pulp and carries out desulphurization reaction, control
PH 11.2, room temperature of sizing mixing leach 60min；Desulfurization slurry enters Wet-type strong magnetic separator, and high intensity magnetic separation slightly sweeps work using one
Skill, it is 1.5T that roughing, which controls magnetic field intensity, and it is 1.8T to scan control magnetic field intensity, obtains magnetic separation slurry and magnetic separation tailings；Magnetic separation
Then gained magnetic separation slurry is concentrated, filtered and is dried, obtain glass lithium matter pyrophillite product.Filter the filtrate of gained
By the filtrate recycle of water balance flow control 10% (v/v) desulfurization process is converted in hybrid reaction；Regulate and control the filter of 10% (v/v)
Liquid is back to substitute industrial water and put forward leaching lithium process in lithium, the leaching rate of acquisition to spodumene using sulfuric acid process
98.3%, reach the production target of spodumene sulfuric acid process leaching lithium.Regulate and control the filtrate recycle of 80% (v/v) in wet magnetic separation；Regulation and control
It is washed for product with the new water of the filtrate equivalent of 10% (v/v), realizes system plumbing balanced recycle.Specific product parameter is shown in
Table 3.
Table 3
Note：The market price of cement admixture is about 50 yuan/ton obtained by the present embodiment.
" a " in table is referred to《Building material mineral products》In (Wang Suli writes, Chemical Industry Press, 2014.P253.)
The quality standard of " glass raw material " project in " quality requirement of the table 5-11 every profession and trades to pyrophillite ".Lithium matter obtained by the present embodiment
Pyrophillite, other than containing lithia, remaining ingredient reaches quality standard requirement.
The production cost of the lithium matter pyrophillite of gained of the invention is 185 yuan/ton, and prepare the pyrophillite micro mist of glass
Market price is 620 yuan/ton.When preparing glass using lithium matter pyrophillite, using glass of the present invention with pyrophillite raw material without adding
Enter spodumene, can significantly reduce the manufacturing cost of glass.Since gained glass pyrophillite raw material (lithium matter pyrophillite) contains
Lithium prepares glass pyrophillite micro mist better than commercially available, estimates market potential value at least at 1000 yuan/ton, realizes lithium
The higher value application that slag recycles
Embodiment 4
Other than dispersant is calgon, remaining is consistent with embodiment 1.The product of gained glass lithium matter pyrophillite
Matter reaches quality standard described in embodiment 1, and glass is 87.58% (based on butt) with lithium matter pyrophillite yield.
Embodiment 5
In addition to activator is sodium carbonate sinker mother liquor, that is, Li2CO3And Na2CO3Mixed liquor (Li2CO37.2g/L
Na2CO3Except 250g/L), remaining is consistent with embodiment 3.The quality of gained glass lithium matter pyrophillite reaches described in embodiment 3
Quality standard, glass with lithium matter pyrophillite yield be 86.8% (based on butt).
Embodiment 6
In addition to activator is NH4CO3Except, remaining is consistent with embodiment 2.Gained glass is reached with the quality of lithium matter pyrophillite
To the quality standard described in embodiment 2, glass is 89.78% (based on butt) with lithium matter pyrophillite.
Embodiment 7
Other than magnetic field intensity is 2.0T, remaining is consistent with embodiment 3.Gained glass is reached with the quality of lithium matter pyrophillite
To the quality standard described in embodiment 2, glass is 86.78% (based on butt) with lithium matter pyrophillite.
Claims (10)
1. a kind of complete mutually high-valued recoverying and utilizing method of lithium slag, the lithium slag is using sulfuric acid process to spodumene through soaking lithium process
Carry gained slag after lithium, which is characterized in that described method includes following steps：
(1) it sizes mixing, stirs to the lithium slag so that sulfate mineral is in dispersion suspended state in lithium slag；
(2) B treatment process is carried out again using A treatment process is first carried out to step (1) gains, or first carries out B treatment process
The mode for carrying out A treatment process again is handled：
The A treatment process is：Soluble carbonate salt is added to be reacted, it is 7~14 to control the pH in slurry so that in slurry
Slag phase sulfur content be no more than 0.5%；
The B treatment process is：Under conditions of 0.5~2.0T of magnetic field intensity, handled using wet-type magnetic separation method so that
The content of di-iron trioxide in slurry obtained by magnetic separation is no more than 0.5%；
(3) gained slurry after step (2) processing is concentrated, filtered and is dried, obtain glass pyrophillite raw material；
The soluble carbonate salt includes Na2CO3、Li2CO3、(NH4)2CO3、NH4HCO3At least one of；
Tailings obtained by magnetic separation is used as construction material in step (2), and the construction material includes that cement admixture or brickmaking are former
Material；
Wet magnetic separation of the filtrate recycle of filtering gained in the leaching lithium process or the B treatment process in step (3)；
The whole components and content that the glass pyrophillite raw material contains the pyrophillite for being used to prepare glass are 0.1~1%
Lithia.
2. lithium slag according to claim 1, which is characterized in that the sulfur content in the lithium slag is not higher than 12%, it is preferred that
Sulfur content in the lithium slag is not higher than 3%..
3. lithium slag according to claim 1, which is characterized in that when sulfur content is more than or equal to 1% in the lithium slag, carry out
When sizing mixing described in step (1), appropriate dispersant is added；The dispersant includes silicate, phosphate, organic acid binary or three
At least one of first low molecule copolymer；Preferably, the additive amount of dispersant is 0.1~2Kg/t lithium slags.
4. method according to claim 1 or 3, which is characterized in that in step (1), when sizing mixing described in progress, by weight hundred
It is 10~65%, preferably 30~60% to divide meter, pulp density.
5. according to the method described in claim 1, it is characterized in that, the soluble carbonate salt is Na2CO3、Li2CO3In at least
It is a kind of.
6. according to the method described in claim 1, it is characterized in that, in the A treatment process of step (2), in carbonate and lithium slag
Sulphur molar ratio be 1.00~1.50.
7. method according to claim 1 or 6, which is characterized in that in the A treatment process of step (2), carry out the reaction
When, the reaction time is 5~120min, and reaction temperature is 5~95 DEG C；And/or the liquid-solid ratio of slurry is 1.5~5.0.
8. according to the method described in claim 1, it is characterized in that, in the B treatment process of step (2), the wet type magnetic is carried out
When selecting, a magnetic separation is at least carried out, it is preferred to use one slightly sweeps technique；When carrying out wet magnetic separation, magnetic field intensity is preferably 1.2-
2.0T。
9. according to the method described in claim 1, it is characterized in that, in step (3), when carrying out the drying, done using flash distillation
Dry method or fluidized bed drying, drying temperature are 100~190 DEG C.
10. according to the method described in claim 1, it is characterized in that, rate-determining steps (3) in filtering gained filtrate in sulfuric acid
Salinity is no more than 50g/L.
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| CN110015855A (en) * | 2019-04-01 | 2019-07-16 | 中国地质科学院郑州矿产综合利用研究所 | Treatment method of lithium slag |
| CN111410202A (en) * | 2020-03-27 | 2020-07-14 | 中国地质大学（北京） | Method for preparing pyrophyllite by using waste residues generated in extraction of lithium from spodumene |
| CN111607254A (en) * | 2020-05-18 | 2020-09-01 | 安徽齐鑫新材料科技有限公司 | Preparation method for filling rubber and plastic by using lithium slag |
| CN113976309A (en) * | 2021-12-01 | 2022-01-28 | 天齐创锂科技(深圳)有限公司 | Method for comprehensively recovering lithium, tantalum-niobium, silicon-aluminum micro powder, iron ore concentrate and gypsum from lithium slag |
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| CN114226413A (en) * | 2020-09-09 | 2022-03-25 | 中冶长天国际工程有限责任公司 | Comprehensive treatment process of lithium slag |
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| CN110015855A (en) * | 2019-04-01 | 2019-07-16 | 中国地质科学院郑州矿产综合利用研究所 | Treatment method of lithium slag |
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| CN111410202B (en) * | 2020-03-27 | 2023-07-21 | 中山市清融嘉创能源科技有限责任公司 | Method for preparing pyrophyllite from spodumene lithium extraction waste residues |
| CN111607254A (en) * | 2020-05-18 | 2020-09-01 | 安徽齐鑫新材料科技有限公司 | Preparation method for filling rubber and plastic by using lithium slag |
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| CN114031090B (en) * | 2021-11-18 | 2023-07-18 | 中山市清融嘉创能源科技有限责任公司 | Method for preparing beta-spodumene from brine with high magnesium-lithium ratio |
| CN113976309A (en) * | 2021-12-01 | 2022-01-28 | 天齐创锂科技(深圳)有限公司 | Method for comprehensively recovering lithium, tantalum-niobium, silicon-aluminum micro powder, iron ore concentrate and gypsum from lithium slag |
| CN114643271A (en) * | 2022-03-25 | 2022-06-21 | 珠海广隆新材料科技有限公司 | Solid waste lithium slag and treatment method and application thereof |
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